CHAPTER I - PHOTOVOLTAIC SOLAR ENERGY CONVERSION 1.

1 Intoduction Of interest to the population at large is the efficient photovoltaic conversion of the 1000 Watts per square meter of solar irradiance incident on the surface of the earth. In Section 1.2, the present author describes an ideal p-n junction solar cell. he present author distinguishes the solar cell!s absorber, its function, and its relation to the other essential components of the solar cell. In Section 1.", the present author revie#s three important approaches that establish upper$limiting efficiencies of solar energ% conversion& the radiationin$ radition$out approach of 'andsberg and onge, the omni$colour approach of (e)os, *rosjean, and +au#els, and the detailed$balance approach of Shoc,le% and -ueisser. he detailed$balance approach establishes the ma.imum$po#er conversion$efficienc% of a single p-n junction solar cell in the terrestrial environment as /0.01. 2et, the omni$colour approach establishes the ma.imum$po#er conversion$efficienc% of solar energ% in the terrestrial environment as 34.31. In Section 1./, the present author revie#s four approaches for reali5ing a global efficienc% enhancement #ith respect to the ma.imum$po#er conversionefficienc% of a single p-n junction solar cell. he current technological paradigm e.perimentall% demonstrates high$ efficiencies b% using stac,s of p-n junction solar cells operating in tandem. Other ne.t$generation approaches propose the incorporation one or more ph%sical phenomena 6 e.g., multiple transitions, multiple electron$hole pair generation, and hot carriers7 to reach high$efficiencies. In Section 1.8, the present author concludes that research and development on ne.t$generation proposals are justified because each ne.t$ generation solar cell ma% offer a global$efficienc% enhancement #hen operating on its o#n and, offer a large efficienc% enhancement per solar cell #hen constituted into a stac, of solar cells operating in tandem. Ideal structure of a solar cell. Sho#n is the absorber, #hich is sand#iched bet#een an n$t%pe emitter and a p$t%pe emitter. 9n Ohmic contact is made to each of the emitters. 9 voltage, V , e.ists bet#een the contacts of the solar cell.

1.2 Ideal p-n Junction Solar Cell In :igure 1, the present author illustrates the ideal electronic structure of a photovoltaic solar cell ;1, 2<, a device that converts the energ% of radiation into electrical energ%. he ideal structure of the solar cell is comprised of several components& an absorber, t#o emitters and t#o contacts. he absorber enables photo$ chemical conversion, the emitters enable electro$chemical conversion, and the contacts enable useful #or, to be performed b% an e.ternal load. In the follo#ing paragraphs, the present author describes an ideal solar cell in more detail. his is done for the special case in #hich the absorber is a medium #ith a single bandgap. 9n absorber is in the center of the solar cell. 9s ma% be seen in :igure 1, the absorber is a medium #hose electronic states form a conduction band and a valence band. he conduction and valence bands are separated b% an energetic gap that is characteri5ed b% the absence of electronic states. he occupanc% of the electronic states of the conduction band and valence band are described b% the quasi$ :ermi energies :,= and :,), respectivel%. he absorber is the region of the solar cell #here the absorption of photons occurs and #here the subsequent generation of electrons and holes ta,es place. %picall%, each photon #ith energ% greater than that of the energetic gap ma% generate a single electron$hole pair. In such case, the energ% of each supra$gap photon is converted to the chemical energ% of an electron$hole pair, e$ h, #here e$h > :,= :,) ;1, 2<. he absorber is sand#iched bet#een t#o semi$permeable emitters ;1, 2<. he emitters are selected to produce an as%mmetr% in the band structure. he electronegativit% and bandgap of the emitter on the right 6 i.e., the n$t%pe emitter7 are selected so that the 6 i7 electrons largel% or completel% permeate through and 6ii7 holes largel% or completel% do not ;1, 2<. 9 small gradient drives the majorit% carriers 6i.e., holes7 to the right so that a beneficial current is produced. 9 large gradient drives minorit% carriers 6i.e., electrons7 to the right so that a detrimental current is produced. he latter current is ver% small, resulting from the relative impermeabilit% of the rightmost emitter to electrons. he emitter on the left is

similarl% selected, e.cept that it is the holes that permeate through and %ield a beneficial current. On the e.ternal surface of both emitters is a metallic contact. he carriers in the contacts are in equilibrium #ith one another, so #here the contact interfaces #ith the emitter the occupanc% of holes and electrons are described b% the same :ermi energ%. hat absolute value of the :ermi energ% at both contacts is roughl% equal to the absolute value of the quasi$:ermi energ% of majorit% carriers #here the absorber interfaces #ith the emitter. hus, bet#een the t#o contacts there is a voltage, V , that is proportional to the potential difference :,= :,) as V > 6:,= :,)7 /q, #here q is the elementar% charge. herefore, the chemical energ% of each electron$hole pair, e$h, is converted to electrical energ% b% a unit pulse of charge current, q, at the voltage V. In the follo#ing subsection, the present author revie#s various limits describing the efficienc% of solar energ% conversion. 1.3 Limits to Ideal Solar Energy Conversion In this section, the present author revie#s three distinct approaches to upper$bound the efficienc% of solar energ% conversion. In Section 1.".1, the present author offers a schematic of a generali5ed converter and uses the schematic to define the conversion efficienc%. In sections 1.".2, 1.".", and 1."./, the present author revie#s the 'andsberg$ onge limit, the Shoc,le%$-ueisser limit, and the omni$colour limit, respectivel%. In Section 1.".8, the present author compares and contrasts these three approaches. :inall%, in Section 1.".4, the present author dra#s conclusions regarding the upper$theoretical efficienc% of converting solar energ% to electricit% in the terrestrial environment. he present author concludes that though the efficienc% limit of a single p-n junction solar cell is large, a significant efficienc% enhancement is possible. his is because, in the first appro.imation, the terrestrial limits of a single p-n junction solar cell are /0.01 and 2/.01, #hereas those of an omnicolour converter are 34.31 and 82.?1 for full%$concentrated and non$concentrated sunlight, respectivel%. 1.3.1 Generalized Energy Con er!er :igure 2 is a schematic of a generali5ed energ% converter 6 c.f. the converter in reference ;"<7. he converter is pumped #ith a po#er flo#, @Ep, and a rate of entrop% flo#, @Sp. 9nalogousl%, the converter, #hich maintains a temperature Tc, sin,s a po#er flo#, @Es, and a rate of entrop% flo#, @Ss. Aean#hile, a rate of useable #or,, @W , is delivered and a rate of heat flo#, @Q , is transmitted to the ambient. Internall%, the converter e.periences a rate change of energ%, @ E , and a rate change of entrop%, @ S . In addition, the converter, b% its o#n internal processes, generates a rate of entrop%, @ Sg. *enerali5ed schematic diagram of an energ% converter. In the radiative limit, the energ% flo#s pumped to and sun, b% the converter 6 i.e. @Ep and @Es7 are limited to the radiant energ% flu. ;Bm 2 s1< pumped to and sun, b% the converter& @Ep and @Es, respectivel%.

he first$la# conversion efficienc%, , is defined as the ratio of the useable po#er over the energ% flo# pumped into the converter, so that ;"<

In the science of solar energ% conversion, no more than t#o radiation flo#s pump the converter 6see :igure "7. 9l#a%s present is a direct source of radiation from the sun, #hich is assumed a blac, bod% #ith a surface temperature TS, %ielding an energ% flu., @ Up,S. Sometimes present, depending on the geometric concentration factor, C, is a diffuse source of radiation scattered from the Carth!s atmosphere, #hich is assumed to be a blac, bod% #ith a surface temperature TC, %ielding an energ% flu., @Up,C. =onsidering the dilution factor of solar radiation, DD2.14 108D, and a geometric solar concentration factor, C, #hich ma% range bet#een unit% and 1 /D ;/<, the total energ% flu. impinging upon the converter, @ Ep, is #ritten #ith the Stefan$Eolt5mann constant, ;8.40 103 W/m2/F/<, as

Aean#hile, the quantification of the po#er densit% generated b% the converter depends on the specific details of the converter. 9s this section onl% discusses a generali5ed converter, no further mathematical form of the po#er densit% is specified. =alculating the performance measure b% substituting the right$hand side of Cquation 617 into the denominator of Cquation 627 is different from the manner of calculating the performance measure as done in the detailed$balance #or, of references ;8, 4, /, 0, 3, ?, 10, 11, 12, 1", 1/<. In the latter references, though the particle flu. impinging upon the solar cell is given in terms of the dual source, the performance measure is calculated #ith respect to the energ% flu. from the sun, @ Up,S. his distorts the performance measure of the device, resulting in efficiencies

times those obtained using the first$la# efficienc% given throughout this dissertation. In the follo#ing subsection, the present author revie#s an approach to upper bound the efficienc% limit of converting solar energ% to useful #or,. 1.3." Land#$erg-Tonge Li%i! 'andsberg and onge present thermod%namic efficiencies for the conversion of solar radiation into #or, ;"<. he converter is pumped #ith all the radiation emitted from a blac, bod%, #hich maintains a surface temperature Tp. he converter is also given as a blac, bod%, ho#ever its temperature is maintained at Tc. he converter, therefore, sin,s blac,bod% radiation associated #ith this temperature. =ross section of an abstracted p-n junction solar cell #ith spherical s%mmetr%. he e.aggerated ph%sical s%mmetr% reinforces the solar geometr%, #here a solid angle of the solar cell!s surface, G, is subtended b% direct insolation from the sun and the remainder of the hemisphere is subtended b% diffuse radiation from the atmosphere. he solid angle ma% be adjusted b% geometrical concentration of the sun!s light. he solar cell is maintained at the ambient temperature, the surface terrestrial temperature, b% a thermal conductor.

With the use of t#o balance equations, for energ% and for entrop%, 'andsberg and onge derive the follo#ing inequalit% for the first$la# efficienc%&

In arriving at the above inequalit%, 'andsberg and onge assume stead%$state conditions. Cqualit% holds for the special case #here there is no internal entrop% generation 6 i.e. @Sg >07. he resulting equalit% is first derived b% +atela b% considering the e.erg% of heat radiation ;18<. he 'andsberg$ onge limit ma% be e.tended so as to model the dual sources of the solar geometr% ;1<. In the case of t#o blac,$bod% sources simultaneousl% pumping the converter, a derivation similar to that of 'andsberg and onge %ields a first$la# efficienc% given as

Cfficienc% limits of ideal solar energ% converters as a function of the ratio of the converter!s temperature, Tc, to the pump!s temperature, TS. Sho#n are the 'andsberg$ onge closed$form efficiencies of the radiation$in$ radiation$out converter, the (e)os$*rosjean$+au#els anal%tic efficiencies of the omni$colour converter, and the Shoc,le%$-ueisser numerical efficiencies of the p-n junction converter. 9ll efficiencies are for full%$ concentrated solar irradiance. 9s a visual aid, the =arnot efficiencies are presented.

:igure / illustrates the 'andsberg$ onge efficienc% limit. In Section 1.".", the detailedbalance method of Shoc,le% and -ueisser is presented and applied to a single p-n junction solar cell. 1.3.3 S&o'(ley-)*ei##er Li%i! Shoc,le% and -ueisser present a frame#or, to anal%5e the efficienc% limit of solar energ% conversion b% a single p-n junction ;8<. he% name this limit the detailed$balance limit for it is derived from the notion that, in principle, all recombination processes ma% be limited to photo$induced processes and balanced b% photo$ induced generation processes. heir ab initi limit H as opposed to a semi$empirical limit based on factors such as measured carrier lifetimes H represents an upper$theoretical limit above #hich a single p-n junction solar cell ma% not perform. In addition, it is a reference for e.perimental measurements of single$junction solar cells in terms of future potential. In their frame#or,, Shoc,le% and -ueisser identif% several factors that ma% degrade the efficienc% of energ% conversion and ideall% allo# that the degrading factors are perfectl% mitigated. herefore, in the detailed balance limit it is permissible that& ! the fractions of recombination and generation events that are coupled to radiative processes are both unit%, ! the probabilit% that incident photons #ith energ% greater than or equal to the semiconductors band$gap are transmitted into the solar cell is unit%, ! the probabilit% #ith #hich a transmitted photon creates an electron$hole pair is unit%, ! the probabilit% that an electron$hole pair %ields a charge current pulse through an e.ternal load is unit%, and, ! the fraction of solid angle subtended b% the sun ma% be unit%$ i.e., the sun!s radiation is completel% concentrated onto the solar cell 6see :igure " on page 47. :igure / illustrates the upper$efficienc% limit of solar energ% conversion b% a single p-n solar cell. his is given for t#o distinct geometric concentration factors& full%$concentrated sun light and non$concentrated sun light. In Section 1."./, the omni$colour limit is presented. 1.3.+ O%ni-Colo*r Li%i! In principle, the detailed$balance method ma% be applied to omni$colour converters ;4, 14, /<. he omni$ colour limit ma% be derived in terms of either photovoltaic processes ;4, 14, /, 10, 2<, photothermal processes ;/<, or h%brids thereof ;/, 13<. In either case, as the number of la%ers in a stac, of photovoltaic converters ;1?, 20, 21, 22, /< or in a stac, of photothermal converters ;2", /< approach infinit%, the solar energ% conversion efficiencies approach the same limit ;4, 2", /<$ the omni$colour limit. :igure / illustrates the upper$efficienc% limit of omni$colour solar energ% conversion. In Section 1.".8, the present author compares and contrasts the efficienc% limits that are heretofore revie#ed. 1.3., Co%-ara!i e Analy#i#

In Section 1.".2 through Section 1."./, the present author revie#s several approaches that quantif% the efficienc% limits of solar energ% conversion. 9t this point, the aforementioned limits are compared and contrasted. 9ll of the limits revie#ed in this Section 1." have in common an efficienc% limit of 5ero #hen the converter!s temperature is that of the pump. In addition, several of the limits approach the =arnot limit for the special case #here the converter!s temperature is absolute 5ero. hese include the 'andsberg$ onge limit and the omni$colour limit 6both for full%$concentrated and non$concentrated solar irradiance7. 9t absolute 5ero the Shoc,le%$-ueisser limit is substantiall% lo#er than the =arnot limit. he large differences bet#een the Shoc,le%$-ueisser limit and the other limits are attributed to the relationship bet#een the energetic gap of the semiconductor comprising the p-n junction and the range of photon energies comprising the broadband spectrum of blac,$bod% radiation. Sub$bandgap photons do not %ield a photovoltaic effect and so do not participate in generating charge current. Aean#hile, the conversion of each supra$bandgap photon uniforml% generates a single electron$hole pair at a voltage limited b% the bandgap. herefore, the portion of each supra$bandgap photon!s energ% in e.cess of the bandgap does not contribute to useful #or,. he difference bet#een the omni$colour limit and the 'andsberg$ onge limit is attributed to the generation of internal irreversible entrop%. C.cept for the t#o temperature e.tremes aforementioned, each la%er of the omni$colour converter generates a rate of irreversible entrop% resulting from its internal processes. his is so even though each la%er of the omni$colour converter operates at its ma.imum$po#er point and converts monochromatic light ;2<. 9s illustrated b% the present author in :igure /, the efficienc% limits revie#ed heretofore ma% be given in descending order as =arnot, 'andsberg$ onge, omni$colour, and Shoc,le%$ -ueisser. +hotovoltaic converters ma% not e.ceed the omni$colour limit for their internal processes are associated #ith a rate of irreversible internal entrop% generation ;2/, 28<. In Section 1.".4, the present author concludes these findings b% describing limits to the conversion of solar energ% in the terrestrial environment. 1.3.. Terre#!rial Con er#ion Li%i!# able 1 lists the upper$efficienc% limits of the terrestrial conversion of solar energ%. 9s is convention in the science of solar energ% conversion, all efficiencies are calculated for a surface solar temperature of 4000 F, a surface terrestrial temperature of "00 F, and a converter maintained at the surface terrestrial temperature. In addition, the geometric dilution factor is ta,en as 2.14 108 ;/<. :or each t%pe of converter listed, the upper$ efficienc% limit is given for full%$concentrated sunlight and, in some cases, for non$concentrated sunlight. he values listed depend onl% on the sun!s surface temperature, the earth!s surface temperature, and the geometric concentration factor, as opposed to consideration regarding the air mass of the Carth and other secondar% phenomena. he present author concludes that though the upper$efficienc% limit of a single p-n junction solar cell is large, a significant efficienc% enhancement is possible. his is true because the terrestrial limits of a single p-n junction solar cell is /0.01 and 2/.01, #hereas the terrestrial limits of an omni$colour converter is 34.31 and 82.?1 for full%$concentrated and non$concentrated sunlight, respectivel%. In Section 1./, the present author defines the notion of high$efficienc% approaches to solar energ% conversion and briefl% revie#s various proposed high$efficienc% approaches. 1.4 High-E iciency !""roaches In this section, Section 1./, the present author revie#s several distinct approaches for highefficienc% solar cells. In Section 1./.1, the present author defines Ihigh$efficienc%J in terms of the upper$conversion efficiencies of the Shoc,le%$-ueisser solar cell and the omni$colour solar cell. In Section 1./.2, the present author revie#s the current technological paradigm to reali5e high$efficienc% solar cells& stac,s of single p-n junction solar cells operating in tandem. In sections 1./.", 1././, and 1./.8, the present author revie#s three ne.t$generation approaches to reali5e high$efficienc% solar cells& the carrier$multiplication solar cell, the hot$ carrier solar cell, and the multiple$transition solar cell, respectivel%. :inall%, in Section 1./.4, the present author dra#s conclusions regarding the justification for researching and developing ne.t$generation approaches. hough stac,s of single p-n junction solar cells operating in tandem are the onl% high$efficienc% approach #ith demonstrated high$efficienc% performance, the present author concludes that development on a ne.t$generation solar cell is justified in that a 6 i7 ne.t$generation solar cells offer a global$efficienc% enhancement in themselves and 6i7 also per la%er if incorporated in a stac, of solar cells operating in tandem. Immediatel% belo# in Section 1./.1, the present author defines #hat is meant b% high$efficienc% performance. Ta$le 1/ Kpper$efficienc% limits of the terrestrial conversion of solar energ%, " er. 9ll efficiencies calculated for a surface solar temperature of 4000 F, a surface terrestrial temperature of "00 F, a solar cell maintained at the surface terrestrial temperature, a geometric dilution factor, D, of 2.14108, and a geometric concentration factor, C, that is either 1 6non$concentrated sunlight7 or 1/D 6full%$concentrated sunlight7.

# 'isted values are first$la# efficiencies that are calculated b% including the energ% flo# absorbed due to direct solar radiation and the energ% flo# due to diffuse atmospheric radiation. he listed values are li,el% to be less than #hat are previousl% recorded in the literature. See Section 1.".1 on page / for a more comprehensive discussion. a =alculated from Cquation 6"7 on page 4. b =alculated from Cquation 6/7 on page 0. c Obtained from reference ;4<and reference ;2<. d 9djusted from the value 43.21 recorded in reference ;4< and independentl% calculated b% the present author. e Obtained from reference ;1/<. f 9djusted from the value "1.01 recorded in reference ;3<. 1.+.1 Glo$al E00i'ien'y En&an'e%en! here are several proposals for high$efficienc% solar cells. In this dissertation, similar to 9nderson in his discussion of the efficienc% enhancements in quantum$#ell solar cells ;24<, the present author defines high$ efficienc% in terms of a global efficienc% enhancement. Sho#n in :igure 8 are the upper$efficienc% conversion limits of the single$junction solar cell and the omni$colour solar cell. In :igure 8, the upper$efficienc% conversion limits are given as a function of the geometrical concentration factor, C. he present author defines Ihigh efficienc%J in terms of the numerical data given in :igure 8. he present author asserts that, for an% and all geometric concentration factor, a proposal for high$efficienc% solar cell must, #hen optimi5ed, offer an efficienc% greater than that of an optimi5ed Shoc,le%$-ueisser solar cell at that same geometric concentration factor. :or e.ample, according to the present author!s definition, under non$concentrated sunlight a high$efficienc% proposal, #hen optimi5ed, must have an upper$efficienc% limit greater than 2/.0.1. =learl%, for ph%sical consistenc%, the optimi5ed theoretical performance of the high$efficienc% proposal must be less than that of the omni$colour solar cell at that geometric concentration factor. :urthermore, the present author asserts that an% fabricated solar cell that claims to be a high$efficienc% solar cell must demonstrate a global efficienc% enhancement #ith respect to an optimi5ed Shoc,le%$-ueisser solar cell. :or e.ample, to substantiate a claim of high$efficienc%, a solar cell maintained at the terrestrial surface temperature and under a geometric concentration of 2/0 suns must demonstrate an efficienc% greater than "8.01$the efficienc% of an optimi5ed Shoc,le%$-ueisser solar cell operating under those conditions. Eefore moving on to Section 1./.2, #here the present author revie#s the tandem solar cell, the reader is encouraged to vie# the high$efficienc% regime as illustrated in :igure 8. he reader #ill note that there is a significant efficienc% enhancement that is scientificall% plausible. 1ig*re ,/ he region of high$efficienc% solar energ% conversion as a function of the geometric concentration factor. he high$efficienc% region is defined as that region offering a global$efficienc% enhancement #ith respect to the ma.imum single$junction efficiencies 6lo#er edge7 and the ma.imum omni$colour efficiencies 6upper edge7. he efficienc% required to demonstrate a global efficienc% enhacnement varies as a function of the geometric concentration factor. :or illustrative purposes, the terrestrial efficiencies 6see able 27 of $$ stac, 6$ > 2, /, and 37 solar cells are given for the t#o e.treme concentration factors 6 i.e., 1 sun and /4,"00 suns7. :inall%, for illustrative purposes, the present #orld record solar cell efficienc% is given 6 i.e., /0.01 under a concentration of 2/0 suns ;20<7.

1.+." Tande% Solar Cell he utili5ation of a stac, of p-n junction solar cells operating in tandem is proposed to e.ceed the performance of one p-n junction solar cell operating alone ;1?<. he upperefficienc% limits for $$stac,

tandems 61 % $ % 37 are recorded in able 2 on page 1/ . 9s the number of solar cells operating in a tandem stac, increases to infinit%, the upperlimiting efficienc% of the stac, increases to the upper$limiting efficienc% of the omni$colour solar cell ;4, 2", /<. his is e.plained in Section 1."./ on page 3. In practice, solar cells ma% be integrated into a tandem stac, via a vertical architecture or a lateral architecture. 9n e.ample of a vertical architecture is a monolithic solar cell. Kntil no#, the largest demonstrated efficienc% of a monolithic solar cell $or for an% solar cell$ is the metamorphic solar cell produced b% Spectrolab ;20<L Spectrolab!s three$junction metamorphic solar cell has a conversion efficienc% of /0.01 under a concentration of 2/0 suns ;20<. 9n e.ample of a hori5ontal architecture is the solar cell of reference ;23<, #hich utili5es a spectral$beam splitter ;2?< and appropriatel% directs the resulting light onto its constituent solar cells. he present author no# revie#s the carrier$multiplication solar cell, the first of three ne.tgeneration proposals to be revie#ed in this dissertation. Ta$le "/ Kpper$efficienc% limits, " er , of the terrestrial conversion of stac,s of singletransition single p-n junction solar cells operating in tandem. 9ll efficiencies calculated for a surface solar temperature of 4000 F, a surface terrestrial temperature of "00 F, a solar cell maintained at the surface terrestrial temperature, a geometric dilution factor, D, of 2.14108, and a geometric concentration factor, C, that is either 1 6non$ concentrated sunlight7 or 1/D 6full%$concentrated sunlight7.

# 'isted values are first$la# efficiencies that are calculated b% including the energ% flo# absorbed due to direct solar radiation and the energ% flo# due to diffuse atmospheric radiation. he listed values are li,el% to be less than #hat are previousl% recorded in the literature. See Section 1.".1 on page / for a more comprehensive discussion. M Necorded values are identical to those of the omni$colour converter of able 1 on page 11. MM Necorded values are identical to those of the Shoc,le%$-ueisser converter of able 1 on page 11. a Obtained from reference ;4< and independentl% calculated b% the present author. b 9djusted from the value 43.21 recorded in reference ;4< and independentl% calculated b% the present author. c Obtained from reference ;1/< and independentl% calculated b% the present author. d 9djusted from the values recorded in reference ;3< and independentl% calculated b% the present author. e =alculated independentl% b% the present author. )alues are not published in the literature. 1.+.3 Carrier-2*l!i-li'a!ion Solar Cell =arrier$multiplication solar cells are theori5ed to e.ceed the Shoc,le%$-ueisser limit ;"0, "1, 0, ?<, thus the% ma% be correctl% vie#ed as a high$efficienc% approach. hese solar cells produce an efficienc% enhancement b% generating more than one electron$hole pair per absorbed photon via inverse$9uger processes ;"1< or via impact$ioni5ation processes ;"0, "2<. he efficienc% enhancement is calculated b% several authors ;"0, "1, 0<. (epending on the assumptions, the upper limit to terrestrial conversion of solar energ% using the carriermultiple solar cell is 38./1 ;0< or 38.?1 ;?<. hough the carrier$multiple solar cell is close to the upper$ efficienc% limit of the omni$colour solar cell, the latter is larger than the former because the former is a t#o$ terminal device. he present author no# revie#s the hot$carrier solar cell, the second of three ne.t$ generation proposals to be revie#ed in this dissertation. 1.+.+ Ho!-Carrier Solar Cell Oot$carrier solar cells are theori5ed to e.ceed the Shoc,le%$-ueisser limit ;"", "/, 28<, thus the% ma% be correctl% vie#ed as a high$efficienc% approach. hese solar cells generate one electron$hole pair per photon absorbed. In describing this solar cell, it is assumed that carriers in the conduction band ma% interact #ith themselves and thus equilibrate to the same chemical potential and same temperature ;"", "/, 28<. he same ma% be said about the carriers in the valence band ;"", "/, 28<. Oo#ever, the carriers do not interact #ith phonons and thus are thermall% insulated from the absorber. Nesulting from a monoenergetic contact to the conduction band and a mono$energetic contact to the valence band, it ma% be sho#n that 6 i7, the output voltage ma% be greater than the conductionto$valence bandgap and that 6 ii7 the temperature of the carriers in the absorber ma% be elevated #ith respect to the absorber. he efficienc% enhancement is calculated b%

several authors ;"", "/, 28<. (epending on the assumptions, the upper$conversion efficienc% of an% hot$ carrier solar cell is asserted to be 381 ;2< or 341 ;"/<. he present author no# revie#s the multiple$ transition solar cell, the third of three ne.t$generation proposals to be revie#ed in this dissertation. 1.+., 2*l!i-le-Tran#i!ion Solar Cell he multi$transition solar cell is an approach that ma% offer an improvement to solar energ% conversion as compared to a single p-n junction, single$transition solar cell ;20<. he multitransition solar cell utili5es energ% levels that are situated at energies belo# the conduction band edge and above the valence band edge. he energ% levels allo# the absorption of a photon #ith energ% less than that of the conduction$to$valence band gap. Wolf uses a semiempirical approach to quantif% the solar energ% conversion efficienc% of a three$ transition solar cell and a four$transition solar cell ;20< 6for a more detailed revie# of this approach, the reader is encouraged to vie# Section 2.2.1 on page 217. Wolf calculates an upper$efficienc% limit of 811 for the three$transition solar cell and 481 four$transition solar cell ;20<. Subsequentl%, as opposed to the semi$ empirical approach of Wolf, the detailed$balance approach is applied to multi$transition solar cells. he upper$efficienc% limit of the threetransition solar cell is no# established at 4".21 ;"8, "4, "0< 6for a more comprehensive revie# of this approach, the reader is encouraged to vie# =hapter 2.7. In addition, the upperconversion efficienc% limits of $$transition solar cells are e.amined ;12, "3<. (epending on the assumptions, the upper$conversion efficienc% of an% multi$transition solar cell is asserted to be 00.21 ;12< or 38.01 ;"3<. hese upper$limits justif% the claim that the multiple$transition solar cell is a high$efficienc% approach. Nesulting from internal current constraints and voltage constraints, the upper$efficienc% limit of the multi$transition solar cell is asserted to be less than that of the omni$colour converter ;12, "3<. 1.+.. 3*#!i0i'a!ion 0or Ne4!-Genera!ion A--roa'&e# In this section, Section 1./, the present author defines the high$efficienc% regime of a solar cell. he onl% approach to demonstrate a high$efficienc% solar cell is the current technological paradigm of stac,s of single p-n junction solar cells operating in tandem. he current #orld record belongs to a stac, of three single p-n junction solar cells operating in tandem. he record efficienc% demonstrated b% this solar cell is /0.01 at 2/0 suns. his efficienc% ma% be compared #ith the optimi5ed Shoc,le%$-ueisser solar cell and the optimi5ed omni$colour solar cell under these same operating conditions& "8.01 and 00.81, respectivel%. Eased on this, the present author concludes that research and development on ne.t$generation approaches is #arranted. he author justifies this conclusion b% noting that even if a three$stac, tandem solar cell achieves its terrestrial efficienc% limit 64".017, it #ill still fall short of the omnicolour limit 634.317. Ksing the current technological paradigm, an% additional significant efficienc% gains #ill require the inclusion of more single p-n junction operating in tandem. Oo#ever, as the number of p-n junctions increases, the current technological paradigms are increasingl% problematic. his is due to the fundamental limitation of compatible materials #ith #hich to fabricate a tandem stac, from man% single$junction devices. he ne.t generation approaches are elegant, because their single absorbing media ma% perform as a tandem stac, of several single junctions. he ne.t$generation approaches represent a paradigm shift, allo#ing for a significant efficienc% enhancement per la%er operating in a tandem stac,. In the follo#ing section, Section 1.8, the present author, #ithin the conte.t of this dissertation, concludes the revie# of photovoltaic solar energ% conversion. 1.# Conclusions he author begins =hapter 1 b% revie#ing the operation of an ideali5ed single$transition, single p-n junction solar cell. he present author concludes that though the upper$efficienc% limit of a single p-n junction solar cell is large, a significant efficienc% enhancement is possible. his is so because the terrestrial limits of a single p-n junction solar cell is /0.01 and 2/.01, #hereas the terrestrial limits of an omni$colour converter is 34.31 and 82.?1 for full%$concentrated and non$concentrated sunlight, respectivel%. here are several highefficienc% approaches proposed to bridge the gap bet#een the single$junction limit and the omni$colour limit. Onl% the current technological paradigm of stac,s of single p-n junctions operating in tandem e.perimentall% demonstrates efficiencies #ith a global efficienc% enhancement. Oo#ever, the gap bet#een the present technological record 6/0.017 and sound ph%sical models indicates significant room to continue to enhance the performance of solar energ% conversion. he current technological paradigm is not li,el% to e.perimentall% demonstrate significant gains in efficienc%. his is a consequence of the inherent limitation of compatible materials #ith #hich to fabricate a tandem stac, from man% single$junction solar cells. In conclusion, research and development on ne.t$generation proposals are justified because ne.t generation solar cells have large efficiencies #hen calculated on their o#n and, in addition, %ield larger 6#ith respect to p-n junctions7 efficiencies per solar cell #hen constituted into hori5ontal or vertical stac,s of solar cells operating in tandem. In the follo#ing chapter, the present author revie#s the three$transition solar cell. CHAPTER II - THREE-TRANSITION SOLAR CELL 2.1 Introduction Increasing the efficienc% of photovoltaic solar cells b% constructing a three$transition solar cell via an absorber #ith intermediate states is a #ell$established abstract notion. Kntil no#, proposed approaches to reali5e the three$transition solar cell do not validate the global efficienc% enhancement that is theori5ed. :or this reason, researchers are e.perimenting to ascertain #here the faults lie. In this chapter, the present author revie#s the theoretical operation of an ideali5ed three$transition solar cell, revie#s proposals to

reali5e a three$transition solar cell, and revie#s the e.perimental characteri5ation of protot%pe three$ transition solar cells. In section 2.2, the present author revie#s the theoretical operation of ideali5ed threetransition solar cells. he major difference bet#een the operations of the three$transition solar cell and the single$junction solar cell results from their distinct absorbers. 9 threetransition solar cell has an absorber #ith electronic states energeticall% bet#een and electronicall% isolated from those of the conduction band and valence band. he present author dra#s t#o conclusions pertaining to the merit of the three$transition solar cell. he present author concludes that the solar energ% conversion efficienc% three$ transition solar cell ma% nearl% reach that of a tandem$stac, of three single$junction, single$transition solar cells. he present author further concludes that an ideali5ed three$transition solar cell is more spectrall% robust than an ideali5ed tandem$stac, of three solar cells electricall% assembled in series. herefore, #hether the absolute optimum band structure ma% or ma% not be practicall% obtainable, the solar energ% conversion efficienc% #ill degrade gentl% as the practicall%$obtainable band structure deviates from the optimum band structure. In section 2.", the present author revie#s proposals to construct a three$transition solar cell. Cach proposal ma% be distinguished b% their respective approach to s%nthesi5e the three$transition absorber. +roposed approaches to reali5e a three$transition absorber include the follo#ing& 617 #here the intermediate states are those of locali5ed states of dopants introduced into a host semiconductor, 627 #here the intermediate states are those that comprise subbands introduced b% quantum$#ell heterojunctions, 6"7 #here the intermediate states are those that comprise a miniband introduced b% quantum$dot heterojunctions, and 6/7 #here the intermediate states are those of e.tended states of dopants introduced into a host semiconductor. Eased on the summar% of these proposals, the present author concludes that a global efficienc% enhancement is not illustrated e.perimentall%. In section 2./, the present author revie#s e.perimental #or,s that aim to confirm the theoretical precepts on #hich the large efficienc% of the three$ transition solar cell is premised. hese precepts relate to the absorption of photons, emission of photons, collection of charge carriers, generation of charge current, production of a photovoltage, and the separation of quasi$:ermi levels. he present author concludes that currentl%, a bod% of e.perimental evidence to support the e.istence of either a three$transition absorber or a three$transition solar cell is absent from the literature. he present author further concludes that the absence of infrared detection #hile recording absorption and emission spectra severel% hampers the abilit% to directl% observe the e.istence of a three$ transition absorber and three$transition solar cell. 2.2 $"eration o the %hree-%ransition Solar Cell In this section, Section 2.2, the present author describes the operation of the three$transition solar cell. In section 2.2.1, the present author revie#s the semi$empirical approach of Wolf ;20<. It is e.plained that b% utili5ing energ% levels in the previousl% forbidden bandgap, the three$transition so lar cell has a potential l% better performance than other single$junction, single$transition solar cells. In section 2.2.2, the present author revie#s the detailedbalance approach of 'uque and AartPQ ;"8<. It is e.plained ho# 'uque and AartPQ quantif% the upper$efficienc% limit of a three$transition solar cell. In section 2.2.", the present author revie#s the relationship bet#een the reduced$band diagram of the solar cell and its general equivalent circuit ;"?, "4, /0, /1<. It is e.plained that the solar cell is equivalent to a tandemstac, of three single$junction solar cells electricall% assembled b% a combined seriesRparallel interconnect ;/2<. In section 2.2./, the present author revie#s the detailed$balance approach of 'ev% and Oonsberg ;"0<. he novelt% of their #or, is in quantif%ing the impact of both finite intermediate band #idth and spectral selectivit% on the optimi5ed detailed$balance conversion efficiencies of the three$transition solar cell solar cell and its associated band structure ;"0<. he #or, is significant as it sho#s that finite band#idths result in a graceful degradation in the efficienc% ;"0<. :inall%, in section 2.2.8, the present author dra#s t#o conclusions. :irst, the three$transition solar cell is attractive because it provides a significant efficienc% enhancement per la%er of a stac, of solar cells operating in tandem. :or e.ample, a t#o$stac, of three$transition solar cell ma% nearl% reach the efficienc% limit of a si.$stac, of single$transition, single$junction solar cells operating in tandem. Second, #hether the absolute optimum band structure ma% or ma% not be practicall% obtainable, the efficienc% #ill degrade gentl% as the band structure deviates from the optimum band structure. his results from the fact that an ideali5ed three$transition solar cell is more spectrall% robust than an ideali5ed tandem$stac, of three solar cells electricall% assembled in series. ".".1 Se%i-E%-iri'al A--roa'& o0 5ol0 In 1?40, Wolf proposes multi$transition solar cells as an approach to reali5e high$efficienc% solar energ% conversion. In this subsection, the present author revie#sWolf!s semi$empirical approach. In :igure 4 the present author illustrates an absorber #ith a bandgap, Eg, and #ith a trap level at an energ% E 1 belo# the conduction band edge. In this discussion, it #ill be assumed, #ithout loss of generalit%, that E 1 & Eg E 1 . Wolf e.plains that, resulting from this trap level, three distinct photo$induced electronic transitions are permissible ;20<& bet#een the conduction band and valence band, bet#een the trap level and the conduction band, and bet#een the trap level and the valence band. Wolf e.plains that a solar cell #ith an optimi5ed three$transition absorber ma% more efficientl% convert the broadband solar irradiance than other p-n junction solar cells. Wolf calculates the ma.imum po#er densit% generated b% the solar cell, W "A+, in terms of the energ% gap, EgL a semi$empirical voltage factor, ).:., #hich is the ratio of the product

of the elementar% charge, q, and the open$circuit voltage to the energ% gapL a semi$empirical curve factor, =.:., #hich is the ratio of the largest rectangle that can be inscribed into the current$voltage characteristic to the product of the short$circuit current and open$circuit voltageL and the light$generated current, '(, as 1ig*re ./ Neduced band diagram of an absorber #ith a single trap level located at an energ% C 1 belo# the conduction band edge. he trap levels result in multiple photoinduced electronic transitions. One trap provides three distinct photo$induced electronic transitions. his figure is essentiall% that presented b% Wolf in reference ;20<.

Wolf e.plains that the voltage factor and curve factor both ma% be large, considering that these solar cells #ould have large bandgaps ;20<. In addition, a large photo$generated current ma% also be obtained resulting from the absorption of both sub$ and supra$bandgap photons ;20<. he light$generated current is given in terms of the number of photons in the sun!s spectrum per square meter per second available for transitions from the valence band to the conduction band, @ $p,6=,)7L the number of photons in the sun!s spectrum per square meter per second available for transitions from the trap level to the conduction band, @ $p,6=, 7L and the number of photons in the sun!s spectrum per square meter per second available for transitions from the valence band to the trap level, @ $p,6 ,)7, as

he generation rate of electronic charge is proportional to the sum of t#o numbers ;20<& the number of transitions generated b% a one$step process from the valence band to the conduction band and the number of transitions generated b% a t#o$step process from the valence band to the conduction band. Nesulting from the t#o$step nature of the subbandgap transitions, the overall number of t#o$step transitions from the valence band to the conduction band is limited b% the smaller of @ $p,6=, 7 and @$p,6 ,)7 ;20<. he numbers of photons in the sun!s spectrum per square meter per second available for each transition is given in terms of the absorptivit%, a)6D*7, and the emission spectrum of the sun, @ nS, as

*iven that the absorption coefficients relating to each transition are non$5ero for all photons #ith energies D* greater than E 1 , the absorber ma% absorb a photon #ith energ% D * greater than the trap energ%, E 1 ;20<. 9dditionall%, if the trap level appropriatel% adjusts the absorption characteristic, then the absorption coefficient describing each of the transitions #ill be high ;20<. In such case, the absorptivit% #ill be unit% and the absorber ma% completel% absorb each photon that has an energ% D * greater than E 1. Wolf notes that to ensure both of the sub$bandgap transitions, the number of filled trap states and the number of empt% trap states must be of the same order of magnitude ;20<. In other #ords, the three$transition absorber ma% be considered to be metallic ;10<. :urthermore, Wolf notes that to maintain a high li,elihood of a t#o$photon process, an absorber #ith a slo# trap level is preferable to a fast trap level ;20<. Wolf calculates an upper$efficienc% limit of 811 for the three$transition solar cell ;20<. Knli,e Wolf!s approach ;20<, the approach of 'uque and AartPQ ;"8< gives the upper$efficienc% limit of a three$transition solar cell, as there is no reference to an% semi$empirical factors. In the paragraphs to follo#, the present author revie#s the particulars of the latter approach. "."." 6e!ailed-7alan'e A--roa'& o0 L*8*e and 2ar!9: In 1??0, 'uque and AartPQ present a detailed$balance anal%sis of a three$transition solar cell ;"8<. heir #or, is novel because the% derive the statistics of photons in equilibrium #ith the three allo#ed photo$induced

electronic transitions of a three$transition absorber ;"8<, use these statistics to #rite the photon flu.es emitted b% the solar cell ;"8<, and calculate the upper conversion efficienc% of a three$transition solar cell. :igure 0 gives the reduced band diagram of the absorber of an intermediate band solar cell, as posited b% 'uque and AartPQ. here, the electronic states bet#een the conduction band and valence band form an intermediate band #ith infinitesimal band #idth. he energetic gap bet#een the conduction band and valence band is 6=,)7. he bandgaps bet#een the intermediate band and the other electronic bands are referenced from the center of the intermediate band. he bandgap bet#een the intermediate band and conduction band is labeled 6=,I7 and the bandgap bet#een the intermediate band and valence band is labeled 6I,)7. In this discussion it #ill be assumed, #ithout loss of generalit%, that 6I,)7 & 6=,I7. 9s e.plained b% Shoc,le% and Nead, the electronic occupanc% of the conduction band, intermediate band, and valence band are each described b% unique quasi$:ermi levels ;/"<& :,=, :,I, and :,), respectivel%. Aean#hile, the net photon flo# absorbed, resulting from electronic transitions bet#een band S and band 2, is the difference bet#een the photon flo# absorbed, @$p,6S,27, and the photon flo# emitted, @ $s,6S,27. 9llo#ing that all the electronic charges that are transfered to an e.ternal load pass through the conduction band and the valence band and allo#ing that the solar cell is in a stead%$state condition, the net photon flo# resulting from sub$bandgap absorption is in balance as ;"8< and the po#er densit% generated b% the intermediate band solar cell, @ W , is given as

1ig*re ;/ Neduced band diagram of an intermediate band absorber #ith an infinitesimal intermediate band #idth. Sho#n are energetic separations bet#een electronic band S and electronic band 2, 6S,27L the quasi$ :ermi level, :,S, that describes the occupanc% of band SL the photon flo#s absorbed that result from electronic transitions bet#een band S and band 2, @ $p,6S,27L and the photon flo#s emitted that result from electronic transitions bet#een band S and band 2, @ $s,6S,27L

Cach of these photon flo#s ma% be given in terms of the Eose$Cinstein integral

he upper$efficienc% limit of the three$transition solar cell at ma.imum po#er is found to be 4".21 ;"8<. his efficienc% limit occurs #hen the conduction$to$valence bandgap is 1.?8 e), the conduction$to$intermediate bandgap is 1.2/ e), and the intermediate$to$valence bandgap is 0.01 e) ;"8<. E% utili5ing the general equivalent circuit of this solar cell, in the follo#ing subsection, the present author places this efficienc% limit into the conte.t of a tandem$stac, of single$junction, single$transition solar cells. ".".3 General E8*i alen! Cir'*i! :igure 3 sho#s the reduced band diagram of a three$transition solar cell. 9s made implicit b% Wolf ;20< and made e.plicit b% 'uque and AartPQ ;10<, a three$transition solar cell is made b% sand#iching the three$ transition absorber bet#een an n$t%pe emitter on one side and a p$t%pe emitter on the other side. Nesulting from the n$t%pe emitter, onl% electrons from the conduction band ma% pass through the n$t%pe emitter. Similarl%, resulting from the p$t%pe emitter, onl% holes from the valence band ma% pass through the p$t%pe emitter ;"8<. hese electronic currents ma% then pass through an e.ternal load via e.ternal contacts to the emitters. he upper efficienc% limit of the three$transition solar cell 64".21 ;"8<7 ma% be understood b% considering its general equivalent circuit ;"?, "4, /0, /1<. 1ig*re </ S,etch of a three$transition solar cell. Sho#n is the absorber sand#iched bet#een n$ and p$t%pe emitters, Ohmic contacts to the emitters, and a voltage, V , across the solar cell.

9s sho#n in :igure ?, the equivalent circuit of a three$transition solar cell is composed of three photodiodes. #o of the photodiodes are electricall% connected in a series string. he third photodiode is connected in parallel to the series$connected photodiodes. Cach of the photodiodes passes a light$generated current densit%, +p,6S,27 > q @$p,6S,27, and a recombination current, +,,6S,27 > q @$,,6S,27. Nesulting from the series connection, the net current densit% generated b% each of the series$connected photodiodes must be in balance. :urther, resulting from the parallel connection, the voltage across the t#o series$connected photodiodes is equal to the voltage across the photodiode in parallel #ith them. 1ig*re =/ Cquivalent circuit diagram of a three$transition solar cell. Sho#n are three diodes, each of #hich pass a recombination current densit%, +p,6S,27, and three current sources, each of #hich pass a light$ generated current densit%, +s,6S,27. he voltage at each of the three nodes is labeled in terms of a quasi$ :ermi level. he voltage, V , across the device is sho#n.

he general equivalent circuit of the three$transition solar cell is the same as that of the series$parallel solar cell ;/2<. Nesulting from its t#o constraints 6one current constraint and one voltage constraint7, the efficienc% limit of the three$transition solar cell 64".217 is upper bounded b% that of a tandem$stac, of three electricall%$ unconstrained single$junction, single$transition solar cells 64".31 see able 2 on page 1/7. Of particular note, the ideal series$parallel solar cell is more spectrall% robust than an ideal tandem$stac, of three solar cells electricall% assembled in series ;/2<. One ma% project that 6a7 because the general equivalent circuit of the three$transition solar cell is the same as the general equivalent circuit of the series$parallel solar cell, that 6b7 the ideal three$transition solar cell is similarl% more spectrall% robust than an ideal tandem$stac, of three solar cells electricall% assembled in series.

".".+ 1ini!e-7and>id!& Analy#i# o0 Le y and Hon#$erg Knli,e previous anal%ses ;20, "8<, 'ev% and Oonsberg ;//, 1", "0< anal%5e the ma.imum po#er performance of three$transition solar cells #here the electronic levels bet#een the conduction band and valence band form an intermediate band of finite #idth 6see the right pane of :igure 107. he #or, of 'ev% and Oonsberg is novel in quantif%ing the impact of both finite intermediate band #idth and spectral selectivit% on the optimi5ed detailed$balance conversion efficiencies of the three$transition solar cell and its associated band structure ;"0<. he inclusion of finite intermediate band#idths is important #hether the three$transition absorber is formed #ith dopants ;/8< or #ith allo%s ;/4, /0, /3, /?, 80, 81<. =andidate allo%s sho# intermediate band #idths of order 100 me) ;/3, /?, 81< or 1 e) ;/4, /0, 80< . 'ev% and Oonsberg conclude that the largest efficiencies result #hen the intermediate band!s #idth is roughl% equal to or less than 300 me) ;"0<. :or e.ample, #hen the #idth of the intermediate band equals 300 me), the first$la# efficiencies reach 80.?1 and "".?1 6compared #ith 4".21 and "4."1 #hen the intermediate band!s #idth is infinitesimall% small7 for full%$concentrated and non$concentrated solar illumination, respectivel%. 9ccording to 'ev% and Oonsberg, #hen the intermediate band!s #idth is roughl% less than or equal to 300 me), to achieve high efficiencies at large concentrations, the smallest and ne.t smallest bandgap ought to be roughl% 100 me) smaller and /00$ 800 me) larger than 300 me), respectivel% ;"0<. In the follo#ing subsection, the present author offers concluding remar,s regarding the operation and potential performance of the three$transition solar cell. 1ig*re 1?/ Neduced band diagram of a three$transition absorber #hose electronic states bet#een those of the conduction and valence bands form an intermediate band #ith infinitesimal #idth 6pane 97 or finite #idth 6pane E7. he #or, of 'ev% and Oonsberg ;"0< moves from the anal%sis of highl% ideali5ed structures #ith infinitesimal intermediate band #idths to more realistic structures #ith finite intermediate band #idths, #hile maintaining the detailed$balance frame#or,.

"."., Con'l*#ion# In this section the present author revie#s the origin and histor% of the theor% pertaining to the theoretical operation and performance of the three$transition solar cell. Similar to a tandem$stac, of three solar cells electricall% assembled b% a combined seriesRparallel interconnect ;/2<, the efficienc% limit of the three$ transition solar cell is 4".21. he present author dra#s t#o conclusions pertaining to the merit of the three$ transition solar cell as an approach to high efficienc% solar energ% conversion. 6 i7 :irst, the three$transition solar cell is attractive because it provides a significant efficienc% enhancement per solar cell operating in tandem. :or e.ample, a single three$transition solar cell ma% nearl% reach the efficienc% limit of a tandem$ stac, of three single$junction, single$transition solar cells. Aoreover, a tandem$stac, of t#o three$transition solar cell ma% nearl% reach the efficienc% limit of a tandem$stac, of si. single$junction, single$transition solar cells. 6ii7 Second, an ideali5ed three$transition solar cell ma% be more spectrall% robust than an ideali5ed tandem$stac, of three solar cells electricall% assembled in series. hus, #hether the absolute optimum band structure ma% or ma% not be practicall% obtainable, the efficienc% #ill degrade gentl% as the band structure deviates from the optimum band structure. In practice, reali5ing a three$transition solar cell presents man% technological hurdles. he central impediment to reali5e a three$transition solar cell is fabricating a three$ transition absorber. In the follo#ing section, the present author revie#s proposals to reali5e a three$transition absorber. 2.3 &eali'ation o a %hree-%ransition !(sor(er and Solar Cell here are several proposals regarding the reali5ation of a three$transition solar cell. he various proposals are at different stages of their developmentL some have protot%pes #hile others do not. Cach proposal ma% be distinguished b% its respective approach to s%nthesi5e the three$transition absorber& a medium #ith intermediate levels that are electronicall% isolated from both the conduction and valence bands. +roposed approaches to reali5e a three$transition absorber include the follo#ing& 617 #here the intermediate levels are those of locali5ed states of dopants introduced into a host semiconductor, 627 #here the intermediate levels are those that comprise subbands introduced b% quantum$#ell heterojunctions,

6"7 #here the intermediate levels are those that comprise a miniband introduced b% quantum$dot heterojunctions, and 6/7 #here the intermediate levels are those of e.tended states of dopants introduced into a host semiconductor. he present author briefl% revie#s these proposals in sections 2.".1, 2.".2, 2.".", and 2."./, respectivel%. he present author concludes in section 2.".8 that, although in some instances these proposals %ield a relative efficienc% enchantment, there is no e.perimental evidence of a global efficienc% enhancement. Eefore continuing, it is #orth noting that Ne%nolds and =5%5a, are the first to postulate an absorbing medium #ith a band of electronic states that is electronicall% isolated from both the conduction band and valence band. he% postulate this as a mechanism for both photovoltaic and photoconductive effects in =dS cr%stals ;82<. ".3.1 Lo'alized-S!a!e# A--roa'& Wolf states the connection bet#een 6a7 the required ph%sical properties of the intermediate levels needed to reali5e the three$transition absorber and 6b7 the absorption resulting from locali5ed centers ;20<. his connection has spa#ned a branch of photovoltaics called impurit% photovoltaics ;8"<. here are t#o reports of relative efficienc% enhancements ;24< via the use of impurit% photovoltaics as compared to reference solar cells. Eruns et a-. illustrate that a solar cell implanted #ith helium dose of 2 1014 cm2 %ields a 81 efficienc% enhancement as compared to a reference solar cell ;8/<. :urther, Fasai et a-. illustrate that a indiumimplanted cr%stalline silicon solar cell %ields a 111 efficienc% enhancement as compared to a reference solar cell 60.381 versus 0.0?17 ;88<. hat said, at the time that this present disseration is #ritten, no global efficienc% enhancement is e.perimentall% observed in solar cells intending to utili5e the impurit%$ photovoltaic effect. ".3." )*an!*%-5ell A--roa'& Eremner et a-. ;84< and *reen ;80< illustrate the connection bet#een quantum$#ell heterojunctions and the reali5ation of a three$transition solar cell. Eremner et a-. ;84< consider that the occupanc% of electrons and holes in the quantum confined region are each described b% t#o distinct quasi$:ermi levels. hus, one single quasi$:ermi level variation e.ists in the quantum confined region. Similarl%, Eremner et a-. ;84< consider that the occupanc% of electrons and holes in the barrier region are each described b% t#o distinct quasi$:ermi levels. hus, one single quasi$:ermi level variation e.ists in the barrier region. In their description, at the junction bet#een the confining material and the barrier material, there is a step in the quasi$:ermi levels describing the occupanc% of electrons ;84<. Oo#ever, at the junction bet#een the confining material and the barrier material, there is no step in the quasi$:ermi levels describing the occupanc% of holes ;84<. Oaving constructed a s%stem #ith three photo$induced electronic transitions, and #ith three quasi$:ermi levels, Eremner et a-. calculate an upper efficienc% limit of 4/1 for the quantum #ell solar cell ;84<. In 1??1 Earnham et a-. illustrate up to a 101 efficienc% enhancement in *a9sR9l*a9s p-i-n multi$quantum$#ell structures ;83< relative to control solar cells. hat said, at the time that this present disseration is #ritten, no global efficienc% enhancement is e.perimentall% observed in quantum$#ell solar cells. ".3.3 )*an!*%-6o! A--roa'& Tanostructured quantum$dot heterojunctions are proposed to implement a three$transition solar cell ;8?, 40, 41<. In this approach, the electronic states of the intermediate band are introduced into the previousl% forbidden bandgap of a host semiconductor b% the threedimensional confining potential created b% quantum$ dot heterojunctions. hree$transition solar cells implemented #ith this proposed approach are most often referred to as quantumdot intermediate$band solar cells 6-( IES=7 ;8?, 40, 41<. In the initial proposal of the quantum dot solar cell, it is suggested that In*a9sR9l*a9s quantum$dot heterojunctions gro#n on *a9s substrates ma% be used to s%nthesi5e the appropriate absorber ;8?<. =ontrar% to the initial proposal, e.perimental protot%pes include the follo#ing heterojunctions& In9sR*a9s ;/1, 42, 4", 4/< and In*a9sR*a9s ;48<, both gro#n on *a9s substrates. hese material s%stems 6 i.e., In*a9sR9l*a9s on *a9s substrates, In9sR*a9s on *a9s substrates, and In*a9sR*a9s *a9s substrates7 have t#o characteristics limiting their usage for development of a -( IES= ;44<& the% have valence band discontinuities and the% accumulate strain. 'ev% and Oonsberg identif% absorbers for multiple transition solar cells that are implemented #ith nanostructured heterojunctions ;44<. heir technical approach introduces a novel design rule that mandates a negligible valence band discontinuit% bet#een the barrier material and confined materials ;44<. 9nother ,e% design rule stipulates that the substrate have a lattice constant in bet#een that of the barrier material and that of the quantum confined material, #hich permits strain compensation ;44<. :our candidate materials s%stems 6confinedRbarrierRsubstrate7 are identified& In+0.38Sb0.18R*a9sRIn+,In9s0./0+0.40R*a9sRIn+,In9sR*a9s0.33Sb0.12RIn+,andIn+R*a9s0.00+0."0R* a9s ;44<. -( IES= e.perimental protot%pes include absorbers composed of In9sR*a9s heterojunctions ;/1, 42, 4", 4/< and In*a9sR*a9s heterojunctions ;48<. 9t the time that this present disseration is #ritten, all protot%pe quantum$dot solar cells sho# a deteriorated efficienc% as compared to a control solar cell fabricated #ithout quantum dots ;/1, 48, 4", 40<. hus, at the time that this present disseration is #ritten, no global efficienc% enhancement is e.perimentall% observed in quantum$dot solar cells. ".3.+ E4!ended-S!a!e# A--roa'& he last proposed approach to fabricate a three$transition absorber involves the s%nthesis of allo%s derived from host semi$conductors. In these proposals, the intermediate states are those of the e.tended states of

dopants introduced into the host$semiconductor. he majorit% of these proposals ;/4, 43, 4?, 00, 80, 01, 02, 0"< are based on first$principle theoretical calculations using a periodic densit% functional theoretic approach ;0/, 08, 04<. Oo#ever, other proposals ;/3, 00, 03< are e.plained b% the band anti$crossing model ;0?, 30, 31, 32<. Of all these proposals, onl% t#o absorbers #ith a band of intermediate states are e.perimentall% s%nthesi5ed& Un1.An.O/ e1/ allo%s ;/3, 00< and *aT/9s1.+. allo%s ;03<. 9t the time that this present disseration is #ritten, these absorbers have not been processed into solar cells. hus, no global efficienc% enhancement is e.perimentall% observed b% using this proposed approach. ".3., Con'l*#ion# In this section, Section 2.", the present author revie#s four proposed approaches to reali5e a three$transition solar cell. In some instances, the proposed approaches %ield a relative efficienc% enhancement #ith respect to a control solar cell. his is the case for impurit%effect photovoltaic solar cells ;8/, 88<, and quantum$#ell solar cells ;83<. Oo#ever, the demonstration of a global efficienc% enhancement is absent from the literature. In the follo#ing section, the present author revie#s e.perimental #or, on multiple transition solar cells. he aim of much of the e.perimental #or, is to verif% the ,e% precepts on #hich the theori5ed global efficienc% enhancement depends. 2.4 E)"erimentation to Con irm the *rece"ts o the %hree-%ransition Solar Cell here are several theoretical precepts on #hich the global efficienc% enhancement of the three$transition solar cell relies. =onsidering that the global efficienc% enhancement of the three$transition solar cell is not %et e.perimentall% demonstrated, it is of acute importance to e.perimentall% verif% these precepts one b% one. In some cases, the verification requires the use of one apparatus 6 e.g. the use of a spectrophotometer to measure the absorptance7 and in some cases, verification requires the use of several apparati combined #ith the use ph%sical models 6 e.g. the use of a electroluminescence spectra and quantum efficienc% measurements to determine the e.tent of quasi$:ermi level splitting7. (epending on the precept, e.perimental data e.ists for one or more of the four proposed approaches to s%nthesi5e the three$transition absorber 6i.e. locali5ed states of dopants, subbands introduced b% quantum$#ell heterojunctions, the intermediate states introduced b% quantum$dot heterojunctions, and e.tended states of dopants7. In section 2./.1, the present author outlines the precepts on #hich the global efficienc% enhancement of the three$transition solar cell relies. he subsequent si. subsections are summaries of e.perimental evidence utili5ed to anal%5e #hether or not these precepts are verified and to #hat e.tent. In section 2./.2, the present author anal%5es the e.tent to #hich the absorption characteristic of protot%pes three$transition solar cells matches the h%pothesi5ed absorption characteristic of theori5ed three$transition solar cells. In section 2./.", the present author anal%5es the e.tent to #hich the emission characteristic of protot%pes three$transition solar cells matches the h%pothesi5ed emission characteristic of theori5ed three$ transition solar cells. In section 2././, the present author anal%5es the e.tent to #hich the collection of electron$hole pairs in protot%pes three$transition solar cells matches the h%pothesi5ed collection of theori5ed three$transition solar cells. In section 2./.8 , the present author anal%5es the e.tent to #hich the generation of charge current in protot%pes three$transition solar cells matches the h%pothesi5ed generation of charge current theori5ed three$transition solar cells. In section 2./.8 , the present author anal%5es the e.tent to #hich the generation of charge current under broadband illumination in protot%pes three$transition solar cells matches the h%pothesi5ed generation of charge current theori5ed three$transition solar cells. In section 2./.4 , the present author anal%5es the e.tent to #hich the voltage factor under broadband illumination in protot%pes three$transition solar cells matches the h%pothesi5ed voltage factor of charge current theori5ed three$transition solar cells. In section 2./.0 , the present author anal%5es the e.tent to #hich the separation of more than t#o quasi$:ermi levels is demonstrated in protot%pes three$transitions solar cells. :inall%, in section 2./.3, the present author concludes that, at the time that this disseration is published, a bod% of e.perimental evidence to irrefutabl% confirm the e.istence of either a three$transition absorber or a three$ transition solar cell is absent from the literature. he present author further concludes that, in order to substantiate these claims, the set of e.perimental methods applied to protot%pe three$transition solar cells must be e.tended, so that both the absorption and emission of photons in the infrared regime of the electromagnetic spectrum ma% be recorded. he present author no# continues to outline the precepts of the three$transition solar cell. ".+.1 I!e%iza!ion o0 T&ree-Tran#i!ion Solar Cell Pre'e-!# he global efficienc% enhancement of a three$transition solar cell is predicated on several central precepts and several supporting conditions. he present author first itemi5es the central precepts and then itemi5es the supporting conditions. he present author no# outlines the si. central precepts on #hich the capabilit% of global efficienc% enhancement is made possible. hese central precepts include that& ! the absorption of photons results from three distinct radiativel%$coupled interband electronic transitions ;20<, ! the emission of photons results from three distinct radiativel%$coupled interband electronic transitions ;/1, 3"<, ! the collection of electron$hole pairs results from each of these three radiativel%$coupled absorption events, ! the generation of a large charge current results from the absorption of broadband illumination ;20, 3", 42<, ! the demonstration of a large voltage factor results from the absorption of broadband illumination ;20, 3"<, and,

! the distribution of carriers in each of the three electronic bands is described b% three distinct quasi$:ermi levels #hen in non$equilibrium conditions ;"8<. he list above contains the precepts that are absolutel% necessar% to achieve a global efficienc% enhancement. Oo#ever, the list above is not sufficient to achieve the efficienc% limit of a three$transition solar cell. In fact, several other conditions are required to achieve the efficienc% limit. he present author no# outlines four additional conditions that ma% guarantee a global efficienc% enhancement and, more specificall%, guarantee an efficienc% near to the limiting efficienc% of the three$transition solar cell. hese conditions are that& ! the absorption characteristic is such that the absorption coefficient relating to each of the three radiativel%$ coupled electronic transitions is high for all photons greater than the smallest energetic gap bet#een t#o electronic bands ;20<, ! the absorption characteristic is such that absorption overlap #ith respect to the absorption coefficients of an% t#o radiativel%$coupled transitions is minimal ;3/<, ! the occupation of the intermediate states under broadband irradiance is such that the number of filled intermediate states and the number of empt% intermediate states are of the same order of magnitude ;20, 10<, and, ! the recombination rate resulting from non$radiative events bet#een an% t#o electronic bands is Islo#J rather than IfastJ ;20<. 6 his #ill have a significant impact on the voltage factor.7 Eased on the fact that a global efficienc% enhancement is not e.perimentall% demonstrated in protot%pe three$transition solar cells, it is of importance to verif% each of these precepts and these conditions in protot%pes solar cells. Oaving itemi5ed the central precepts and additional conditions on #hich the potential for a global efficienc% enhancement of the three$transition solar cell is premised, the present author no# revie#s e.perimental studies on protot%pe three$transition solar cells that relate to the first of these fundamental precepts& those studies that relate to the absorption of photons. ".+." A$#or-!ion o0 P&o!on# One of the central precepts of the three$transition solar cell is that the introduction of intermediate states ma% adjust the absorption characteristic so that the absorption coefficient describing each electronic transition is high ;20<. his precept ma% be demonstrated b% measuring the optical absorption absolutel% or b% measuring the optical structure #ith modulation techniques. he literature includes absorption measurements for t#o classes of protot%pe three$transition solar cells& those #ith states intending to %ield an impurit%$photovoltaic effect ;38< and those #ith states intending to %ield a band of e.tended states ;/3, 34, 00, 03<. he present author #ill no# discuss the t#o approaches of measuring the absorption characteristics. he absorption characteristic of an absorber ma% be significantl% altered via the introduction of intermediate states. his ma% be demonstrated b% measuring the absolute reflectance ;30< and absolute transmittance ;30< before and after the introduction of the intermediate states and comparing the respective absorptance spectra 6absorptance > 1 $ transmittance $ reflectance7. 9 perfect demonstration #ould sho# that 6a7 the absorptance of the sample #ith intermediate states has an onset that is much lo#er than the onset of the sample #ithout intermediate states 6i.e., photons #ith lo#er energies are absorbed in a sample #ith the intermediate states as compared to a control sample #ithout the intermediate states7 and 6b7 the absorptance of the sample #ith intermediate states is equal to or nearl% equal to unit% over the entire domain that its absorptance is non$5ero. hough the absorption characteristic ma% be modified b% the introduction of intermediate states, in some instances the observation of a change in the absolute absorptance ma% be some#hat obscured. In such cases, the use of modulation techniques ;33, 3?, ?0< ma% be used to determine the change in the dielectric constant. 9n indication of the correct s%nthesis of a three$transition absorber #ould be the presence of three abrupt changes in the measured modulated spectra. Cach of these three abrupt changes corresponds to one of the energetic gaps of the three$transition absorber 6see :igure 4 and :igure 07. he present author no# revie#s e.perimental results of protot%pe three$transition absorbers. 9bsolute absorptance is measured b% Uundel et a-. in solar cells intending to use locali5ed states to implement a three$transition solar cell ;38<. Uundel et a-. sho# that the absorptance spectra of proton$implanted solar cells and control solar cells are the same 6#ithin the bounds of e.perimental error7 for photons #ith energies in the range of 0./? e) to 4 e). +hotomodulated reflectance is measured in protot%pe three$transition absorbers ;/3, 34, 00, 03<. Ksing photomodulated reflectance spectroscop%, 2u et a-. ;/3, 34< and Walu,ie#ic5 et a-. ;00< illustrate the onset of t#o band$to$ band optical transitions in Un0.33An0.12 e& one at 1.3 e) and the other at 2.4 e). Similarl%, 2u et a-. illustrate the onset of t#o band$toband optical transitions in =d0 .33UnO e0.12 e& one at 1.0 e) and the other at 2.8 e) ;34<. :inall%, 2u et a-. use photomodulated reflectance spectroscop%, to illustrate the onset of t#o band$to$band optical transitions in *aT9s+ quaternar% allo%s ;03<. E% comparing several samples #ith distinct molar concentrations of phosphorus, 2u et a-. sho# that these t#o onsets increase as the molar concentration of phosphorus increases. he present author no# summari5es these findings and dra#s one conclusion. he global efficienc% enhancement of the three$transition solar cell relies on the premise that the introduction of intermediate states ma% adjust the absorption characteristic so that the absorption coefficient describing each electronic transitions is high ;20<. he introduction of intermediate states is e.perimentall% demonstrated to alter the absorption characteristic in several protot%pe three$transition absorbers ;/3, 34, 00, 03<. Ksing direct e.perimental measurements, the authors of references ;/3, 34, 00, 03< onl% illustrate t#o of

the three absorption onsets that are required of a three$transition absorber. he third onset, #hich #ould be detected in the infrared regime of the electromagnetic spectrum, is assumed to e.ist #ithout the support of direct e.perimental observation. Eased on the e.perimental data revie#ed in this section, Section 2./.2, the present author concludes that 6i7 the literature contains onl% a #ea, proof of the e.istence of a three$ transition absorber and 6ii7 a stronger proof #ould require the direct e.perimental observation of an absorption onset in the infrared regime. In the ne.t section, section 2././, the present author revie#s e.perimental results regarding the emission of photons b% protot%pe three$transition solar cells. ".+.3 E%i##ion o0 P&o!on# One of the central precepts of the three$transition solar cell is that the introduction of intermediate states ma% adjust the absorption characteristic so that the absorption coeffi$ cient describing each electronic transition is high ;20<. his precept ma% be demonstrated b% measuring the optical luminescent emission spectra of protot%pe three$transition solar cells ;/1, 3"<. he literature includes e.perimental measurements for t#o classes of protot%pe three$transition solar cells. In section 2./.".1, the present author h%pothesi5es the e.pected results of these measurements #hen performed on a three$transition solar cell. In section 2./.".2, the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum #ells ;83, ?1, ?2, ?", ?/<. In section 2./.".", the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum dots ;/1, 42, 4", ?8, 48, 40<. In section 2./."./, the present author presents a comparative anal%sis #ith concluding remar,s based on these e.perimental results. he e.pected results of these measurements are no# discussed b% the present author. 2.4.3.1 Hy"othesi'ed &esults he luminescent emission spectra from three$transition absorbers and three$transition solar cells are h%pothesi5ed to be characteri5ed b% significant emission #ithin three distinct spectral bands ;/1, 3"<. Cach of these three distinct spectral bands corresponds to one of the three interband electronic transitions #ithin the three$transition absorber ;/1, 3"<. Aoreover, a spectral band #ill be observed at photon energies near to the minimum energetic gap that separates each of absorber!s three electronic bands ;/1, 3"< C,ins$(au,es, Oonsberg and 2amaguchi propose four photoluminescent tests to determine #hether the required optical coupling e.ists, the relative strengths of the coupling, and #hether the intermediate is electronicall% isolated from both the conduction band and valence band ;3"<. he most rudimentar% of these test involves the use of standard noncontact photoluminescence spectroscop% #ith a laser source #hose emission #avelength is lo# enough to induce all three interband electronic transitions. he resultant optical spectra ma% be compared #ith the luminescent signature of a three$transition absorbers #ith an ideali5ed absorptance 6see pane 697 of :igure 117. +roof$positive results #ould reveal luminescence in three #ell$separated spectral bands& one band for each of the three interband electronic transitions ;/1, 3"<. Cach of these bands #ould e.ist near to the minimum energetic gaps separating each of the three electronic bands comprising the three$transition absorber ;/1, 3"< 'ev%, C,ins$(au,es, and Oonsberg also present theoretical photoluminescent spectra of three$transition absorbers ;?3<. he novelt% of their #or, lies in illustrating the spectroscopic consequences of multi$gap absorbers #hose quantum states form parabolic bands ;?3< 6see pane 6E7 of :igure 117. 'ev% et a-. conclude that the photoluminescent intensit% of a three$transition absorber ma% be apparent #ithin four distinct and #ell$separated spectral bands ;?3<. he fourth spectral band, #hich is not visible in the spectrum illustrated in pane 6E7 of :igure 11, is related to photo$induced intraband electronic transitions and appears in the far$infrared regime of the electromagnetic spectrum. One additional spectroscopic consequence of the parabolic$band appro.imations is that the photon energ% associated #ith the pea, of each spectral band occurs at a slightl% higher energ% than the photon energ% associated #ith the luminescence onset of the same spectral band. hus, the photon energ% at #hich a pea, is observed is larger than the minimum energetic gap bet#een the corresponding electronic bands 6see pane 6E7 of :igure 117. he present author no# revie#s e.isting e.perimental results relating to the emission of photons from protot%pe three$transition absorbers and three$transition solar cells. 1ig*re 11/ +hotoluminescence spectra of ideali5ed three$transition absorbers. 697 +hotoluminescence spectra of three$transition absorber #ith a semi$infinite length and ideali5ed absorptance. :or this e.ample, the bandgap 6I,)7 > 0.0 e), the bandgap 6=,I7 > 1.2/ e), and the bandgap 6=,)7 > 1.?8 e). he onsets of each spectral band occur at one of these three energies. :igure ta,en from reference ;3"<. 6E7 +hotoluminescence spectra of a three$transition absorber of finite length and #ith absorption coefficients derived from parabolic$band appro.imiations ;?4, ?0<. :or this e.ample, the #idth of the intermediate band is 0.1 e), the bandgap 6I,)7 > 1.08 e), the bandgap 6=,I7 > 0.18 e), and the bandgap 6=,)7 > 1."0 e). he onsets of each spectral band occur at one of these three energies.

2.4.3.2 +uantum ,ell Several authors measure the luminescent emission of photons from protot%pe three$transition solar cells implemented #ith quantum #ells ;??, 100, 101, ?/, 102, 10", 10/, 108<. sui et a-. record the photoluminescence of *a9sR9l*a9s single$quantum$#ell p-i-n photodiodes ;??<. sui et a-., observe luminescence in one spectral band located at roughl% 1.8 e) in structures #ith a quantum #ell #hose #idth is 1/0 9ngstroms and in one spectral band around 1.4 e) in structures #ith a quantum #ell #hose #idth is 80 9ngstroms ;??<. Aean#hile, several authors observe luminescence from *a9sR9l*a9s structures in one spectral band #hose pea, is roughl% located at 1./" e) ;100, 101<. :urther, Telson et a-. ;100<, C,ins$ (au,es et a-. ;101<, and Earnham et a-. ;?/, 10/<, observe luminescence from In$*a9sR*a9s structures in t#o spectral band #hose pea,s are roughl% located at roughl% 1.23 e) and 1./" e), respectivel%. Fluftinger et a-. ;102, 10"< observe luminescent photon emission from *a9sR9l*a9s as%mmetrical double$quantum$ #ell structures. Fluftinger et a-. ;102, 10"< also illustrates photo$emission in one spectral band from the narro# quantum #ell and illustrate photo$emission in one spectral band from the #ide quantum #ell. he emission pea, in these spectral bands occurs at an energ% of 1./8 e) in the #ide quantum #ell and 1.48 e) in the narro# quantum #ell, respectivel% ;102, 10"<. In the ne.t paragraph, the present author revie#s results obtained from protot%pe three$transition solar cells implemented #ith quantum dots. 2.4.3.3 +uantum -ot Several authors measure the photon emission from protot%pe three$transition solar cells implemented #ith quantum dots;/1, 48, 42, 4"<. Torman et a-. record photoluminescence from In*a9sR*a9s structures ;48<. he% record emission #ithin one spectral band located roughl% bet#een 1 e) 612/0 nm7 and 1./ e) 63?0 nm7 ;48<. 'uque et a-. measure the luminescent emission of photons from protot%pe three$transitions solar cells implemented #ith In9sR*a9s quantum dot structures ;/1, 42, 4"<. In all cases, the emission appears to derive from one spectral band. In one electroluminescence spectrum, the emission of photons are recorded in one broad spectral roughl% bet#een the #avelengths 380 nm 61./4 e)7 and 1280 nm 6??0 me)7 ;/1<. In all cases, the electroluminescence spectra is recorded in one broad spectral band. he spectral band begins at a #avelength of roughl% 380 nm 61./4 e)7 ;/1, 42, 4"< and ends at a #avelength of roughl% 1280 nm 6??0 me)7 ;/1, 42< or 1/00 nm 63?0 me)7 ;42, 4"<. he present author no# offers a comparative anal%sis of the emission of photons #ith respect to the various proposed approaches to reali5e a three$ transition absorber and solar cell. 2.4.3.4 Com"aritive !nalysis he global efficienc% enhancement of the three$transition solar cell relies on the premise that the introduction of intermediate states ma% adjust the absorption characteristic so that the absorption coefficient describing each electronic transitions is high ;20<. he introduction of intermediate states is, though e.perimentation, demonstrated to alter the emission characteristic in several protot%pe three$transition absorbers ;??, 100, 101, ?/, 102, 10", 10/, /1, 48, 42, 4"<. he measured spectra illustrate emission in one ;??, 100, 101, ?/, 102, 10", 10/, /1, 48, 42, 4"< spectral band, or t#o spectral bands ;100, 101, ?/, 10/<. With respect to quantum$#ell protot%pes, #hen there is emission from t#o distinct spectral bands ;100, 101, ?/, 10/<, one band relates to emission from the quantum #ell and the other from the barrier ;104<. With respect to some quantum$dot protot%pes, the emission of photons illustrate narro#l% separated and overlapping pea,s in one spectral band, rather than the luminescent signature of a three$transition absorber or solar cell. Eased on the e.perimental data revie#ed in this section, Section 2./.", the present author concludes that 6 i7 the literature contains no proof of the e.istence of a three$transition absorber and 6 ii7 a stronger proof #ould require the direct e.perimental observation of an emission onset in the infrared regime. In the ne.t section, section 2././, the present author revie#s e.perimental results regarding the collection of charge current in protot%pe three$transition solar cells. ".+.+ Colle'!ion o0 Ele'!ron-Hole Pair#

One of the central precepts of the three$transition solar cell is that once a photon is absorbed b% an% of the three inter$band electronic transitions, an electron$hole pair is collected in the form of a charge current. his precept ma% be demonstrated b% several related e.perimental techniques& internal$quantum$efficienc% measurements, e.ternal$quantum$efficienc% measurements, and spectral$response measurements. he literature includes e.perimental measurements for three classes of protot%pe three$transition solar cells. In section 2././.1, the present author h%pothesi5es the e.pected results of these measurements #hen performed on a three$transition solar cell. In section 2././.2, the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% locali5ed states ;100, 8/, 103, 10?, 88<. In section 2././.", the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum #ells ;83, ?1, ?2, ?", ?/<. In section 2./././, the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum dots ;/1, 42, 4", ?8, 48, 40<. In section 2././.8, the present author presents a comparative anal%sis #ith concluding remar,s based on these e.perimental results. he e.pected results of these measurements are no# discussed b% the present author. 2.4.4.1 Hy"othesi'ed &esults he quantum efficienc% of an absorber is the ratio of induced current densit% to the incident photon flu.. In solar energ% research, a quantum efficienc% spectra is obtained b% repeatedl% measuring the quantum efficienc% of an absorber under monochromatic radiation, e.cept that for each measurement, the #avelength of the incident radiation is altered. 9s applied to protot%pe three$transition solar cells, it is important to distinguish the quantum efficiencies for photons greater than its absorber!s largest energetic gap from the quantum efficiencies for photons less than its absorber!s largest energetic gap but greater than the absorber!s smallest energetic gap 6see :igure 4 on page 22 or :igure 0 on page 287. 9ttention is no# turned to photons #ith energies in the range 6D *, D * V 0D *7 #here D * is greater than the largest energetic gap in the solar cell. 9 positive quantum efficienc% indicates that the absorptivit%, a)6D *7 6see equation 607 on page 2"7, is non$5ero. In addition, the nearer to unit% the quantum efficiencies, the better. his is because it is more li,el% that the electron$hole pairs are e.tracted before the% recombine resulting from non$radiative mechanisms. 9ttention is no# turned to photons #ith energies in the range 6D *, D * V 0D *7 #here D * is less than the largest energetic gap in the solar cell and greater than the smallest energetic gap in the solar cell. If the quantum efficiencies are non$5ero, then this #ould be an indication that the three$transition solar cell ma% %ield ver% large solar energ% conversion efficiencies. :urther, the nearer to unit% that these measurements are, the more li,el% it is that the three$transitions solar cell ma% %ield ver% large solar energ% conversion efficiencies. Oo#ever, if the measured quantum efficiencies are near to or e.actl% null, then this does not conclusivel% indicate that the device #ould not %ield large solar energ% conversion efficiencies. In fact, there are three possibilities that need to be considered. :irst, it ma% indicate that the absorptivit%, a)6D *7, is 5ero, #hich #ould deter large solar energ% conversion efficiencies. Second, it ma% indicate that a)6D *7 is non$5ero and that the radiative processes act to balance the absorption #ith the emission of photons. In such case there is no net conversion of the incident photon to a charge current, %et the device ma% still operate as an efficient three$transition solar cell. hird, it ma% indicate that a)6D *7 is non$5ero and non$ radiative recombination act to balance the generation #ith the recombination of charge. In such case, there is no net conversion of the incident photon to a charge current. :urthermore, the device is unli,el% to operate as an efficient three$transition solar cell. he present author no# revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% locali5ed states. 2.4.4.2 Locali'ed States Several authors report enhanced quantum efficiencies in solar cells #ith deep impurities as compared to their respective control solar cells ;100, 8/, 103, 10?, 88<. Summonte et a-. illustrate that helium$implanted solar cells sho# both an improvement in light$induced generation and up to a 101 enhancement in quantum efficienc% in the red side of spectrum ;100<. Eruns et a-. illustrate that helium$implanted solar cells sho# up to a 101 improvement in the spectral response for both sub$ and supra$bandgap photons ;8/<. Feevers et a-. ;103< and Fasai et a-. ;10?, 88< illustrate that indium incorporated into solar cells demonstrate enhanced photoresponse in the infrared. Fasai et a-. also illustrate an enhanced photoresponse for supraband gap photons as #ell ;10?, 88<. In the ne.t paragraph, the present author revie#s the results obtained from three$ transition solar cells implemented #ith quantum #ells. 2.4.4.3 +uantum ,ell he present author no# summari5es e.perimental observations of the collection of photogenerated charges in quantum$#ell solar cells. he present author first summari5es results for photons #ith energies less than the bandgap of the barrier material of the quantum$#ell solar cell, and then summari5es results for photons #ith energies greater than the bandgap of the barrier material of the quantum$#ell solar cell.With respect to photons #ith energies less than the bandgap of the barrier materials, several authors report enhanced quantum efficiencies in quantum$#ell solar cells as compared to their respective control solar cells that are fabricated #ith the respective barrier material of the quantum$#ell solar cells ;83, ?1, ?2, ?", ?/<. Earnham et a-. ;83< illustrate this in *a9sR9l*a9s p-i-n multiple$quantum$#ell structuresL Naga% et a-. ;?1< and C,ins$ (au,es et a-. ;?2< illustrate this in In*a9sR*a9s p-i-n multiple$quantum$#ell structuresL and C,ins$(a,es et a-. ;?"< and Earnham et a-. ;?/< illustrate this in strain$balanced multiple$quantum$#ell In*a9sR*a9s+ p-i-n

structures. With respect to photons #ith energies greater than the bandgap of the barrier materials, the results of quantum$efficienc% measurements of quantum$#ell solar cells var% greatl% as compared to the quantum efficiencies of their respective control solar cells that are fabricated #ith the respective barrier material of the quantum$#ell solar cells. Naga% et a-. ;?1<, C,ins$(a,es et a-. ;?", ?2<, and Earnham et a-. ;?/< all illustrate multiple$quantum#ell structures #hose quantum efficiencies are either enhanced or reduced H depending on the e.act energ% of the photon being considered. Naga% et a-. ;?1< and Earnham et a-. ;10/< illustrate multiple$quantum$#ell structures #hose quantum efficiencies are al#a%s diminished. Earnham et a-. illustrate multiple$quantum$#ell structures #hose quantum efficiencies are roughl% unaltered ;10/<. In the ne.t paragraph, the present author revie#s the results obtained from three$transition solar cells implemented #ith quantum dots. 2.4.4.4 +uantum -ot he present author no# summari5es e.perimental observations of the collection of photogenerated charges in quantum$dot solar cells. he present author first summari5es results for photons #ith energies less than the bandgap of the barrier material of the quantum$#ell solar cell, and then summari5es results for photons #ith energies greater than the bandgap of the barrier material of the quantum$dot solar cell. With respect to photons #ith energies less than the bandgap of the barrier materials, several authors report enhanced quantum efficiencies in quantum$dot solar cells as compared to their respective control solar cells that are fabricated #ith the respective barrier material of the quantum$dot solar cells ;/1, 42, 4", ?8, 48<. 'uque et a-. ;/1, 42, 4"< and 'ope5 et a-. ;?8< illustrate this in In9sR*a9s p-i-n multila%er quantum$dot structures, #hile Torman et a-. ;48< illustrate this in In*a9sR*a9s p-i-n multila%er quantum$dot structures. In some cases, e.perimental results indicate that as the number of multila%ers increases to fift% la%ers, the subbandgap response increases as #ell ;48<, #hile in other cases, this monotonic trend is absent ;?8, 40<. With respect to photons #ith energies greater than the bandgap of the barrier materials, several authors report reduced ;48, 40< or comparable ;/1, 42, 48, 4"< quantum efficiencies in quantum$dot solar cells, as compared to their respective control solar cells, #hich are fabricated #ith the barrier material of the respective quantum$dot solar cells. :rom a comparison of multila%er samples #ith and #ithout silicon doping, Torman et a-. infer that the cause of the reduced e.ternal quantum efficienc% is related to the silicon doping ;48<. AartPI et a-. e.plain this same phenomena in terms of a diminishing charge current generated b% the p$t%pe emitter, #hich is caused b% an increasing number of dislocations that propagate to#ard the p$t%pe emitter from the quantum dot region ;40<. he present author no# offers a comparative anal%sis of the collection of charge current #ith respect to the various proposed approaches to reali5e a three$transition solar cell. 2.4.4.# Com"aritive !nalysis he present author observes three trends in the summar% of e.perimental data revie#ed in section 2././. :irst, protot%pe three$transition solar cells e.hibit the collection of charge carriers resulting from the absorption of photons #ith energies less than the bandgap of their respective host semiconductors ;83, ?1, ?2, ?", ?/, /1, 42, 4", ?8, 48<. Second, each protot%pe three$transition solar cell %ields greater collection efficiencies for photons #ith energies larger than the bandgap of the host semiconductor as compared to the collection efficiencies for photons #ith energies smaller than the bandgap of the host semiconductor ;100, 8/, 88, 83, ?/, 10/, 108, ?1, ?2, ?", /1, 42, 4", ?8, 48<. hird, depending on the details, the collection of carriers resulting from the absorption of supra$bandgap photons ma% be diminished, enhanced, or unaltered as compared to their respective control solar cells. he global efficienc% enhancement of a three$transition solar cell depends on the precept that once a photon is absorbed b% an% of the three inter$band electronic transitions, an electron$hole pair is collected in the form of a charge current. he present author concludes that measured quantum efficienc% spectra of protot%pe three$transition solar cells do not conclusivel% demonstrate that these protot%pes are, in fact, three$transition solar cells. his is because an induced charge current is not demonstrated for photons #ith energies less than a fe# 100 me) less than the largest energetic gap in the s%stem. In the follo#ing section, section 2./.8, the present author revie#s the e.perimental results of protot%pe three$transition solar cells under broadband illumination. ".+., Genera!ion o0 C&arge C*rren! One of the central precepts of the three$transition solar cell is that, compared to a single p-n junction solar cell, a larger portion of the broadband solar spectrum ma% be absorbed so that a larger light$generated current is produced ;20, 3", 42<. his precept ma% be demonstrated b% first measuring the short$circuit of the protot%pe solar cell #hen irradiated b% a broadband source of illumination and then b% comparing the value of the short$circuit current to the total number of of photons in the spectrum 1. he literature includes e.perimental measurements for three classes of protot%pe three$transition solar cells. In section 2./.8.1, the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% locali5ed states ;100, 8/, 10?, 88<. In section 2./.8.2, the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum #ells ;83, ?1, ?2, ?"<. In section 2./.8.", the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum dots ;48, 40, ?8, /1<. In section 2./.8./, the present author

presents a comparative anal%sis #ith concluding remar,s based on these e.perimental results. he present author no# revie#s e.perimental results of protot%pe three$transition absorbers. 2.4.#.1 Locali'ed States Summonte et a-. conclude that solar cells implanted #ith a h%drogen la%er ma% or ma% not %ield an increase in generated current depending on the location of the h%drogen$implanted la%er ;100<. he% conclude that an% increase in generated current results from sub$bandgap absorption resulting from the states of implanted h%drogen ;100<. Oo#ever, the% conclude that there is a concomitant increase in recombination such that the h%drogen$implanted la%er %ields no increase in short$circuit current ;100< #ith respect to reference solar cells. Eruns et a-. conclude that solar cells implanted #ith a la%er of helium atoms %ield an increase in short$circuit current #ith respect to reference solar cells #ithout such la%ers ;8/<. Similarl%, Fasai and Aatsumora conclude that silicon solar cells implanted #ith indium ma% or ma% not e.perience an enhancement in short$ circuit current, as compared to silicon solar cells implanted #ith boron ;10?<. :or t#o solar cells #ith identical carrier concentrations, the enhancement in photocurrent is observed onl% #hen the carrier concentration is roughl% less than or equal to " 1014 cm" and the photocurrent enhancement ma% be as large as "01 ;10?<. his conclusion is re$enforced in reference ;88< #here Fasai et a-. illustrate a short$circuit enhancement of an indium$implanted solar cell as compared to a reference solar cell. In the ne.t paragraph, the present author revie#s results obtained from threetransition solar cells implemented #ith quantum #ells. 2.4.#.2 +uantum ,ell Earnham et a-. are the first to illustrate the short$circuit current enhancement of p-i-n multiple quantum$#ell solar cells composed of *a9s quantum #ell enveloped in 9l*a9s barriers, as compared to a reference #ithout quantum #ells ;83<. Subsequentl%, Naga% et a-. ;?1< and C,ins$(au,es et a-. ;?2< illustrate the short$ circuit current enhancement of p-i-n multiple quantum$#ell solar cells composed of In*a9sR*a9s as compared to a reference #ithout quantum #ells. Cnhancements to the short$circuit current are also observed in strain$balanced *a9s+RIn*a9s multiple quantum #ell solar cells as compared to reference *a9s solar cells ;?"<. In the ne.t paragraph, the present author revie#s results obtained from three$transition solar cells implemented #ith quantum dots. 2.4.#.3 +uantum -ot +rotot%pe three$transition solar cells implemented #ith quantum$dot technolog% almost e.clusivel% %ield diminished short$circuit current in comparison to their respective control solar cells ;48, 40, ?8<, e.cept for one case ;/1< in #hich there is a measured increase of 0.31. Torman et a-. illustrate that protot%pe In*a9sR*a9s quantum$dot intermediateband solar cells have significantl% diminished short$circuit current, as compared to a control solar cell ;48<. he same results are sho#n b% AartPQ et a-. ;40< and 'Pope5 et a-. ;?8< for protot%pe In9sR*a9s quantum$dot intermediate$band solar cells. :urther, a general trend e.ists indicating that the more quantum$dot multi$la%ers incorporated into the solar cells, the more degradation is present in the short$circuit current densit% ;48, 40, ?8<. he present author no# offers a comparative anal%sis of the generation of charge current #ith respect to the various proposed approaches to reali5e a three$transition solar cell. 2.4.#.4 Com"aritive !nalysis In this section, Section 2./.8./, the present author presents a comparative anal%sis and offers concluding remar,s based on the e.perimental data revie#ed in section 2./.8. he present author offers a broad assessment of this data follo#ed b% a specific assessment of the e.perimental data from protot%pe three$ transition solar cells implemented #ith quantum dots. he latter is necessar% because the present author!s dissertation focuses on the quantum dot implementation. One of the broad trends that the present author observes is that man% protot%pe threetransition solar cells %ield an enhanced short$circuit current, as compared to their respective controls ;8/, 10?, 88, 83, ?1, ?", ?2, /1<. he global efficienc% enhancement of a threetransition solar cell depends on the precept that a large portion of the photons in broadband illumination are converted so as to %ield a large light generated charge current. he present author concludes that measured light$generated currents of protot%pe three$transition solar cells demonstrate this precept #hen referenced to their respective control solar cells. Oo#ever, even in those protot%pes #ith an enhancement in light$generated current as compared to their respective solar cells, the ratio of the light$ generated current 6normali5ed #ith respect to the elementar% charge7 to the number of photons in the broadband illumination is smaller than #hat is theoreticall% ;20, 3"< e.pected. he present author observes that one of the trends particular to the quantum dot approach is that it generall% %ields a diminished short$ circuit current, as compared to a control solar cell ;48, 40, ?8<, #ith one e.ception ;/1<. he present author concludes that the s%nthesis of three$transition solar cells implemented #ith quantum$dot technolog% has significant room for improvement. Nesulting from the formation of quantum$dot la%ers an% number of processes are either increasing the average amount of reflection of incident photons before the% are absorbed or, more li,el%, once photons are absorbed, photo$generated carriers are recombining via non$ radiative processes before the% are e.tracted from the contacts. 9mong a plethora of possible improvements to the design of quantum$dot three$transition solar cells, it plausible that the use of strain$compensating techniques andRor the use of surfactants ma% improve the short$circuit degradation of quantum$dot three$ transition solar cell protot%pes. he present author no# revie#s the voltage factors of protot%pe threetransition solar cells. he present author concludes that e.perimental results relating to the generation

of a large charge current does not definitivel% justif% the assertion that the devices are threetransition solar cells. his conclusion is based on the fact that, #here an enhancement e.ists #ith respect to a control, the enchantment is not sufficientl% large to assert that photons across the broadband illumination source are causing this. 9n enhancement ma% also be caused, for e.ample, b% thermal up$conversion ;110<. ".+.. 6e%on#!ra!ion o0 Vol!age 1a'!or One of the central precepts of the three$transition solar cell is that it #ill have a large voltage factor ;20<. his precept ma% be demonstrated b% measuring the open$circuit voltage of protot%pe solar cells #hen illuminated b% a simulated solar spectrum. he literature includes e.perimental measurements for three classes of protot%pe three$transition solar cells& those implemented #ith locali5ed states, quantum #ells, and quantum dots. Eased on the revie# of e.perimental data, the present author dra#s t#o conclusions. he theori5ed global efficienc% enhancement of a three$transition solar cell integrall% depends on a large voltage factor ;20<. Wolf asserts this based on the argument that an optimi5ed three$transition solar cell has a large conduction$ to$valence bandgap and that, based on empirical data, a single$junction, single$transition solar cell #ith large bandgap is li,el% to have a large voltage factor ;20<. C,ins$(au,es illustrates that the ma.imumpo#er voltage of an ideali5ed three$transition solar cell is greater than the second largest of the three$transition absorber!s three bangaps $ though not much larger ;3"<. Oaving summari5ed the theoretical predictions of the voltage factor of the three$transition solar cell, the present author no# summari5es the e.perimental data. he present author observes t#o trends based on a summar% of e.perimental data from protot%pe three$ transition solar cells. :irst, the recorded values of the open$circuit voltages and ma.imum$po#er voltages of all protot%pe three$transition solar cells are reduced compared to those of their respective controls. his is true of the helium$implanted solar cells of Eruns et a-. ;8/<, the indium$implanted solar cells of Fasai et a-. ;88<, the *a9sR9l*a9s quantum$#ell solar cells of Earnham et a-. ;83, 111<, the In*a9sR*a9s quantum$#ell solar cells of Naga% et a-. ;?1<, the *a9sR*aIn+ quantum$#ell solar cells of Earnham et a-. ;111<, the In*a9sRIn+ quantum$#ell solar cells of Earnham et a-. ;111<, the In9sR*a9s quantumdot solar cells of 'uque et a-. ;/1, 4", ?8<, and the In*a9sR*a9s quantum$dot solar cells of Torman et a-. ;48<. Second, the larger the number of quantum$dot multila%ers present in protot%pe quantum$dot three$transition solar cells, the larger the reduction in the voltage factor ;48, 40, ?8<. he present author offers conclusions based on these observations. he present author dra#s t#o conclusions. :irst, it is unclear if the voltage factors required for a global efficienc% enhancement are obtained in protot%pe three$transition solar cells. his lac, of clarit% results from imprecise evaluations of the absorbers! respective band structures. Second, the quantum$dot approach to reali5e a three$transition solar cell is faced #ith a fundamental parado.. his parado. is that a large number of multi$la%ers is essential for a high absorptivit% of sub$bandgap photons ;112<, but observations indicate that as the number of multila%ers increases, the voltage factor decreases. he present author no# revie#s e.perimental data relating to the presence of more than one quasi$:ermi level separation in protot%pe three$transition solar cells. ".+.; Se-ara!ion o0 )*a#i-1er%i Le el# One of the central precepts of the three$transition solar cell is that, under non$equilibrium conditions, the occupanc% of electronic states comprising each of the three bands ma% be described b% three distinct quasi$ :ermi levels. he literature includes e.perimental measurements of more than one quasi$:ermi level separation for t#o classes of protot%pe three$transition solar cells. In section 2./.0.1, the present author revie#s the theoretical basis for the assertion that an absorber ma% maintain more than one quasi$:ermi level separation. In section 2./.0.2, the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum #ells ;??, 100, 101, 102, 10"<. In section 2././.", the present author revie#s e.isting e.perimental results for protot%pes #here the intermediate levels are introduced b% quantum dots ;/1, 42<. In section 2./.0./, the present author presents a comparative anal%sis #ith concluding remar,s based on these e.perimental results. he e.pected results of these measurements are no# discussed b% the present author. he present author no# revie#s e.perimental evidence focused on demonstrating the e.istence of more than t#o quasi$:ermi levels in protot%pe three$transition solar cells. his is discussed first for protot%pes #here the intermediate levels are introduced b% quantum #ells, and ne.t for protot%pes #here the intermediate levels are introduced b% quantum dots. 2.4...1 %heoretical /asis In the majorit% of te.tboo,s on semiconductors and semiconductor devices, it is e.plained that the non$ equilibrium occupanc% of electronic states in a semiconductor ma% be described b% t#o distinct quasi$:ermi levels& one describing the occupanc% of electrons in the conduction band, and another describing the occupanc% of electrons in the valence band. his is so #hether the semiconductor is intrinsic, p-t%pe or nt%pe. 2et, in their discussion of the statistics of recombination of holes and electrons in semiconductors, Shoc,le% and Nead ;/"< e.plain that occupanc% of trap levels #ithin the semiconductor!s bandgap is described b% a third quasi$:ermi level& one that is uniquel% associated #ith those traps ;/"<. o the best of the present author!s ,no#ledge, it is Fettemann and *uillemoles ;11"< #ho first e.plicitl% state the importance of more than t#o$quasi :ermi levels #ith respect to the capabilit% of a multi$transition solar cell to overcome the upper$efficienc% limit of the Shoc,le%$-ueisser solar cell ;8<. In their discussion of multiple$ transition solar cells implemented #ith lo#dimensional structures 6 e.g. quantum #ells7, Fettemann and *uillemoles consider multiple electronic bands #here each electronic band is comprised of delocali5ed

quantum states and #here the distribution of carriers in each electronic band is described b% a unique quasi :ermi level ;11"<. In the particular case of a three$transition solar cell, the upper$theoretical efficienc% limit is fundamentall% premised on three quasi$:ermi levels ;11", "8, 84<. C.perimentall% verif%ing the e.istence of more than t#o quasi$:ermi levels is fundamentall% important in demonstrating the feasibilit% of developing the three$transition solar cell. he present author no# revie#s e.perimental evidence focused on demonstrating the e.istence of more than t#o quasi$:ermi levels in protot%pe three$transition solar cells implemented #ith quantum #ells. 2.4...2 +uantum ,ell sui et a-. assert that the absolute value of the quasi$:ermi$levels separation ma% be obtained from calibrated photoluminescence spectra or calibrated electroluminescence spectra ;??<. he% further appl% this method to determine the quasi$:ermi$levels separation in single$quantum$#ell structures b% using photoluminescence spectra in particular ;??<. Ksing the method e.plained b% sui et a-. ;??<, Telson et a-. state that if one assumes that the quasi$:ermi$level separation in the quantum #ell is that of the voltage across the structure the the emission resulting from single$quantum$#ell structure is overestimated ;100<. Nather, the calibrated emission spectrum implies that the quasi$:ermi$level separation in the quantum #ell is less than that of the voltage across the cell ;100<. In fact, e.perimental investigations from In*a9sR*a9s and *a9sR9l*a9s quantum #ell structures %ield evidence that the difference bet#een the voltage and quasi$ :ermi$level separation in the quantum #ell is a fe# tens of me) less than the applied voltage ;100, 101<. :rom calibrated luminescent spectra, Fluftinger et a-. infer that quasi$:ermi$level variations e.ist in as%mmetric double$quantum$#ell structures ;102, 10"<. In the ne.t paragraph, the present author revie#s results obtained from protot%pe three$transition solar cells implemented #ith quantum dots. 2.4...3 +uantum -ot 'uque and AartPQ assert the presence of three distinct quasi$:ermi levels in protot%pe threetransition solar cells implemented #ith quantum dot technolog% ;/1, 42<. he% infer this based on t#o distinct anal%ses. In the first anal%sis, the% infer the presence of three distinct quasi$:ermi levels based on the fit of e.perimental data to generali5ed circuit diagram of the three$transition solar cell ;/1<. (epending on both the operating point of the protot%pe three$transition solar cell and one of four fitting cases, 'uque and AartPQ infer that the voltage bet#een the conduction band and intermediate band in protot%pe three$transition solar cells implemented In9sR*a9s quantum dot structures ma% be an%#here bet#een 5ero and 200 me) ;/1<, and that the voltage bet#een the conduction band and intermediate band ma% be an%#here bet#een 00 me) and 1.2 e)7. In the second anal%sis, the% present evidence for the presence of three distinct quasi$:ermi levels in protot%pe three$transition solar cells b% placing values of measured e.perimental data into closed$form e.pressions for the quasi$:ermi level separation ;42<. In particular, from quantum efficienc% measurements and electroluminescence spectra recorded from protot%pe three$transition solar cells implemented In9sR*a9s quantum dot structures, 'uque and AartPQ infer that the voltage bet#een the conduction band and intermediate band is bet#een 1?0 me) and 230 me) ;42<. 2.4...4 Com"aritive !nalysis In this section, Section 2./.0./, the present author presents a comparative anal%sis and offers concluding remar,s based on the e.perimental data revie#ed in section 2./.0. he present author observes that several authors assert the e.istence of more than one quasi$:ermi$level separation in three$transition solar cells implemented #ith nanostructures ;??, 100, 101, 102, 10", /1, 42<. he global efficienc% enhancement of a three$transition solar cell depends on the precept that #hen the absorber is not in equilibrium, the distribution of carriers in the solar cell are described b% three distinct quasi$:ermi levels, and hence three distinct quasi$ :ermi$level separations. he present author concludes that three$transition solar cells implemented #ith quantum #ells ma% have a fundamental characteristic preventing them from reali5ing a global efficienc% enhancement. his characteristic is that onl% t#o 6rather than three7 quasi$:ermi$level separations are observed& one in the quantum confined region and one in the barrier region ;100, 101, 102, 10"<. he present author no# revie#s the emission of photons from protot%pe three$transition solar cells. ".+.< Con'l*#ion# In this section, Section 2./, the present author revie#s e.perimental results aimed at confirming several of the central precepts 6see section 2./.1 on page "/7 on #hich rests the global efficienc% enhancement of the three$transition solar cell. Eased on a revie# of those results, the present author asserts that the absorption and emission of photons from three distinct transitions is not verifiedL that the collection of electron$hole pairs generated from three distinct absorption events is not verifiedL that, though an increase in charge current #ith respect to a control is observed, the magnitude of the charge current is not commensurate #ith the conversion of a significant faction of broadband illuminationL that the maintenance of a large voltage factor is not verifiedL and that, though e.perimental evidence is purported, the e.istence of three distinct quasi$:ermi levels is not irrefutabl% verified. he present author concludes, that at the time that this disseration is published, a bod% of e.perimental evidence to support the e.istence of either a three$transition absorber or a three$transition solar cell is absent from the literature. he present author further concludes that e.perimental results relating to both the absorption and emission of photons is severel% hampered b% the lac, of photo$detection in the infrared regime of the electromagnetic spectrum. 2.# Conclusions

In this chapter, the present author revie#s the theoretical operation of an ideali5ed threetransition solar cell, revie#s proposals to reali5e a three$transition solar cell, and revie#s the e.perimental characteri5ation of protot%pe three$transition solar cells. Eased on a summar% of the theoretical operation of ideali5ed three$ transition solar cells, the present author concludes that there are t#o principle merits that justif% research and development of the three$transition solar cell. :irst, the three$transition solar cell is a single p-n junction device that is capable of achieving solar energ% conversion efficiencies equivalent to that of a stac, of three single$junction, single$transition solar cells. Second, the spectral robustness of the three$transition solar cell is greater than that of a tandem$stac, of three single$junction, single$transition solar cells electricall% assembled in series. herefore, in practice, a three$transition solar cell #ith a band structure that deviates from the optimum band structure #ill have less deterioration than a tandem$stac, of three single$junction, single$transition solar cells electricall% assembled in series #ith a comparable deviation in its band structures as compared to the optimal band structures. Eased on a summar% of the four proposals to reali5e a three$transition solar cell, the present author concludes that a global efficienc% enhancement is not e.perimentall% demonstrated in protot%pe three$transition solar cells. With respect to the above conclusion, it is imperative to e.perimentall% verif% each of the si. fundamental precepts and four ancillar% conditions 6see section 2./.1 for more details7 on #hich the global efficienc% enhancement is theoreticall% based. Kntil a global efficienc% enhancement is e.perimentall% demonstrated, this should be done for an% and all protot%pe three$transition solar cells. Eased on a summar% of the e.perimental characteri5ation of protot%pe three$ transition solar cells, the present author dra#s t#o conclusions. :irst, the present author concludes that at present, a bod% of e.perimental evidence to irrefutable support the e.istence of either a three$transition absorber or a three$transition solar cell is, in fact, absent from the literature. Second, the present author concludes that the absence of infrared detection #hile recording absorption and emission spectra severel% hampers the abilit% to directl% observe the e.istence of a three$transition absorber and three$transition solar cell. Without the present of infrared detection, researchers ma%, at best, infer the presence of three absorption edges or the presence of emission #ithin three distinct spectral bands. CHAPTER III - 6ETAILE6-7ALANCE E11ICIENCY O1 THE INTER2E6IATE 7AN6 SOLAR CELL @N6ER NON-OPTI2AL CON6ITIONS 3.1 Introduction his chapter e.amines the detailed$balance conversion efficienc% of a solar cell #ith an intermediate band 6IE7 under non$optimal conditions. In Section ".2 the author presents a thermod%namic treatment of an intermediate band solar cell. he novelt% is the inclusion of photo$induced electronic transitions bet#een t#o distinct states of the intermediate band. he treatment allo#s for t#o blac,bod% sources, intraband and interband photo$induced electronic transitions, overlapping absorption coefficients, multiple electronhole pair generation, and non$radiative processes. 9 schematic of the device!s thermod%namic configuration sho#s that the solar cell operates as a tandem stac, of three p$n junctions. In Section "." the author considers solar cells #ith ideal electro$chemical conversion, #hose absorbers are intermediate bands media #ith finite band#idths, #hich permit both interband and intraband photo$induced electronic transitions at states #ithin the IE. o comprehend the effect of the IE #idth, three classes of IE absorbers are constructed, each of #hich is distinguished b% its spectral selectivit%. It is sho#n that 6 i7 the ma.imum po#er efficienc% tends graduall% to#ards 5ero #ith increasing band#idth #hen photo$induced interband transitions and intraband transitions e.ist at parit%L 6ii7 #ith respect to the former, a relative efficienc% enhancement ma% occur #hen photo$induced intraband transitions dominate interband transitionsL and 6 iii7 though thermod%namicall% consistent, efficiencies ma% be ph%sicall% inconsistent #ithout including photo$induced intraband transitions. he emphasis on both finite band#idth and spectral selectivit% enhances the scientific understanding of opto$ electronic devices #ith intermediate states. 3.2 Intra(and !(sor"tion in Solar Cells 0ith an Intermediate /and 3.".1 In!rod*'!ion he novelt% #ithin Section ".2 is the inclusion of photo$induced electronic transitions bet#een t#o distinct quantum states of an electronic band that is intermediate bet#een the conduction band 6=E7 and valence band 6)E7 6see :igure 127. his innovation is significant for t#o reasons. :oremost, #hen intraband transitions are absent, #hich is the case in reference ;"8<, the detailed$balance anal%sis of an intermediate band 6IE7 solar cell 6IES=7 %ields results inconsistent #ith ph%sical realit% ;1"<. 9dditionall%, in the case #here the IE #idth e.ceeds the smallest bandgap in the s%stem, #hich is the case for man% candidate IE absorbers 6see reference ;/4< and citations b% those authors7, the calculation of efficienc% #ithout these transitions fails to account for degradation resulting from parallel absorption paths ;?3<. he formalism here accounts for that portion of incoming photons that e.cite intraband electronic transitions that generate no photovoltaic po#er densit%. he approach here emphasi5es the emission spectrum of the IE material. hus, Section ".2 ma% appl% to photovoltaic devices, such as up$ ;11/< and do#n$converters ;118< and multi$band solar cell ;"4<, as #ell as electron devices that operate in different regimes of the current$voltage characteristic ;/<. hese ma% include unstac,ed multi$color light emitting diodes ;114< and unstac,ed multi$color photo$detectors ;110<. 1ig*re 1"/ Interaction of light #ith the states of an intermediate band absorber. :or each of the four electronic transitions 6 i.e. 6I,I7, 6I,)7, 6=,I7, and 6=,)7 7, there are three t%pes of photon interactions& 6from left to right7 stimulated absorption, stimulated emission, and spontaneous emission.

9s sho#n in :igure 12, an IE absorber permits four photo$induced electronic transitions& an intra$band transition bet#een t#o distinct states in the IE, 6I,I7L and three interband transitions bet#een a state in the =E and )E, 6=,)7, bet#een a state in the =E and IE, 6=,I7, and bet#een a state in the IE and )E, 6I,)7, respectivel%. he set of allo#ed photo$induced electronic transitions, T , is thus defined as T.>16I,I7 , 6I,)7 , 6=,I7 , 6=,)721. Shoc,le% and Nead ;/"< e.plain that the statistics of the absorber!s conduction, intermediate, and valence states are each described b% a unique quasi$:ermi level, :=, :I, and :), respectivel%. he ideal structure ;2< of an IES= 6see :igure 1"7 contains an IE absorber that is sand#iched bet#een a n$ and a p$t%pe semiconductor ;10<. he quasi$:ermi level separation, := :), ma% bias a load voltage, V . he device ma% then pass a current densit%, +, and deliver a po#er densit%, @W > V +. Wolf e.plains that the performance of a solar cell permitting multiple photo$induced electronic transitions ma% surpass that of a single p-n junction solar cell #ith a single interband transition ;20<. E% using the statistics of photons in equilibrium #ith the allo#ed photo$induced electronic transitions ;2/<, 'uque and AartPQ #rite the photon flu.es absorbed and emitted b% the solar cell ;"8<, %et onl% for a narro# case, #hich does not include intraband transitions at intermediate levels. In Section ".2.2, the present author treats intraband transitions as #ell as a host of phenomena relevant to the practical operation of these solar cells. hese are& interband electronic transitions at intermediate states ;"8<, non$ma.imal geometric solar concentration ;/<, overlapping absorption coefficients ;3/<, multiple electron$hole pair generation ;113<, and averaged non$radiative recombination ;/"<. In Section ".2.", conclusions are dra#n from the results of detailed$balance calculations. 3."." T&er%odyna%i' Con0ig*ra!ion In this section, the performance measure of the device is defined in terms of the e.ternal e.trinsic thermod%namic variables. Te.t, the photon emission spectrum of the absorbing medium is given implicitl% as a function of the solar cell!s internal intrinsic variables. his is required to finall% establish the internal thermod%namic configuration of the solar cell and to specif% the po#er densit% generated. 1ig*re 13/ Ideal device structure of a solar cell #hose quantum states form an intermediate band of finite #idth. Sho#n are the quasi$:ermi levels, :S, chemical potential differences, S 2, voltage, V , and current densit%, +.

he author considers an engine driven b% particle conversion& photons to electron$hole pairs. he first$la# efficienc%, , is #ritten as the photovoltaic po#er densit% generated b% the converter, @ W , over the energ% flu. impinging on the converter, @Up 6see :igure 1/7 ;"<. hus

#o radiation flo#s pump the converter. he first is a direct source of radiation from the Sun, #hich is assumed a blac, bod% #ith a surface temperature TS, %ielding a photon flu., @$ p,S, and energ% flu., @Up,S. he second is a diffuse source of radiation scattered from the Carth!s atmosphere, #hich is assumed a blac, bod% #ith a surface temperature TC, %ielding a photon flu., @ $p,C, and energ% flu., @Up,C. =onsidering the

dilution factor of solar radiation, DD2.14 108D, and a geometric solar concentration factor, C, #hich ma% range bet#een unit% and 1/D ;/<, the total energ% flu. impinging upon the converter, @ Up, is #ritten #ith the Stefan$Eolt5mann constant, D8.40 103 W/m2/F/D, as he converter sin,s a radiative energ% and particle flu., @ Us and @$s, respectivel%, and a heat flo#, @ Q, #hich tends to elevate the converter!s temperature, T', above that of the ambient. he performance measure, as defined in Cq. 6127, diverges from previous detailed$balance #or, ;1", /, 10<. In these, though the particle flu., @$p, impinging upon the solar cell is given in terms of the dual source, the performance measure onl% considers the energ% flu. from the Sun, @Up,S. 1ig*re 1+/ hermod%namic configuration of a solar cell #ith an intermediate band of quantum states. he engines 6circles7 generate electric po#er b% the net absorption of photons resultant from radiativel% coupled interband electronic processes. Ton$radiative interband recombination 6circles #ith bars7 ultimatel% onl% increase the rate of heat flo#. Sho#n are the heat flo#s, @ Q6),)7, @Q6I,I7, and @Q6=,=7, resultant from the irreversible equilibration of thermali5ed carriers via non$radiative intraband processes in the valence, intermediate, and conduction band, respectivel%.

his distorts the performance measure of the device, resulting in efficiencies

times those obtained using the first$la# efficienc% given here. 9n equilibrium anal%sis ;2/< reveals ;1"< that the equilibrium emission spectrum of an IE absorbing medium, @ n), is the direct sum of four 6more generall% the number of elements in T 7 summands, @ n),6S,27. hese are

#here i is an inde. into the set T , D ;1.0810"/ B 3 s< is +lanc,!s constant, * is the radian frequenc% of the photons, 46S,27 are the absorption coefficients ;"8, 1"<, a is the absorptivit% of the absorber ;1"<, 5) is the number of photons per energ% per second per area hitting the boundar% surface of the absorbing medium ;/<, and f),6S,27 are the Eose$Cinstein distributions that describe the photons! statistics ;"8<, #hich ma% include for multiple electron$hole pair generation ;113<. he po#er densit% delivered to a matched load b% the solar cell is the product of the e.ternal voltage across the device and the charge current densit% generated b% particle conversion as

his is obtained b% generali5ing the ideal photo$chemical and electro$chemical conversions ;"8, 2< to include an averaged ;/"< rate of net non$radiative recombination per volume bet#een the states of the S and 2 bands, he po#er densit% is given in terms of the elementar% charge, q ;1.40101? =<, thic,ness of the solar cell, -, and the components of the photon flu. emitted and absorbed b% the device resultant from photon interactions #ith allo#ed 6S,27 electronic transitions, @ $s,6S,27 and @$p,6S,27, respectivel%. hese are given as

#here @ n),S and @ n),C are the emission spectra of the Sun and Carth, respectivel% ;/<. Cq. 6187 ta,es into account that the IES= is internall% biased so that ;"8< the net rate of charge injected and e.tracted from the IE is in balance as

and also that ;"8< the potential differences sum as follo#s #ith respect to the e.ternal voltage, V , across the solar cell 6see :igure 1"7 :igure 1/ presents the internal thermod%namic configuration of a photovoltaic solar cell #ith an intermediate band of quantum states. It sho#s that a solar cell #ith an intermediate band of quantum states operates as three particle engines #or,ing together. Cach of the internal reservoirs is ascribed a unique chemical potential, S ;/<, #hich is related to the electrochemical potential, :S ;2/<. 3.".3 Re#*l!# and Con'l*#ion# :igure 18 gives the optimi5ed conversion efficiencies at ma.imum po#er, "A+, of IES= as a function of IE #idth. In computing these results, it is assumed that #hen there is the ph%sical possibilit% of both photo$ induced intra$ and interband electronic transitions at intermediate levels that the latter predominate. It is sho#n that 617 detailed$balance approaches that ignore the energ% flo# incident on the converter from the earth, @Up,C, result in efficiencies greater than those obtained from the first$la# efficienc% b% a factor

and 627 as the IE #idth increases, the efficiencies saturate to those of t#o$stac, tandem solar cells ;1"<. :rom these results, the author dra#s three conclusions. 6 i7 he performance of an IES= is limited b% that of a tandem stac, of three electricall%$unconstrained single$junction solar cells. 6 ii7 he assumption that interband transitions predominate over intra$band transitions, #hich is equivalent to ignoring or e.cluding intraband transitions, %ields results inconsistent #ith ph%sical realit%. When the IE #idths approach infinit%, the band structures approach that of a blac, bod%. +lease note, ho#ever, that the efficiencies do not approach those of a blac, bod% H though a blac, bod% ma% generate a heat flo#, it generates no photovoltaic po#er. 6 iii7 (etailed$balance methods that ignore the radiant energ% transfer bet#een the converter and the earth ma% %ield efficiencies larger than those calculated #ith the first$la# efficienc%.

1ig*re 1,/ Optimi5ed efficiencies of an intermediate band solar cell for t#o geometric concentrations, C, and #ith the assumption that interband transitions predominate over intraband transitions. (etailed$balance approaches that ignore the energ% flo# incident on the converter from the earth, @ Up,C, %ield efficiencies greater than or equal to those obtained b% the first$la# efficienc%.

3.3 Solar Cell 0ith an Intermediate /and o 1inite ,idth 3.3.1 In!rod*'!ion he novelt% #ithin Section "." is quantif%ing the impact of both finite intermediate band 6IE7 #idth and spectral selectivit% on the optimi5ed detailed$balance conversion efficiencies of the IE solar cell ;"8< 6IES=7 and its associated band structure. he #or, is sigificant as it sho#s that 6 i7 finite band#idths result in a graceful degradation in the efficienc% and 6 ii7 the most suitable band structures for solar energ% conversion differ significantl% depending on the IE #idth and on the spectral selectivit% of the absorbing medium. he inclusion of finite band#idths is important #hether the IE absorber is formed #ith dopants ;/8< or #ith allo%s ;/3, /?, 81, /3, /?, 81<. =andidate allo%s sho# IE #idths of order 100 me) ;/3, /?, 81< or 1 e) ;/3, /?, 81<. In an earlier #or, ;//<, the author e.aminea IE #idth and sho#a that though thermod%namicall% consistent ;11?<, the results of detailed$balance calculations are ph%sicall% inconsistent #hen photo$induced, intraband transitions are e.cluded or ignored ;//<. he author demonstrates here that the inclusion of intraband transitions %ield full% consistent results. hree classes of absorbers are postulated, each #ith a distinct spectral selectivit%& 6i7 #here intraband absorption coupled to t#o distinct states of the IE is at parit% #ith interband absorption coupled to a state of the IE, 6ii7 #here interband absorption dominates intraband absorption, and 6 iii7 8ice 8e9,a. Ee%ond its use in identif%ing materials for an IES=, resulting from its emphasis on an absorber that permits both intra$ and interband transitions at intermediate levels, Section "." provides a more comprehensive understanding of a general class of opto$electronic devices #ith intermediate states& i.e., up$ ;11/< and do#n$converters ;120<, and multi$band solar cells ;"3<. he IES= is a solar cell #hose efficienc% limit 64".21 ;"8<7 surpasses the Shoc,le%$-ueisser efficienc% limit 6//1 ;8<7. 9s sho#n in :igure 14, the absorber of this cell contains quantum states forming an IE of #idth, WIE. Nesulting from the states of the IE, there are three allo#ed photo$induced, interband electronic transtions ;"8<& bet#een a state in the IE and one in the valence band, 6I,)7, bet#een a state in the conduction band and one in the IE, 6=,I7, and bet#een a state in the conduction band and one in the valence band, 6=,)7. In addition there are photo$induced, intraband electronic transistions bet#een t#o distinct states in the IE, 6I,I7. hus, the set of allo#ed photo$induced electronic transitions of an IES= absorber, T , is defined as T .>16I,I7 , 6I,)7 , 6=,I7 , 6=,)72 ;//<. Nesulting from the three interband transition, the IES= absorbing region is thermod%namicall% equivalent to three constrained particle engines operating in tandem ;//<, so that its efficienc% limit has an upper ceiling at the limit of a tandem stac, of three unconstrained single$junction, single$transition solar cells 64".317 ;3<. he efficienc% of an IES= is obtained b% calculating si. photon flo#s ;"8<& one photon flo# absorbed b% and one photon flo# emitted from the converter resulting from each of the three interband electronic transitions. o describe each photon flo# resulting from 6S,27 transitions, the absorption coefficients are relavent t#ice. :irst, the sum of all the absorption coefficients, DiT 4i 6D *7, appears in the e.pression of the absortivit% ;1"<. Second, the aborption coefficient 46S,27 appears normali5ed in terms of the sum as ;//<

#here i is an inde. into the set T , D is +lanc,!s constant, and * is the radian frequenc% of the photons. 1ig*re 1./ Neduced band structure of an intermediate band solar cell absorber. he bandgaps bet#een bands S and 2, 6S,27, are sho#n as #ell as the intermediate band!s #idth, W IE. 9lso illustrated is the set, T , of photo$induced electronic transtions& 16I,I7 , 6I,)7 , 6=,I7 , 6=,)72.

In the follo#ing sections, the author constructs the three distinct IE absorbers #here each is distinguishing b% its spectral selectivit% and then gives and discusses their ma.imumpo#er solar energ% conversion efficeincies. 3.3." S-e'!ral Sele'!i i!y Oere, the author constructs three classes of IE absorbers, each class distinguished b% its normali5ed absorption coefficients. o do this, attention is first directed t#o a band structure #here the bandgaps 6S,27 spread #ithin the domain of large solar irradiance. Te.t, the interpla% bet#een spectral selectivit% and absorption overlap ;3/< is considered. :inall%, the interpla% bet#een spectral selectivit% and intraband transitions is considered. When 6I,)7, 6=,I7, and 6=,)7 6see :igure 147 are spread #ithin the domain of high solar irradiance, it is ideal if photons join t#o electronic states seperated b% the largest bandgap less than the photons! energies. his is because photon interaction #ith matter is In the follo#ing sections, the author constructs the three distinct IE absorbers #here each is distinguishing b% its spectral selectivit% and then gives and discusses their ma.imumpo#er solar energ% conversion efficeincies. 3.3." S-e'!ral Sele'!i i!y Oere, the author constructs three classes of IE absorbers, each class distinguished b% its normali5ed absorption coefficients. o do this, attention is first directed t#o a band structure #here the bandgaps 6S,27 spread #ithin the domain of large solar irradiance. Te.t, the interpla% bet#een spectral selectivit% and absorption overlap ;3/< is considered. :inall%, the interpla% bet#een spectral selectivit% and intraband transitions is considered. When 6I,)7, 6=,I7, and 6=,)7 6see :igure 147 are spread #ithin the domain of high solar irradiance, it is ideal if photons join t#o electronic states seperated b% the largest bandgap less than the photons! energies. his is because photon interaction #ith matter is associated #ith a rate of irreversible entrop% generation, #hich itself increases monotonicall% #ith ;2/<, #here 6S,27 is the potential difference of the carriers in bands S and 2. he normali5ed absorption coefficients %ield this spectral selectivit% if, beginning at the onset of 6=,I7 transitions, the product of the matri. elements of momentum and joint densit% of states ;121< governing 6=,I7 transitions is several orders of magnitude larger than the corresponding product governing 6I,)7 transitions. Similarl%, beginning at the onset of 6=,)7 transitions, the 6=,)7 product must be orders greater that the corresponding 6=,I7 product. With regard to absorption overlap the author considers a band structure #here 6=,I7 is equal to 6I,)7. In this e.ample, the ideal selective selectivit% for photons in the range is such that there are equal probabilities of photon absorption due to 6I,)7 transitions and 6=,I7 transitions. In this case, the overlap bet#een the 6I,)7 and 6=,I7 absorption, is best if vp > 6=,)7 6I,)7. vp adjusts the I$) characteristics due to 6I,)7 and 6=,I7 e.citations so at the cell!s ma.imum po#er point 6A++7, the constituent engines operate at their individual A++. With regard to the allo#ed intraband transitions, the author considers IE absorbers classified in one of three #a%s. :or the situation #here the IE #idth is larger than the smallest bandgap in the s%stem, the absorbers ma% be distinguished b% the absorption properties for photons #ithin the range he first class of absorber is distinguished b% a parit% of photo$induced, intraband electronic transitions and photo$induced, interband electronic transitions. :or this class, for photons in the specified range, all of the non$5ero absorption coefficients are of equal value. he second class of aborbers is distinguished so that photon e.change #ithin this range is solel% coupled to intraband transitions. hus, in this range, the absorption coefficients 46I,)7, 46=,I7, and 46=,)7 are null. he third is distinguished so that photo$induced electronic transitions are solel% coupled to interband transitions, so that the absorption coefficient 46I,I7 is null #ithin this range. he author, therefore, #rites the ideal normali5ed absorption coefficients as

#here the unit step functions, :, indicate the ideal absorption onsets and offsets for each of the three classes of IE aborbers. he onset and offset of photon e.change due to 6S,27 transitions begins #ith photons #ith energies greater than or equal to 4on 6S,27 and 4off 6S,27 respectivel%. able " gives these values for each class of IE aborber, #here it is uniforml% assumed that 6=,I7 ; 6I,)7. In obtaining these results, a simplif%ing assumption is made& for an% range of photon energies, all non$5ero absorption coefficients #ithin this range are of equal value. he normali5ed absorption coefficients thus ta,e one of the follo#ing values& 0, 1R", 1R2, or 1. he follo#ing section presents and e.plains the results of the detailed$balance anal%sis. Ta$le 3/ his table gives the onsets, of photon e.change due to 6S,27 transitions that lead to optimum ma.imum$po#er efficiencies. he% are given for the three classes of intermediate band solar cell absorbers, such that #hen there is the possibilit% of both photo$induced interband and intraband electronic transitions, the transitions e.ist at parit%, the% are limited to interband electronic transitions, or the% are limited to intraband electronic transitions.

3.3.3 Re#*l!# and 6i#'*##ion :igure 10 presents optimi5ed detailed$balance conversion first$la# efficiencies at ma.imum po#er, "A+ ;//<, of the IES= as a function of the IE #idth. In calculating the efficiencies, the formalism of reference ;//< is used #here& non$radiative recomibination is nullL multiple electron$hole generation is non$e.istantL and, for photons in those ranges that join electronic transtions, the absorptivit% is unit%. 9ll results are calculated for a surface solar temperature of 4000 F, a surface terrestrial temperature of "00 F, and a converter #hose lattice is held at that of the surface terrestrial temperature. :or each value of W IE, the efficienc% at ma.imum po#er is found #ith an optimi5ation routine that treats 6I,)7, 6=,I7, and vp as parameters in the search space. In precisel% computing the photon flo#s, the method of reference ;122< is used. Nesults are given for the three classes of IE aborbers and t#o values of geometric concentration& the ma.imum ph%sicall% reali5able concentration ;8< 6/4,"007 and non$concentrated 617 solar illumination.With respect to the class of IE aborber such that photo$induced interband transitions and intraband transitions e.ist at parit% #henever there is the ph%sical possibilit% of both, :igure 10 sho#s that the optimum detailed$balance efficienc% monotonicl% decreases to 5ero as a function of the IE #idth. 9lthough not visible, the data indicates that for the case of the ma.imum concentration there is a short lived increase in efficienc%, so that the limiting IES= efficienc% 64".2 17 is achieved for a band#idth of 18 me). Ero#n et a-. first note this perceptible increase ;"4<. 9s sho#n in :igure 13, the bandgaps generall% increase #ith the band#idth. :or band#idths greater than Wein!s energ% for a blac,bod% at 4000 F, 6I,)7 maintains the value of WIE so as to minimi5e losses due to non$#or, producing intraband transitions. :igure 1? sho#s that, in general, an absorption overlap, vp, of order me) is associated #ith the ma.imum po#er efficiencies throughout their trajectories. With respect to the class of IE aborber such that photon e.change is limited to interband electronic transitions #henever there is the ph%sical possibilit% of both inter$ and intraband transitions, :igure 10 sho#s a monotonic decrease in the efficienc% as a function of the IE #idth. 9s the #idth of the IE increases, the optimum efficiencies and their associated bandgaps, 6I,)7 and 6=,I7 6see :igure 137, saturate. On saturating, the efficienc% and these associated bandgaps are those of an optimi5ed t#o$junction tandem electricall% assembled in series ;11<. his indicates that as the IE #idth increases, the po#er absorbed due to 6=,)7 electronic e.citations steadil% decreases. Kltimatel%, the photo$

induced 6=,)7 e.citations offer negligible contribution as there are relativel% fe# photons in the solar spectrum #ith such high energies. hat the IES= operates as a t#o$junction solar cell results from the stringent condition that photo$induced electronic transitions are limited to interband transitions and the solar cells current and voltage constraints ;"8, //<. 1ig*re 1;/ Aa.imum po#er efficienc% of intermediate band solar cell as a function of the intermediate band!s #idth. =urves are given for t#o geometrical concentrations factors and for three classes 6see ab. "7 of intermediate band aborbers. he concentrations are the ma.imum ph%sicall% reali5able concentration 6/4,"007 and non$concentrated 617 solar illumination. 'imiting efficienc% of 4".21 occurs #hen W IE is 18 me).

1ig*re 1</ Eandgaps 6I,)7 and 6=,I7 associated #ith efficiencies given in :igure 10. Nesults given for a concentration of 6/4,"007.

1ig*re 1=/ Overlap 6see ab. "7 bet#een 6I,)7 and 6=,I7 absorption. Nesults associated #ith ma.imum po#er efficiencies of :igure 10 for a concentration of 6/4,"007.

hough the detailed$balance method is thermod%namicall% consistent, the results obtained for this class are not ph%sicall% coherent for large band#idths. 9s the band#idth increases a0 ab,:90:<, the electronic band structure appears as that of a blac, bod%. hough a blac, bod% ma% produce a heat flu., no photovoltaic #or, ma% be produced from such aborbers, for all the carriers are in thermod%namic equilibrium. he more the band#idth e.ceeds Wien!s energ% for a blac,bod% at 4000 F, the more ph%sicall% inconsistent are the results. With regards to the class of IE aborber #ith photon e.change limited to intraband electronic transitions #henever there is the ph%sical possibilit% of both inter$ and intraband transitions, :igure 10 sho#s

that the trajectories of the efficiencies follo# similar courses as those of class parit% up until a band#idth of 0./4 e) and 0.48 e), respectivel%, for concentrations of 6 /4,"007 and 617. 9t these band#idths this class offers a relative efficienc% enhancement #ith respect to class parit%. 9 solar cell #ith this class of absorber e.ploits the fact that the absorption onset due to 6I,)7 transitions is limited b% W IE rather than 6I,)7. he upshot is that the internall% biased chemical potential difference, 6I,)7, is no longer limited from above b% 6I,)7, but rather b% WIE. 9dditionall%, 6I,)7 is no longer relevant in calculating the net photon flu. absorbed due to 6I,)7 transitions, so it ma% be decreased if it enhances the performance of the solar cell. :igure 13 sho#s that a performance gain is indeed obtained b% a concomitant reduction of 6=,I7 and 6=,)7, so that the onsets of optical absorption are spaced more evenl% across the range of high solar irradianceL consequentl%, there is an increase in the net photon flu. absorbed due to both 6=,I7 and 6=,)7 transitions. In theor%, the value of 6I,)7 ma% not approach arbitraril% close to 5ero because at some threshold ;12"< the rate of non$radiative, interband transitions induced b% phonon emission ma% no longer be ignored. In such case, the premises of the equilibrium anal%sis ;2/< are violatedL for the carriers in the valence band and IE #ould be brought to thermod%namic equilibrium b% the phonon e.changes. 3.3.+ Con'l*#ion# Section "." quantifies the effect of the intermediate band!s #idth, W IE, and spectral selectivit% on ideali5ed intermediate band solar cells. he author concludes that, irrespective of the geometric concentration factor, resulting from the solar surface temperature of 4000 F, the largest efficiencies result #hen W IE D =6D *W" 4000 F > 328 me)7, #here = is the order of Wein!s energ%, D *W, of a blac,$bod% #ith a surface temperature T+ > 4000 F. When WIE > 328 me), the first$la# efficiencies ma% reach 80.?1 and "".?1 6as compared #ith 4".21 and "4."1 #hen WIE > 07 for full% concentrated and non$concentrated solar ilumination, respectivel%. When WIE D =6D *W7, to achieve high efficiencies at large concentrations, the smallest and ne.t smallest bandgap ought be roughl% 100 me) smaller and 800 me) larger than =6D *W7, respectivel%. :inall%, #hen WIE is greater than the smallest bandgap, photo$induced, intraband transitions are necessar% to present a ph%sicall% consistent model of the solar cell!s operation. 3.4 Conclusions he author begins =hapter " b% e.amining the detailed$balance conversion efficienc% of a solar cell #ith an intermediate band 6IE7 under non$optimal conditions. his e.amination allo#s for t#o blac,bod% sources, intraband and interband photo$induced electronic transitions, overlapping absorption coefficients, multiple electron$hole$pair generation, and nonradiative processes. he author concludes that ignoring or e.cluding intraband transitions ma% %ield results inconsistent #ith ph%sical realit% and that ignoring the radiant energ% transfer bet#een the converter and the earth ma% %ield efficiencies greater than those calculated #ith the first$la# efficienc%. he author continues =hapter " b% quantif%ing the effect of the intermediate band!s #idth and spectral selectivit% on ideali5ed intermediate band solar cells. Irrespective of the geometric concentration factor and resulting from the solar surface temperature, the author concludes that the largest efficiencies result #hen the intermediate band!s #idth is roughl% equal to or less than 328 me)& Wein!s energ% of a blac,$bod% #ith a surface temperature of 4000 F. he author further concludes that #hen the intermediate band!s #idth is appro.imatel% less than or equal to 328 me), in order to achieve high efficiencies at large concentrations, the smallest and ne.t smallest bandgap ought to be roughl% 100 me) smaller and /00$800 me) larger than 328 me), respectivel%L and that #hen the intermediate band!s #idth is greater than the smallest bandgap, photoinduced, intraband transitions need to be included for ph%sical consistenc%. he results of this =hapter " are used in =hapter / to calculate the iso$efficienc% contour plot of an intermediate band solar cell. CHAPTER IV - NANOSTR@CT@RE6 A7SOR7ERS 1OR 2@LTIPLE TRANSITION SOLAR CELLS 4.1 Introduction his chapter identifies absorbers for multiple transition solar cells that are implemented #ith nanostructured heterojunctions 6e.g. quantum #ell solar cells #ith quasi$:ermi level variations and quantum dot intermediate band solar cells7. In the radiative limit the solar cells implemented #ith these absorbers are capable of achieving a conversion efficienc% ;801 #ith a geometric solar concentration of at least 1000. he technical approach enumerates a set of quantitative design rules and applies the rules to the technologicall% important III$) semiconductors and their ternar% allo%s. 9 novel design rule mandates a negligible valence band discontinuit% bet#een the barrier material and confined materials. 9nother ,e% design rule stipulates that the substrate have a lattice constant in bet#een that of the barrier material and that of the quantum confined material, #hich permits strain compensation. Strain compensation allo#s a large number of quantum dot la%ers to be incorporated into the solar cell because each la%er is freer of defects. :our candidate materials s%stems 6confinedRbarrierRsubstrate7 are identified& In+0.38Sb0.18R*a9sRIn+, In9s0./0+0.40R*a9sRIn+, In9sR*a9s0.33Sb0.12RIn+, and In+R*a9s0.00+0."0R*a9s. Nesulting from the design features, the candidate s%stems ma% also find use in other opto$electronic applications. he remainder of this chapter is organi5ed as follo#s. Section /.2 presents detailed bac,ground information. Section /." enumerates and details the quantitative design rules, Section /./ e.plains ho# these rules are applied to the technologicall% III$) material s%stems. Section /.8 follo#s #ith concluding remar,s.

4.2 /ac2ground +h%sical phenomena that ma% increase the efficienc% of a single junction solar cell above the Shoc,le%$ -ueisser limit ;8< include proposals such as multiple transitions ;20<, multiple electron$hole pair generation ;"0<, and hot carriers ;""<. Identif%ing materials that ma% be used to implement these phenomena is of significant interest. :or e.ample, multiple electron$hole pair generation is demonstrated in several materials ;12/, 128<. Several approaches are proposed to implement multiple transition solar cells, all of #hich require the introduction of valid quantum states deep into the previousl% forbidden bandgap of a host semiconductor ;20<. #o of these, #hich rel% on nanostructured heterojunctions, are the quantum #ell solar cell #ith quasi$ :ermi level variations ;84< and the quantum dot 6-(7 intermediate band solar cell 6IES=7 ;8?<. It is important to note that both of these approaches ma% be sho#n to be thermod%namicall% consistent ;11?<. Kntil no#, material s%stems that are most suitable to implement these t#o solar cells are not %et identified. his chapter identifies absorbers for solar cells that utili5e nanostructured heterojunctions to generate multiple transitions ;84, 8?<, and that are theori5ed ;84, 8?< and e.perimentall% inferred ;100, 42< to maintain more than one quasi$:ermi level separation. Specificall%, the material s%stems identified here ma% lead to devices capable, in principle, of conversion efficiencies ;801 #ith a geometric solar concentration of at least 1000. he technical approach ta,en here identifies candidate material s%stems b% enumerating quantitative design rules and b% appl%ing these design rules to the technologicall% important III$) semiconductors and their ternar% allo%s. hough the remainder of this chapter gives pronounced emphasis to the -( IES=, the chapter ma% find use in developing related photovoltaic technologies and in other opto$electronic communities. In the -( IES= ;8?, 40, 41<, the intermediate states #ithin the formerl% forbidden bandgap are introduced b% the three$dimensional confining potential created b% the -( heterojunctions. he states introduced b% the -( heterojunctions ma% either form a band of e.tended states, #hich #ould %ield beneficial transport properties, or a collection of locali5ed states as sho#n in :igure 20. he material s%stems identified here #ould be appropriate regardless of #hether a band of e.tended states is formed or not. With respect to the former case, a band of e.tended states #ith #ell$defined band edges and band #idth requires some measure of order ;/8< 6for a general discussion, see reference ;124< and references therein7. 9llo#ing that the required order e.ists, then one ma% consider a -( cr%stal #ith miniband formation resultant from coupling bet#een -( ;120< and ne.t consider the design constraints of a -( IES= ;123<. With respect to the latter, a collection of locali5ed states ma% result if there #ould e.ists non$uniformities in the -( matri. or if the inter$-( distance is large. If the locali5ed intermediate states #ithin the heterojunctions! confining potentials e.ist energeticall% close to one another, then the% #ill create an energetic interval of allo#ed intermediate states, WIE 6see :igure 207. With respect to either of the t#o cases, assuming that all the carriers in the intermediate states are in electro$chemical equilibrium, the population of carriers at intermediate states ma% be described b% a single quasi$:ermi level, :I. If :I is energeticall% close to the intermediate states, #hich ma% require the inclusion of dopants ;40, 123, 12?<, then there is strong li,elihood that absorbed photons ma% induce electronic transitions bet#een the intermediate states and the conduction and valence band continua, respectivel%. +revious #or, on the -( IES= revolves around the In9sR*a9s 6confinedRbarrier7 ;/1, 42, 4", 4/< and In*a9sR*a9s ;48< material s%stems, both gro#n on *a9s substrates. hese choices derive from the s%stems being relativel% #ell understood. In addition, the bandgap of a *a9s barrier is near to the optimum conduction$to$valence bandgap associated #ith the upper limiting efficienc% of an IES= ;"8<. hese materials s%stems have t#o characteristics limiting their usage for development of an -( IES=& the% have valence band discontinuities and the% accumulate strain. he first characteristic 6t%pe$I heterojunction7 enables the luminescent spectra of -( IES= samples ;/1, 42< to illustrate narro#l% separated and overlapping pea,s, rather than the luminescent signature of an intermediate band material. he most rudimentar% signature is the appearance of three ;3"< 6or four ;?3<7 strong luminescence pea,s separated across a #ide energ% rangeL each of the three pea,s corresponds to one of three allo#ed interband electronic transitions 6#hereas the fourth pea, corresponds to an intraband transition ;?3<7. he second characteristic 6strain accumulation7 causes the open$circuit voltage to degrade as the number of quantum$ dot multi$la%ers increases ;48<. his is a problem to the design of a high$efficienc% -( IES=, for a large number of multi$la%ers is essential for a high absorptivit% of sub$bandgap photons ;112< $ the high absorptivit% of sub$bandgap photons ma% be vie#ed e.perimentall% b% an increase in their e.ternal quantum efficiencies #ith an increase in the number of -( la%ers ;48<. his chapter!s design rules identif% candidate material s%stems that ma% overcome these t#o characteristics. 1ig*re "?/ Cnergetic structure of an arra% of non$uniform quantum dot heterojunctions that #ould be favorable for a multiple transition solar cell!s absorbing medium. Oere, the valence band discontinuit% is negligible, #hich precludes the e.istence of hole states in the formerl% forbidden bandgap. Eound intermediate states #ithin the heterojunctions! confining potentials, #hich are formed from the conduction band discontinuities, W=E, e.ist energeticall% close to one another. Inhomogeneities 6 e.g non$uniform dot si5es7 broaden the interval of allo#ed intermediate states 6gra% hue7 and create an energetic interval of allo#ed intermediate states, WIE. he minimum energetic distances bet#een the intermediate states and the conduction band continuum and valence band continuum are =I and I), respectivel%. 9ssuming that all

the carriers in the intermediate states are in electro$chemical equilibrium, their occupanc% statistics ma% be described b% a single quasi$:ermi level, :I.

he candidate material s%stems identified here %ield heterojunctions at the transition bet#een t%pe$I and t%pe$II heterojunctions and the potential for strain compensation. Oeterojuntions at the transition bet#een t%pe$I and t%pe$II e.clusivel% permit bound states due either to hole6s7 or to electron6s7, but not both. his choice is meritorious for several reasons. :irst, it abates the difficult% in interpreting data from inter$band, optical e.perimental methods that e.ists if both holes and electrons are involved ;1"0<. Second, it ma% limit the e.tension of the band edge into the previousl% forbidden bandgap ;41<, #hich #ould reduce the open$ circuit voltage #hen compared to a control cell #ithout -( ;1"1<. hird, it ma% limit the accumulation of e.cess miniband formation ;1"1<. :urther, material s%stems that compensate strain accumulation permit the reali5ation of longer, opticall%$active, multi$la%ered -( structures fabricated #ithout generating ;1"2, 1"", 1"/, 1"8, 1"4< and propagating large number of defects, #hich decrease the open$circuit voltage. he literature presents several techniques to introduce strain compensating epita.ial la%ers ;1"0, 1"3, 1"?<, #hich permit fabricating opticall%$active -( structures comprised of 100 or more -( multila%ers ;1/0, 1/1<. Ee%ond the quantum #ell solar cell #ith quasi$:ermi level variations ;84< and the -( IES= ;8?<, the design features and candidate material s%stems identified here ma% find use in developing related photovoltaic technologies and other opto$electronic devices. In addition, the candidate s%stems are of import to the fundamental ph%sical stud% of heterojunctions. Within the photovoltaic field, the operating principles of several devices 6i.e. multi$band solar cells ;"3<L and up$;1/2< and do#n$converters;120<7 all rel% on absorbers admitting multiple photo$induced electronic transitions. With respect to the ph%sical import, t%pe$II heterojunctions are theoreticall% predicted ;1/"< and e.perimentall% verified ;1//< as having relativel% long radiative lifetimes resulting from the spatial division of confined electrons and holes. In addition, the nature of electronic conduction is sho#n to differ in t%pe$I and t%pe$II heterojunctions ;1/8<. herefore, the stud% of s%stems at the transition bet#een t%pe$I and t%pe$II s%stems #arrants attention and ma% eventuall% lead to novel devices and device applications. 4.3 -esign &ules Seven quantitative design rules are specified to identif% candidate material s%stems for nanostructured absorbers that are suitable for solar cells #ith multiple transitions. he first and second design rules are discussed e.tensivel% in the introductor% section. he third and fourth design rules pertain to the placement of the intermediate states to permit, in principle, ; 801 conversion under a solar concentration of at least 1000 Suns. he remaining rules assist in identif%ing candidates that offer an advantage in terms of minimi5ing the technological comple.it% of fabrication and characteri5ation. Negligi$le alen'e $and di#'on!in*i!y he first design rule specifies that the upper )E edge of the confined material must be continuous #ith the upper )E edge of the barrier material 6see :igure 207. he absence of a valence band discontinuit% eliminates the possibilit% of introducing intermediate states resulting from quantum confined holes. here are t#o reasons #h% the )E discontinuit% is set to a negligible value rather than the =E discontinuit%. :irst, in the technologicall% reali5able interval of -( radii, for even a small )E discontinuit%, man% hole states appearL ho#ever fe#er electron states appear #ith a similar magnitude =E discontinuit%. his result stems from the fact that the technologicall% important III$) semiconductors have larger hole effective masses than electron effective masses ;1/4<. hus, #ithin technologicall% reali5able -( radii, it is possible to provide a single electron state #ithin the confining potential, #hereas, at those same

radii, man% hole states #ould e.ist. Second, in general, for the technologicall% important III$) semiconductors, the hole mobilities are less than the electron mobilities. In an actual device, the higher the mobilit% of the carriers is, the higher the diffusion length is for a given carrier lifetime. hus, the mobilit%, through the diffusion length, enhances the collection of generated electron$hole pairs, and hence the performance of the device. S*$#!ra!eA# la!!i'e 'on#!an! $e!>een !&o#e o0 !&e 'on0ined %a!erial and !&e $arrier %a!erial he second design rule specifies inequalities relating the lattice constants of the confined, barrier, and substrate materials. Specificall%, the lattice constant of the substrate must be bet#een the lattice constants of the barrier and the confined materials. Aaterial s%stems compl%ing #ith this rule ma% allo# the incorporation of tensile strain to compensate for compressive strain accumulated during the gro#th of the multi$la%er quantum #ell ;?", 1/0< and -( structures ;1"0<. Strain compensation reduces the densit% of defects in multi$ la%er -( structures ;1/3<. hus, strain compensation is relevant to the number of -( la%ers, #hich has a direct impact upon the absorptivit% of sub$bandgap photons ;112<, that can be incorporated into multi$la%er structures before rela.ation occurs. :urther, the reduced densit% of defects in multi$la%er -( structures ;1/3< abates large open$circuit voltage losses in e.perimental samples ;/1, 48<. 7arrierA# $andga- $e!>een 1.", eV and 3.13 eV he third design rule specifies the required interval of the conduction$to$valence bandgap, =). In a previous e.amination of the -( IES= ;8?<, a bandgap of 1.?8 e) is considered necessar% for candidate barrier materials. his consideration is derived from detailed balance calculations ;"8< #here the solar irradiance is concentrated at /4 000, #hich is the ph%sical limit of geometrical concentration 6i.e. the reciprocal of the geometrical dilution factor ;8<7. he bandgap of 1.?8 e) is associated #ith the ape. of the efficienc% curve found there. Oere, the present author considers a more practical geometrical concentration factor of 1000. In addition, unli,e previous calculations ;"8<, #hen obtaining the ma.imum$po#er detailed balance efficiencies, the author includes the follo#ing as parameters in the search space& the energetic #idth of intermediate states ;"4<, and the spectral e.tent of absorption overlap ;3/<. Similar to previous calculations ;"8<, all calculations here are performed in the limit #here electronic transitions are coupled to radiative interactions #ith the absorber. o #hat e.tent this is actuall% the case ma% be determined b% future e.perimental investigation. :igure 21 sho#s the upper theoretical ma.imum po#er iso$efficienc% contour plot of an IES= under a geometric concentration of 1000. 9llo#ing that the energetic #idths of intermediate states corresponding to these efficiencies are negligible $ #hich is the case in the high efficienc% regime 6 ; 8017 $ inspection of :igure 21 reveals that conduction$to$valence bandgap must be bet#een 1.28 e) and ".1" e). Eefore moving on to the ne.t design rule, the author points out an advantage of computing a t#o$dimensional iso$efficienc% contour plot as compared to the one$ dimensional plot previousl% presented in the literature ;"8<. his advantage stems from the fact that the complete set of ordered pairs 6I), =I7 that result in efficiencies greater than 801 is visible. he upshot is a larger search space #ith #hich to appl% the design rules, and hence a greater li,elihood of obtain suitable material s%stems. 1ig*re "1/ Aa.imum po#er iso$efficienc% contour plot of an intermediate band solar cell under a geometric solar concentration of 1000 6sho#n here are the 801 and 881 contours7 as a function of the energetic gaps, I) and =I 6see :igure 207. =ontours obtained using the rapid and precise computation method of Nef. ;122<

Cond*'!ion $and di#'on!in*i!y a''o%%oda!e# #!a!e# a##o'ia!ed >i!& &ig& e00i'ien'ie# he fourth design rule specifies the minimum value of the conduction band discontinuit%, W=E, #hich defines the confining potential 6see :igure 207. his rule demands that the confining potential!s depth accommodates positioning the intermediate states to enable high$efficienc% solar energ% conversion. he minimum quantitative value for the conduction band discontinuit% depends upon the conduction$to$valence bandgap. hese values are obtainable from the data comprising the iso$efficienc% contour plot 6see :igure 217. 6ire'! $andga-# he fifth design rule demands that both the confined material and barrier material must be direct bandgap materials. :or high$efficienc% approaches, especiall% #here the height of the absorbing medium ma% be limited b% e.isting fabrication techniques, it is essential to have the largest absorptivit% possible. :or this reason, indirect bandgap materials, #hich require phonon e.change for light absorption, are e.cluded because their absorption coefficients are lo#er than those of direct bandgap materials. :urther, the use of an indirect bandgap barrier requires thic,er devices to significantl% trap light and a longer duration of epita.ial gro#th, #hich ma% increase the opportunit% for defect formation. Con0ined %a!erial or $arrier %a!erial i# a $inary #e%i'ond*'!or he si.th design rule simplifies the technological comple.it% of the multi$stac, fabrication process. It is indubitabl% simpler to epita.iall% fabricate a binar% semiconductor than a ternar% or quaternar% semiconductor. S*$#!ra!e i# 'o%%er'ially a aila$le he seventh design rule stipulates that the substrate must be commerciall% available. In general, the cr%stalline qualit% of devices gro#n b% molecular beam epita.% is much better if the substrate is commerciall% available. In addition, the e.perimental repeatabilit% of measurements is more li,el% if the substrate is subject to industrial process control. 9t the time of #riting, the follo#ing materials are commerciall% available& In+, *a9s, and In9s. he design rules offer quantitative criteria to identif% material s%stem suitable for multiple transition solar cells implemented #ith nanostructures. hese rules ma% be applied to a set of sufficientl% characteri5ed materials, as is done belo#. 4.4 !""lication to the III-3 Semiconductors and their %ernary !lloys he design rules are applied to the technologicall% important III$) 5inc$blend and #urt5ite compound semiconductors and their ternar% allo%s. Specificall%, the follo#ing compounds and their ternar% allo%s are considered for an% of the three components 6 i.e., confined, barrier, or substrate7 of the material s%stem& *a9s, *aSb, *a+, *aT, 9l9s, 9lSb, 9l+, 9lT, In9s, InSb, In+, and InT. he follo#ing parameters for all these binaries and their ternar% allo%s are required to identif% material s%stems that conform to the design rules& alc, the lattice constantL EX g , the band in the X valle%L E> g , the bandgap in the > valle%L E( g , the bandgap in the ( valle%L )EO, the valence band offsetL and, #hen available, 4 6X7, ? 6X7, 4 6>7, ? 6>7, 4 6(7, and ? 6(7, the )arshni parameters of the X, >, and ( bandgaps, respectivel%. he revie# of )urgaftman et. a-. is the sole source of information used b% the author in modeling these material properties ;1/4<. he design rules are applied to the technologicall% important III$) semiconductors at t#o distinct temperatures. hese temperatures are "00 F, the terrestrial operating temperature of a solar cell, and / F, a temperature at #hich a significant amount of research and development of these t%pes of material s%stems is li,el% to be performed ;3", ?3<. 9t both temperatures onl% the follo#ing material s%stems are identified& In+0.38Sb0.18R*a9sRIn+, In9s0./0+0.40R*a9sRIn+, In9s0./0+0.40R*a9sRIn+, In9sR*a9s0.33Sb0.12RIn+, and In+R *a9s0.00+0."0R*a9s. able / gives the conduction$to$valence bandgaps and conduction band discontinuities of these material s%stems at both "00 F and / F. It need be noted that at "00 F the band alignments of both the In9sR*a9sSbRIn+ and In+R*a9sR*a9s material s%stems ma% %ield, in principle, a conversion efficienc% bet#een /31 and 801. he% are included here to provide material s%stems #hose quantum confined regions are composed of a binar% semiconductor. Tegligible valence band discontinuities are e.perimentall% inferred for t#o of these four s%stems& In9s+R*a9s ;1/?, 180<, and In9sR*a9sSb ;181, 182<. 9s regards the -( IES=, In9sR*a9sSb structures offer the most promise. here are t#o reasons for this. :irst, antimonide acts as surfactant ;18", 18/<, #hich inhibits the generation of interfacial defects and thus leads to superior optical activit% ;188<. Second, it is indubitabl% less comple. to constitute binar% -( #ithin a ternar% barrier than 8ice 8e9,a. he follo#ing concludes these findings. Ta$le +/ Aaterial s%stems #ith #hich to implement nanostructured absorbers for multiple transition solar cells. *iven for each s%stem is the confined material, the barrier material, and the optimum ma.imum$po#er conversion efficienc%, opt, at "00 F and 1000 concentration. 9dditionall% given are the conduction$to$ valence bandgap, =), and the conduction band discontinuit%, W=E, at both "00 F and / F 6"00 FR/ F7. he s%stems given in the first three ro#s require In+ substrates, #hereas that of the fourth ro# requires a *a9s substrate.

4.# Conclusions :our candidate material s%stems are identified for further development of multiple transition solar cells implemented #ith nanostructures. he materials s%stems provide heterojunctions at the transition bet#een t%pe$I and t%pe$II heterojunctions, resulting from their negligible valence band discontinuities, and offer the possibilit% for strain compensation during the gro#th of multi$la%er quantum dot structures. Nesultant from several advantageous properties, the In9sR*a9sSb is particularl% suited to further investigation of a quantum dot intermediate band solar cell. 9 ,e% tool used to identif% these material s%stems is a ma.imum po#er iso$ efficienc% contour plot of an intermediate band solar cell under a geometric concentration of 1000. CHAPTER V - A7SORPTION AN6 E2ISSION 7ASE6 ON PARA7OLIC 7AN6S #.1 Introduction In this chapter the author details the absorption and emission of three$transition absorbers based on parabolic$band appro.imations. In Section 8.2, the author models the absorption coefficients of an intermediate$band absorbing medium. In addition, equilibrium absorption coefficients are presented for several absorbers, each distinguished b% their energ%#avevector dispersion and equilibrium temperature. Several simplif%ing assumptions are made including that the energ%$#avevector dispersions are parabolic. he model requires the absolute locations of three quasi$:ermi levels. his is made possible b% using t#o balance equations. One of these, a charge$neutralit% condition, requires the numerical computation of the carrier statistics in each band of the absorbing medium. he use of :ermi$(irac integrals ma,e this possible. =onclusions are dra#n regarding the completeness of absorption, the e.istence of absorption overlap, and the temperature$dependence of the absorption. In Section 8.", the author presents theoretical photoluminescent spectra of absorbing media, each #ith valid quantum states forming an intermediate band. he novelt% is illustrating the spectroscopic consequences of multi$gap absorbers #hose quantum states form parabolic bands. +hotoluminescent spectroscop% allo#s the band$edges of multiple transition solar cells to be investigated #ithout the additional complication of fabricating electrical contacts. Nesults are presented for absorbers #ith the same bandgaps, %et the% each have distinct absorption characteristics, temperatures, and lengths. he author dra#s t#o conclusions. :irst, the photoluminescent intensit% of an intermediate band absorber ma% be appreciable #ithin four distinct and #ell$separated spectral bands. Second, the full #idth at half ma.imum of the spectral band in the infrared regime appro.imates the #idth of the intermediate band. #.2 !(sor"tion Coe icients o under *ara(olic-/and !""ro)imations ,.".1 In!rod*'!ion In this section the author models the absorption coefficients of intermediate$band ;82< 6IE7 absorbing media. Such media ma% permit multiple photo$induced electronic transitions ;20<. he literature offers several candidate material s%stems to implement such media ;/4, /3, 03, 02, 0", 8?, 40, /1, 44<. hough the% differ on a case$b%$case basis, the electronic structures of the candidate materials s%stems have similarities. Oere, the technical approach is to model the gross electronic features #ith parabolic bands and to consider the absorption resulting from momentum$conserving photo$induced electronic transitions. he absorption coefficients are necessar% to determine the radiative flo#s pumped into and sun, out of such media ;//<, and hence are pertinent to the performance of a variet% of potential applications. In particular, Section 8.2 addresses t#o open questions in the science of solar energ% conversion and distinguishes the absorption at distinct equilibrium temperatures. Ne%nolds and =5%5a, postulate an absorbing medium #ith a band bet#een the conduction band 6=E7 and valence band 6)E7 as a mechanism for photovoltaic and photoconductive effects in cr%stals ;82<. he reduced band diagram of such a medium is illustrated in :igure 22. Oere, the IE has #ell$defined band edges and band #idth, #hich ma% require some measure of order ;/8< 6for a general discussion, see ;124< and references therein7. Shoc,le% and Nead ;/"< e.plain that the occupanc% of the conduction, intermediate, and valence states are described b% distinct quasi$:ermi levels. Oere the author labels these as :,=', :,IO or :,I', and :,)O, respectivel%. Nesulting from the e.istence of the intermediate quantum states, multiple photo$induced transitions ma% be possible #ithin the medium ;20<. +hoto$induced electronic transitions are possible bet#een the states of the IE and the states of =E and )E states, respectivel%, as #ell as bet#een states of the =E and )E. In addition, resulting from the possible e.istence of occupied and unoccupied states ;124<, photo$induced intraband electronic transitions are li,el% bet#een t#o distinct states in the IE ;//<. Several approaches are given to reali5e an absorber #ith a band of intermediate quantum states. hese include III$) semiconductor allo%s #ith transitional metal substitution ;/4<, highl% mismatched allo%s ;/3, 03<, II$)I semiconductors allo%s #ith transitional metal substitution ;02<, transition metal doped chalcop%rite semiconductors ;0"<, and quantum dots cr%stals ;8?, 40, /1, 44<. @b initi

theoretical surve%s of semiconductor allo%s using periodic densit% functional theor% ;/4, 184, 02, 0"<, and a band anticrossing model of the o.ide semiconductor allo%s ;/3<, both indicate the e.istence of an IE of quantum statesL #hereas Fronig$+enne% solutions of quantum dot cr%stals ;120< indicate the possibilit% of one or more minibands. he energ%$#avevector dispersion curves of the intermediate states, var% on a case$ b%$case basis, but the% have in common clearl% defined energetic band #idths and band edges. he energetic #idth of the minibands formed b% the quantum dot cr%stals ma% be up to the order of tens of me) ;120<, depending on the inter$dot spacing. he energetic #idths of the IEs of semiconductor allo%s range from the order of hundreds of me) ;/3, 184, 02, 0"< to the order of 1 e) ;/4<. he technical approach ta,en here is to treat the intermediate quantum states as a continuum of states. Similar to the pioneering #or, on inter$band absorption of semiconductors and insulators ;121, 180, 183, 18?<, the present author appro.imates the $A dispersion of the bands as parabolic functions. he author uses these appro.imations #ith cogni5ance that these are less and less realistic proceeding further from the band edges. :urther, the approach utili5es effective mass parameters to quantif% the concavit% of the $A curves. he author notes that the applicabilit% of the effective mass appro.imation to semiconductor allo%s #ith deep quantum states ma% be limited to those #hose deep states result from isocoric substitutions ;140<. Similar to the $A dispersion given else#here ;141<, the present authors! approach allo#s direct transitions at intermediate levels onl% #ithin a #ell$defined and continuous interval of #avevectors. he ma.imum #avevector ma% be related to the effective Eohr radius ;141, 124< and the IE #idth ma% be related to the concentration of atoms contributing to the intermediate states ;/8<. he technical approach here contrasts #ith previous models of quantum dot absorption ;142, 14", 14/< and also #ith previous absorption models of impurit% absorption ;141<. In those, the absorption coefficients are given for discrete intermediate levels, rather than a band of intermediate quantum states. 9n additional important contrast is that the model here is unique in that it allo#s for the calculation of the absorption coefficients far from equilibrium. he approach here provides insight into the gross features of the absorption in IE absorbing mediaL more detailed treatments of the absorption characteristics of such absorbers ma% be determined on a case$b%$case basis b% fundamental absorption studies ;184<. 1ig*re ""/ Neduced band diagram of an intermediate$band absorbing medium. Clectronic levels are confined to three electricall% isolated band continua. Sho#n are the quasi$:ermi levels, :,S, and allo#ed photo$induced electronic transition 6three interband and one intraband7.

he normali5ed absorption coefficients and the cumulative absorption coefficient 6via the absorptivit% ;1"<7 determine ho# incident radiative flo#s are pumped into an IE absorber ;//<. 9dditionall%, the% are e.plicitl% related to the emission spectrum of an IE absorber, #hich determines the radiative flo#s sun, b% the IE absorber ;//<. he absorption coefficients are thus pertinent to the performance of a host of devices that ma% emplo% such absorbers. hese applications include up$ ;148< and do#n$converters ;118<, multi$transition solar cells ;20, "8, "4<, unstac,ed multi$color light emitting diodes ;114< and unstac,ed multi$color photo$ detectors ;144, 140, 143, 110<. he remainder of Section 8.2 is organi5ed as follo#s. In Section 8.2.2 the simplif%ing assumptions of the approach are made e.plicit. Te.t, in Section 8.2." the absorption coefficients are #ritten e.plicitl% based on these assumptions. Te.t, in Section 8.2./ the approach is emplo%ed to illustrate several salient features of the equilibrium absorption coefficients. Oere, the author addresses t#o open questions in the science of solar energ% conversion. he first is determining to #hat e.tent the concentration of intermediate quantum states adjusts the absorption characteristic so that photons #ith energies greater than the smallest bandgap are full% absorbed ;20<. he second is determining to #hat e.tent the intermediate quantum states produce absorption overlaps ;3/<, #hich is directl% related to the normali5ed absorption coefficients;//<. Te.t, in Section 8.2.8 conclusions are offered. ,."." Si%-li0ying A##*%-!ion# he appro.imation of the absorption coefficients is premised upon several simplif%ing assumptions regarding the absorbing medium. :irst, it is assumed that the HA dispersions ma% be defined as parabolic #ith respect to the #avevector and further that the HA dispersion of the IE is continuous #ith respect to the energ% levels comprising the IE. Second, it is assumed that the bandgaps bet#een the bands are direct 6 i.e., the onsets of all inter$band optical transitions occur at a single #avevector7. hird, it is assumed that the matri. elements of momentum ma% be given b% the electric dipole appro.imation 6see for e.ample the reference here ;14?<7

#ith the further simplification that the electric dipole matri. elements are constant #ith respect to the #avevector. :ourth, it is assumed that momentum$conserving electronic transitions 6direct transitions7 are allo#ed and further that the% predominate over indirect transitions, so that indirect absorption ma% be ignored. he follo#ing section presents the formalism of calculating the absorption coefficients based on these simplif%ing assumptions. ,.".3 1or%ali#% his section is divided into three subsections. Subsection 8.2.".1 illustrates the energ%#avevector dispersion curves of the model, #ith all important features labeled and defined. Subsection 8.2.".2 quantifies the absorption coefficients. here it is sho#n that calculating the absorption coefficients requires the absolute locations of the quasi$:ermi levels. Subsection = provides a method to determine the absolute locations of the quasi$:ermi levels. #.2.3.1 -is"ersion Curves Eased on the first t#o assumptions, the resulting HA dispersion model of an IE absorber is illustrated graphicall% in :igure 2". he energ% versus #ave$vector dispersion is given b% four curves& the conduction and valence bands are each given b% a single parabolic function, #hile the IE is given as t#o piece#ise$ continuous parabolic functions. he =E edge, ='L the )E edge, )OL and the upper and lo#er IE edge, respectivel% IO and I', are labeled. he reader ma% note b% inspection that the absorber is uniforml% a directbandgap materialL thus, all the bandgaps are defined at an identical #avevector, namel%, A0. he bandgaps are defined as 9dditionall% defined at A0 are the energetic differences bet#een the =E and the lo#er intermediate subbandL the upper intermediate subband and the valence bandL and the upper and the lo#er intermediate subbands, #hich are , respectivel%. he concavit% of the =E, the upper and the lo#er intermediate subbands, and the valence band dispersions are given b% their respective effective masses& <=', <IO, <I', and <)O. hat the HA dispersion of the IE is continuous, the subbands comprising the IE meet at a specific #avevector. his #avevector, Ama., and the absolute energetic position of the intermediate states there, Ama. , ma% be solved algebraicall% ;100<. he results are

#here is +lanc,!s constant. 9t Ama. the energetic distances bet#een the intermediate levels and the conduction and valence bands, respectivel%, ma% also be solved algebraicall% ;100<. he results are

respectivel%. 9s constructed, photo$induced electronic transitions at intermediate levels are impermissible be%ond Ama.. he effects of this are seen clearl% in the illustrations of the equilibrium absorption coefficients found in section 8.2./.". Inspection of :igure 2" indicates that the simplif%ing assumptions must %ield a total of si. possible momentum$conserving photo$induced electronic transitions. he set of allo#ed momentum$ conserving transitions, T , is thus given as T > 16=',)O7, 6=',IO7, 6I',)O7, 6IO,I'7, 6=',I'7, 6IO,)O7 2. he elements of set T refer to electronic transitions bet#een the =E and valence bandL =E and upper subband of the IEL upper subband of the IE and valence bandL upper subband of the IE and lo#er subband of the IEL =E and lo#er subband of the IEL and upper subband of the IE and valence band, respectivel%. 1ig*re "3/ Cnerg%$#avevector 6$A7 dispersion diagram of a direct$gap intermediate$band absorbing medium under parabolic appro.imations. he intermediate band is comprised of t#o subbands.

he follo#ing subsection utili5es the dispersion curves and renders e.pressions for the absorption coefficients of the absorbing medium. #.2.3.2 !(sor"tion Coe icients he approach ta,en here derives the absorption coefficients for each of the momentumconserving electronic transitions in a manner similar to the derivation for a direct bandgap semiconductor near its absorption edge ;121, 180, 183, 18?<. In general, modeling the absorption coefficients of semiconductors #ith parabolic$band appro.imations is tenuous a#a% from the band edgesL nonetheless, the gross features manifest. Eased on the four simplif%ing assumption, the absorption coefficients, 46S,276D*7, of a simplified IE absorber are modeled in 9ppendi. =. o utili5e this model, certain parameters, #hich are listed in able 8, are required. hese parameters include the absolute energetic positions of the quasi$:ermi levels, #hich ma% be obtained #ith the method detailed in 9ppendi. =. Oaving outlined the formalism required to model the absorption coefficients of an IE absorbing medium, attention is no# turned to an e.plicative e.ample of its usage. Ta$le ,/ Ainimum set of scalar variables required to appro.imate the absorption coefficients of an intermediate$band absorbing medium. hese variables ma% be obtained from empirical data, theoretical considerations, or semi$empirical models.

,.".+ E4-li'a!i e E4a%-le In this section, e.plicative e.amples are offered to illustrate and e.plain several salient features ;101< of the absorption characteristic of IE absorbers. Oere the author addresses t#o open questions stated in the introduction, as #ell as distinguish the absorption characteristics at distinct temperatures. In Section 8.2./.1, the model parameters are given and justified. In Section 8.2./.2, the equilibrium carrier statistics of this s%stem are e.plained. :inall%, in Section 8.2./.", the equilibrium absorption coefficients are presented and e.plained. #.2.4.1 4odel *arameters he model parameters of the e.amples are given in able 4. +arameters relating to the =E and )E are those relating to *a9s0.33Sb0.12, #hich is the host semiconductor of an IE absorbing medium identified for high$ efficienc% solar energ% conversion ;44<. hese are calculated at room temperature from the band parameters of III$) semiconductors and their ternar% allo%s ;1/4<. he location of the IE is centered at the value corresponding to high$efficienc% solar energ% conversion ;44<. he #idth of the IE is t%pical of several of the identified IE absorbing medium ;/3, 184, 02, 0"<. he matri. elements are given in terms of the Fane energ%, EB , #hich ta,es a value #ithin the accepted range of those for various semiconductors ;102<. In addition, it

is assumed that onl% 2R/ 6each photoinduced electronic transition occurs bet#een onl% t#o of the four dispersion curves7 of the oscillator strength contributes to the matri. elements. he model assumes that the hole and electron effective masses in the IE!s subbands are equal. :or pedagogical simplicit%, the model parameters are not altered #ith temperature. he follo#ing subsection describes the carrier statistics of this s%stem. Ta$le ./ Aodel parameters for the e.plicative e.amples. Some parameters given in terms of the electron rest mass, < .

#.2.4.2 E5uili(rium 1ermi Energy Fno#ledge of the equilibrium :ermi energ% of an IE absorber is prerequisite to interpret its equilibrium absorption coefficients. o locate the equilibrium :ermi energ%, :i, Cquation 6"47 is solved for the special case #here the quasi$:ermi levels are all equal to :i. :igure 2/ illustrates the equilibrium :ermi energ% as a function of temperature for absorbers #ith distinct concentrations of intermediate states, CI, #hic h is defined in Cquation 6/27. 9t one e.treme, #hen the concentrations of electrons in the =E and holes and )E are both ver% small compared #ith the concentration of intermediate states, the chargeneutralit% condition indicates that the concentration of holes and electrons in the IE are in balance. herefore, at lo# temperatures, #here the thermall% generated population of =E and )E carriers is lo#, the equilibrium :ermi level is #ithin the IE. In this e.ample, b% construction, the carrier statistics of holes and electrons in the IE are s%mmetricL therefore, the intrinsic :ermi level appears directl% in the center of the band at lo# temperatures. 9t a second e.treme, #hen the concentrations of electrons and holes in the =E and )E band are ver% large compared to the concentrations of the IE carriers, the charge$neutralit% condition ma% be determined b% the number of electrons and holes in the =E and )E, respectivel%. hus, the position of the equilibrium :ermi level reduces to that determined from the canonical e.pression of the :ermi level of an intrinsic semiconductor. :or cases bet#een the t#o e.tremes, the equilibrium :ermi level #ill be located bet#een those of the t#o e.tremes. :or an% given temperature, the larger the concentration of intermediate states, the closer is the :ermi energ% to the first e.treme and 8ice 8e9,a. his investigation reveals that an IE absorbing medium ma% be metallic ;10< or insulating. :urther, the metal$insulator transition depends upon the concentration of intermediate states, the energetic #idth of the IE, and the carrier statistics of the =E and )E. In continuing to the ne.t section, the reader should note that the IE media there are assured to be metallic at and belo# room temperature so long as the concentration of intermediate states is of order 1010 cm " or greater. #.2.4.3 !(sor"tion Characteristics In #hat follo#s is a discussion of several salient features of the absorption characteristics. :irst, is a discussion of the completeness of light absorption and absorption overlap. Second, is a discussion that compares the absorption characteristics at distinct temperatures. :igure 28 presents the absorption coefficients of four distinct samples& in the first three panes 6a$c7 are samples in equilibrium at room temperature 6"00 F7, #hereas in the fourth pane 6d7 the sample is in equilibrium at a temperature closer to absolute 5ero 610 F7. :or each sample, the concentration of intermediate states is sufficient to ensure that the :ermi energ% is #ell #ithin the IE. hus, the electronic occupanc% is favorable for absorption resultant from photons joining each of the interband electronic transitions ;10<. 1ig*re "+/ Cquilibrium :ermi energ% of intermediate$band absorbers as a function of temperature. Cach medium is distinguished b% its concentration of intermediate states, CI.

Co%-le!ene## and O erla- o0 A$#or-!ion Of general importance to high$efficienc% solar$energ% conversion are t#o criteria. :irst, is the absorption of photons #ithin the broad range of high solar irradiance. Second, to first appro.imation, is that #hen multiple absorption paths e.ist, that photons interact #ith matter across the largest bandgap less than the photons! energies. his is because photon interaction #ith matter is associated #ith a rate of internal irreversible entrop% generation, #hich increases monotonicall% #ith :igure 28 illustrates that sample 6a7 does not permit light absorption for all photons greater than the absorber!s smallest bandgap. Sample 6b7, ho#ever, does permit light absorption for all these photons. Oo#ever, for photons in the range the absorption resultant from photo$induced interband electronic transitions bet#een states in the )E and IE overlaps the absorption resultant from transitions bet#een states in the IE and =E. Similarl%, for photons in the range the absorption resultant from photo$induced interband electronic transitions bet#een states in the )E and IE overlaps the absorption resultant from photo$induced interband electronic transitions bet#een states in the )E and =E. Sample 6c7 sho#s an additional absorption overlap, namel% for photons in the range

Oere the absorption resultant from photo$induced interband electronic transitions bet#een states in the IE and =E overlaps the absorption resultant from photo$induced interband electronic transitions bet#een states in the =E and )E. In these e.plicative e.amples there is no situation that satisfies the t#o stated criteria. 9ccording to the parabolic$band appro.imations, to obtain the complete absorption of photons greater than the smallest bandgap in the s%stem #ithout overlap, the follo#ing inequalit% and t#o equalities must be satisfied 6see :igure 2"7

Oere it is assumed absorption is guaranteed so long as

+lugging in from Cquation 62"7, the e.istence of the desired

he ne.t paragraph compares the absorption coefficients at distinct temperatures. Co%-ara!i e A$#or-!ion a! 6i#!in'! Te%-era!*re# here are noticeable differences in the absorption characteristic at room temperature and at temperatures closer to absolute 5ero. In particular, as illustrated b% comparing :igure 286b7 and :igure 286d7, the absorption coefficients 46=I,IO7 and 46I',)O7 are significantl% reduced at temperature near absolute 5ero. his is resultant from the sharpness of the :ermi$(irac statistics f6=I,IO7 and f6I',)O7, respectivel%, at temperatures near absolute 5ero. hough the joint densities of states coupled to transitions 6=',IO7 and 6I',)O7 are appreciable, the states of the IE!s upper subband are almost completel% void of electrons #ith #hich to couple to the holes of the =E and the states of the IE!s lo#er subband are almost completel% void of holes #ith #hich to couple to the electrons of the )E. hus, though

rigorousl% the onsets of interband transition are those given in able ?, the thresholds of appreciable absorption have much to do #ith the energetic difference bet#een the location of the :ermi energ% and the lo#er =E edge and upper )E edges, respectivel%. hus, in the particular case of lo#$temperature absorption, the absorption edges ma% be depicted as in here ;10<. he author no# concludes the findings of Section 8.2. ,."., Con'l*#ion# Eased upon four simplif%ing assumptions the author models an intermediate$band absorbing medium!s absorption coefficients. :rom this, it is concluded that 6i7 if the concentration of intermediate states is at least of order of the intrinsic carrier concentration of an equivalent medium that e.cludes the intermediate states, then the :ermi energ% #ill e.ist #ithin the band of intermediate quantum states. In such case, absorption resulting from each of the allo#ed photo$induced electronic transitions ma% be appreciable. In addition, it is concluded that 6ii7 it is possible that an absorbing medium #ith a multi$bandgap electronic structure ma% absorb all photons #ith energies greater than the smallest bandgap in the s%stem. :urther, it is concluded that 6iii7 though in principle there e.ists a criterion for complete absorption #ithout concomitant absorption overlaps, achieving this criterion is non$trivial. :inall%, 6iv7 it is concluded that at temperatures near absolute 5ero, the absorption edges resulting from transitions at intermediate levels ma% appear blue$shifted as compared #ith room$temperature absorption. his is resultant from a sharp change in the electronic occupanc% of the states of the intermediate band around its quasi$:ermi level. In Section 8.", the author uses the parabolic$band appro.imations to model the photo$emission from intermediate$band absorbers. #.3 *hotoluminescence (ased on *ara(olic-/and !""ro)imations ,.3.1 In!rod*'!ion his section presents theoretical photoluminescent spectra of intermediate band 6IE7 absorbing media. he #or, is relevant to several approaches that aim for high$efficienc% solar energ% conversion. hese include multi$transition solar cells ;20, "8, "4<, and colloidal and epita.ial quantum dot solar cells ;10"<, #hich ma% include multiple electron$hole pair generation ;12/<. +hotoluminescent spectroscop% allo#s the band edges of absorbers to be investigated. herefore, properties of an absorber that are relevant to photovoltaic solar energ% conversion ma% be e.amined #ithout the additional complication of processing an absorbing medium into an actual solar cell ;3"<. +revious research e.amining the photoluminescent properties of IE absorbing media does so onl% for the most ideal case ;3"<, #here, for e.ample, the absorptivit% is given as a linear combination of unit step functions. he core novelt% here is to illustrate the spectroscopic consequences of a multi$gap absorber #hose energ%$#avevector dispersion is given b% parabolic bands ;?4, ?0< 6see :igure 247. In particular, the author utili5es absorption coefficients based on parabolic$band appro.imations to calculate the photon flo#s pumped into and sun, out of the IE absorber ;//<. he author stresses that calculating the absorption coefficients under the parabolic$band appro.imations requires the absolute locations of three quasi$:ermi energies. his as opposed to calculations of the photon flo#s of IE absorbers based on ideali5ed absorption coefficients ;"8, "4, 3", //, 10<, #here onl% the three quasi$:ermi energ% separations need be identified. he remainder of this section is organi5ed as follo#s. In section t#o, the author revie#s relevant assumptions of the parabolic$band appro.imations. here, specific details of the absorption characteristics of the IE absorber are highlighted. Subsequentl%, in section three, the author describes the procedure used to obtain the photoluminescent spectra. In section four, the author offers the spectroscopic consequences of the parabolic bands. he results presented are largel% invariant #ith respect to an% particular absorption characteristics. In section five, the author utili5es the invariance of the results to dra# t#o conclusions. 1ig*re "./ Cnerg%$#avevector dispersion of a direct$gap intermediate$band absorbing medium under parabolic$band appro.imations. +hotoluminescent spectra present here include contributions from si. momentum$conserving photo$induced electronic transitions.

,.3." Para$oli'-7and A--ro4i%a!ion# he +' spectra obtained here utili5e absorption coefficients for an IE absorbing medium based on parabolic$ band appro.imations, #hich are described in more detail in references ;?4, ?0<. his section is divided in

three parts. :irst, the author revie#s the major assumptions of the parabolic$band appro.imations. Second, the author e.plains the phenomenon of parallel absorption paths and distinguish this from ideal spectral selectivit%. hird, the author clarifies the consequences of Ama. and e.plain the role of Ama. in the subsequent presentation of data. #.3.2.1 &elavent *ara(olic-/and !ssum"tions :igure 24 depicts the parabolic energ%$#avevector dispersion that is here considered. he IE is comprised of t#o subbands 6IE1 and IE27 and has a non$infinitesimal band#idth, W IE. he IE is separated from the conduction band 6=E7 and valence band 6)E7 b% energetic gaps =I and I), respectivel%. 9s sho#n, the model supposes a direct$gap medium so that the band e.trema occur at the same #avevector, namel% ,o, #hich can be, for simplicit% and #ithout loss of generalit%, assumed to equal 5ero. he parabolic$band appro.imation assumes that each quantum state in the IE has a #avevector bet#een Ao and Ama. 6see :igure 247. as sho#n in :igure 24, si. momentum$conserving, photo$induced electronic transitions resulting from the parabolic$band appro.imations. #.3.2.2 *arallel !(sor"tion *aths Cach of the momentum$conserving, photo$induced electronic transitions has a quantifiable onset and offset of optical absorption. Eoth depend on the difference bet#een Ao and Ama. ;?4, ?0<. he onset of absorption is that energ% at #hich the absorption coefficient transitions from 5ero to a non$5ero value and 8ice 8e9,a for the offset. 9 photon #ith an energ% in the range ma% induce an% electronic transition #hose onset of optical absorption is less than or equal to the photon!s energ% and #hose offset of optical absorption is greater than the photon!s energ%. In other #ords, if in the range the IE absorber!s absorption characteristic has an absorption overlap ;3/<, more than one of the absorption paths are available to photons #ithin this range H thus parallel absorption paths e.ist for the photons #ithin this range. his contrasts #ith the notion of ideal spectral selectivit%, #hereb% a photon definitivel% generates an electron$ hole pair across the largest bandgap less than or equal to the photon!s energ%. #.3.2.3 &ole o ,avevector6 2ma) he absorption characteristic of an IE absorbing medium that is %ielded b% the parabolicband appro.imations is intimatel% related to the value of Ama. of the IE absorbing medium. In the first place, Ama. is related to the cube root of the concentration ;YRm"< of quantum states in the IE. his itself is lin,ed to the absorption coefficients via the joint densit% of states ;?4<. In the second place, all else being equal save the effective masses of the intermediate band!s subbands, the value of Ama. ma% adjust the onsets and offsets of optical absorption ;?4, ?0<7. 9s an e.ample of the role of Ama., the author no# describes #hich of the absorption paths is most li,el% to convert a photon in the range 61 ./0, 1./0 V 0D *7 e) into an electronhole pair. he energ% range around 1./ e) is of particular import as it is the threshold of the non$blac, emitter 6see :igure 207 used to obtain the results present here. Eased on the band parameters of the absorbers, #hich are roughl% those given in able III of reference ;?4, ?0<7, #hen Ama. is 1 103 m1, photons near 1./ e) e.cite carriers from the )E to the =E. When Ama. is 1 10? m1, there are three parallel absorption paths available to these photonsL ho#ever, the% #ill most li,el% e.cite carriers from the IE to the =E. When Ama. is " 10? m1, there are five parallel absorption paths available to these photonsL ho#ever, these photons #ill primaril% e.cite carriers from the )E to the IE. Aan% of the major results given in this section are given for distinct values of Ama. 6see :igure 237 or plotted #ith respect to Ama. 6see :igure "07. In either case, the author utili5es Ama. to identif% photoluminescent features that are entirel% or largel% invariant #ith respect to Ama., and hence invariant #ith respect to the particularities of the absorption characteristics. In this #a%, the author identifies features that have high li,elihoods of being general photoluminescent properties of an IE absorbing medium as opposed to photoluminescent properties specific to a particular IE medium. Eefore offering the major results, the author first outlines the necessar% steps to calculate photoluminescent spectra. his is the topic of the follo#ing section. ,.3.3 S-e'!ro#'o-i' Pro'ed*re his section details the method used to obtain the photoluminescent spectra. :irst, the emission spectrum of a light emitting diode is chosen for the incident beam. Second, three 6one each to describe the occupanc% of the quantum states of each of the three electronic bands7 quasi$:ermi levels are adjusted until t#o conditions are simultaneousl% obtained& 6i7 the carrier concentrations in the bands %ield a charge neutral IE medium ;?4, ?0< and 6ii7 the net rate of electronic charge injected into each band of the IE medium is null. On converging to a solution, the emission spectrum ;2/< of the IE absorber is used to obtain its photoluminescent spectrum. hese steps are no# e.plained in more detail. #.3.3.1 Incident /eam he incident spectrum used to illuminate the samples is that emitted b% a non$blac, emitter ;2/<. In determining the absorptivit% of the non$blac, emitter, a null surface reflectivit% is assumed and the absorption coefficients are calculated as for a semi$conductor ;102<. Oere, the length, temperature, and quasi$:ermi level separation of the non$blac, emitter are adjusted so that the photon flu. ;10/< emitted is of the order of the solar irradiance at the Carth!s surface concentrated 1000 times 6Z100 WRm27 and so that the full$#idth at half$ma.imum 6:WOA7 is 10 me) 6see :igure 207. o generate this large photon flu.,

the non$blac, emitter is biased so that population inversion results. Oere, the bandgap of the non$blac, emitter is set to 1./ e), #hich is greater than the largest bandgap of the IE absorbing media under test. It is assumed that the all of the photons emitted from the non$blac, emitter are incident on the IE samples. 1ig*re ";/ Simulated emission spectrum of the non$blac, emitter used to irradiate the intermediate band absorbers.

#.3.3.2 7et Charge Current he net charge current injected into each band is calculated from the radiative flo#s and as in reference ;//<. Oere, it is assumed that onl% those photons emitted from the nonblac, emitter are incident on the IE samples, that multiplicit% ;113< does not result from photon absorption, and that the net averaged non$ radiative recombination rates are null. In calculating the photon flo#s pumped into and sun, out of each IE medium ;//<, the absorption coefficients resulting from the parabolic$band appro.imation are emplo%ed ;?4, ?0<. hese absorption coefficients are used to calculate the absorptivit% ;1"< of each IE sample. In so doing, surface reflectivit% is assumed to be null. #.3.3.3 *hotoluminescent s"ectra On converging to a simultaneous solution of the conditions stated in the introduction of this section, the photoluminescent spectra are obtained. he photoluminescent spectra for photons in the range are given as the product of the photon energ%, ,multiplied b% the photon emission spectrum #ithin this range ;2/<. he author no# gives the results of the ongoing investigation. ,.3.+ In arian! P&o!ol*%ine#'en! 1ea!*re# In this section, the author illustrates and discusses t#o photoluminescent features that are invariant #ith respect to the value of Ama.. :irst, is the number of spectral bands that are present in the +' spectra. Second, is the :WOA of the infrared component of the +' spectra. In obtaining the results present here, the model parameters that are used are nearl% those emplo%ed in reference ;?4, ?0<. #.3.4.1 7um(er o S"ectral /ands :igure 23 sho#s the photoluminescent spectra of three semi$infinite 1 IE absorbing media at / F. Cach of these three samples have similar band structuresL the onl% difference is that the effective masses of the intermediate band!s subbands are adjusted to %ield distinct values of Ama.. hough there are differences in the e.act appearances of the +' spectra of each of these three absorbers, the author concentrates attention on contrasting the gross characteristics of these spectra #ith the +' spectra obtained from previous studies of the luminescent properties of such media ;3"<. 1ig*re "</ +hotoluminescent spectra for three distinct semi$infinite 1 IE absorbing media at / F. Cach absorber is distinct #ith respect to the ma.imum valid #avevector in the intermediate band& 697 Ama.> 1.1 103 m1, 6E7 Ama.> 1.2 10? m1 and 6=7 Ama.>"10? m1. +lease note that for visual clarit% the magnitudes of plots E and = are scaled b% 1 10/4 and 1 102", respectivel%.

L*%ine#'en'e >i!& 1o*r S-e'!ral 7and# he first ne# characteristic is that each sample %ields four, rather than three, spectral bands, #ithin #hich are contained a signifi$ cant photoluminescent response. he leftmost spectral bands, +'6I,I7, #hich are absent in references ;3"<, result from momentum$conserving, intraband photo$induced electronic processes bet#een t#o distinct states in the IE. he remaining three pea,s, +'6=,I7, +'6I,)7, and +'6=,)7, result from photo$induced interband electronic processes bet#een the =E and IE, the IE and )E, and the =E and )E, respectivel%. he onsets of all four spectral bands are identical to the onsets of absorption that are defined in reference ;?4, ?0<. Similarl%, the offset of the spectral band associated #ith the intraband processes is equal to the #idth of the IE ;?4, ?0<. P&o!ol*%ine#'en'e a! A$#or-!ion On#e! he second ne# characteristic is that the ape. of each luminescent pea, in each spectral band does not, in general, occur at the optical absorption edge. Nather, the ape.es occur at slightl% larger energies. his results from the fact that under the parabolic$band appro.imations, the joint densit% of states at the absorption edges are null. Eefore moving on to the third major difference, the author stresses that the absorption edges of optical transitions are most fundamentall% associated #ith the minimum energetic difference bet#een an% t#o distinct bands 6see :igure 2?7. his is in contrast to a previous discussion of the absorption edges ;10<, #here there the absorption edges are referenced to the quasi$:ermi level associated #ith the IE. Rela!i e In!en#i!y o0 L*%ine#'en'e he third ne# characteristic is that the orders of magnitude of the ape.es associated #ith the interband transitions at intermediate states are several orders of magnitude larger than those associated #ith the other electronic transitions. his results from the fact that the potential difference bet#een the carriers in the =E and IE, :,=I, is near to if not greater than the onset of optical absorption governing those photo$induced electronic transitions. 9 similar argument ma% be made regarding the potential difference bet#een the carriers in the IE and )E, :,I). +ane 9 of :igure 2? illustrates a case #here t#o distinct population inversions e.ist, #hich are illustrated b% the negative absorptivit% for photons in the ranges 6=I % D* & :,=I7 and 6I) % D* & :,I)7. :urther, for photons #ithin the range 6 =I % D* & =I VWD *7, the absorptivit% contains a sharp spi,e. he upshot is that e.tremel% large emission results #ithin these t#o spectral bands. =ontrar% to the results of pane 9 of :igure 2?, the author notes that onl% a single range of negative absorptivit%, namel% bet#een 6 =I % D* & :,=I7, is observed #hen parallel interband absorption paths e.ist for photons in the range 6I) % D* & :,I)7 . 1ig*re "=/ 9bsorptivit% of intermediate band absorbing media #ith Ama. equal to 1.1 103 m1. +ane 697 illustrates the non$equilibrium absorptivit% of a semi$infinite medium at / F. +ane 6E7 illustrates the absorptivit% of media #ith distinct lengths each of #hich is in equilibrium #ith a blac,bod% of the temperature listed.

he absorptivit% given in pane 9 of :igure 2? ma% be compared #ith the three given in pane E of :igure 2?. he absorptivit% of each of the latter is obtained #hen the IE medium is in equilibrium #ith a blac,bod%. Tote that at temperatures near absolute 5ero t#o of the optical edges appear shifted to higher energies. In particular, one edge appears at the energetic difference bet#een the =E edge, =', and the :ermi energ%, :iL #hile a second edge appears at the energetic difference bet#een the :ermi energ% and the )E edge, )O. hough on close inspection, the% are non$5ero at the onsets given in able I of reference ;?4, ?0<. In the follo#ing subsection, the author ma,es observations regarding the :WOA. #.3.4.2 1ull ,idth at Hal 4a)imum :igure "0 illustrates the :WOA of the spectral band associated #ith the photo$induced, electronic transitions bet#een t#o distinct states of the IE. Sho#n are nine curves plotted #ith respect to Ama.. Cach of the curves is associated #ith an absorber #hose temperature and length are distinct from all the others. It is clear that the :WOA increases #ith increasing temperature. 9t temperatures near absolute 5ero, the :WOA range bet#een 1 me) and / me), #hich are less than the :WOA of the incident beam. :inall%, at room temperature the :WOA range bet#een 80 me) and 30 me), #hich are less than the #idths of the IE considered here 6i.e. here, as in reference ;?4, ?0<, the #idths of the IE are uniforml% 100 me)7. he follo#ing section provides concluding remar,s. 1ig*re 3?/ he full #idth at half ma.imum 6:WOA7 of the spectral band associated #ith intraband electronic transitions bet#een distinct states of the intermediate band 6 i.e. +'6I,I77. Cach of the nine plots is associated #ith an absorber #hose temperature and length are distinct from all the others 6see legend7.

,.3., Con'l*#ion# his section illustrates the spectral consequences of intermediate band absorbers under parabolic$band appro.imations. he results presented here are obtained for absorbers #ith similar band structures. Oo#ever, the absorbers are distinct #ith respect to their temperatures, their lengths, and their absorption characteristics. E% directing attention to those results that are largel% or completel% invariant #ith respect to the nuances of the absorption characteristics, the author is able to dra# conclusions. he author dra#s t#o conclusions regarding the photoluminescent spectra of an absorber #ith quantum states forming a band of a

non$infinitesimal #idth that is electronicall% isolated from both the conduction and valence bands and that has a band#idth smaller than the smallest bandgap in the absorber. :irst, the resulting +' spectra #ill have content #ithin four #ell$separated spectral bands. Second, the full$#idth at half$ma.imum of the spectral band in the infrared regime is less than the energetic band#idth of the quantum states forming the intermediate band. his is important as it allo#s an empirical measure of the energetic #idth of the deep quantum states. #.4 Conclusions he author begins =hapter 8 b% modelling the absorption coefficients of an intermediateband absorbing medium. Several simplif%ing assumptions are made, one of #hich is that the energ%$#avevector dispersions are parabolic. he author concludes that an absorbing medium #ith a multi$bandgap electronic structure ma% absorb all photons #ith energies greater than the smallest bandgap in the s%stem and, although, in principle, a criterion for complete absorption #ithout concomitant absorption overlaps e.ists, achieving this criterion is non$trivial. he author continues =hapter 8 b% presenting theoretical photoluminescent spectra of absorbing media. he absorbing media are simplified according to the parabolic$band appro.imations. he author concludes that photoluminescent intensit% of an intermediate band absorber ma% be appreciable #ithin four distinct and #ell$separated spectral bands. CHAPTER VI - REPORT O1 IN6I@2-ARSENI6E )@ANT@2 6OTS ENVELOPE6 IN GALI@2ARSENI6E-ANTI2ONI6E 7ARRIERS 8.1 Introduction 9 nanostructured quantum$dot absorber intended for a three$transition solar cell is reported. Aolecular beam epita.% is emplo%ed to fabricate In9s quantum dots completel% enveloped in a barrier of *a9s1 /Sb/ 6/ D 0.127 matri. gro#n on a *a9s substrate. he absorber design is presented and the gro#n structures are characteri5ed b% transmissionelectron microscop%, atomic$force microscop%, photoreflectent spectroscop%, and time$integrated and time$resolved photoluminescent spectroscop%. he author inferrs that the conductionband discontinuit% of the quantum dot heterojunctions is roughl% 280$"00 me)L and that the quantum$dot heterojunctions are either t%pe$II heterojunctions or near to the transition bet#een t%pe$I heterojunctions and t%pe$II heterojunctions. he author concludes that detecting photons #ithin the infrared regime of the electromagnetic spectrum is necessar% to confirm that the In9sR*a9s1 /Sb/ 6/ D 0.127 absorber is, in fact, a three$transition absorber. he outline for the remainder of this chapter is as follo#s. In Section 4.2, the author presents detailed bac,ground information. In section 4.", the author describes the In9sR*a9s1/Sb/ 6/ D 0.127 quantum$dot absorber. In section 4./, the author disscusses the various e.periments that are performed on the the In9sR*a9s1 /Sb/ 6/ D 0.127 quantum$dot absorber as #ell as a control absorber. In section 4.8, the author discusses the e.perimental results in relation to the theor% of the three$transition absorber. In section 4.4, the author offers concluding remar,s. 8.2 /ac2ground he abstract notion of increasing the efficienc% of photovoltaic solar energ% conversion #ith a three$transition solar cell is #ell$established ;20, "8<. In addition to offering a global efficienc% enhancement #hile operating on its o#n, #hen comparing la%ers #ithin tandem stac,s, a la%er comprised of a three$transition solar cell is theori5ed to offer a greater efficienc% enhancement than a la%er comprised of a standard p-n junction solar cell ;108<. 9t the time that this disseration is published, an e.perimental demonstration of a globalefficienc% enhancement is absent from the literature. he primar% impediment in reali5ing a three$transition solar cell is the fabrication of an appropriate three$transition absorber. he use of quantum$dot technolog% is offered as a means to reali5e a three$transition solar cell ;8?, 40, 41<. +revious #or, on three$transition solar cells implemented #ith quantum$dot technolog% 6 i.e., a quantum$dot intermediate$band solar cell 6IES=77 revolves around the In9sR*a9s 6confinedRbarrier7 ;/1, 42, 4", 4/< and In*a9sR*a9s ;48< material s%stems. he% are both gro#n on *a9s substrates. One characteristic limiting the usage of these material s%stems is that the% are t%pe$I heterojunctions. his enables the luminescent spectra of these protot%pe -( IES= samples ;/1, 42< to illustrate narro#l% separated and overlapping pea,s, rather than the luminescent signature ;3"< 6 i.e., luminescence in three ;3"< 6or four ;?3<7 #ell$separated spectral bands7 of a three$transition material ;44<. he author reports on the In9sR*a9s1/Sb/ 6/ D 0.127 material s%stem, #hich is identified as a material s%stem for protot%pe three$transition solar cells ;44<. he author emphasi5es t#o beneficial properties of this material s%stem. :irst, it is theoreticall% calculated ;44< and e.perimentall% inferred ;181, 182< to %ield heterojunctions at the transition bet#een t%pe$I and t%pe$II heterojunctions. Second, antimonide acts as a surfactant ;18", 18/<. he former 6band alignment7, is advantageous because it abates the difficult% in interpreting data from inter$band, optical e.perimental methods that e.ists if both holes and electrons are involved ;1"0<. he latter 6surfactant7 is advantageous, because it inhibits the generation of interfacial defects and thus leads to superior optical activit% ;188<. In the ne.t section, the author describes the intended structure of the In9sR*a9sSb absorber. 8.3 -escri"tion o the !(sor(er In this section, section 4.", the author depicts 6section 4.".17 and predicts 6section 4.".27 the intended electronic structure of the absorber. ..3.1 6e-i'!ion o0 !&e A$#or$er

9 cross section of the intended structure of the absorber is depicted in :igure "1. here are five distinct regions that comprise the absorber& a *a9s la%er 6includes both the *a9s substrate and a *a9s buffer7, a *a9s0.33Sb0.12 barrier la%er, an In9s quantum dot la%er, a second *a9s0 .33Sb0.12 barrier la%er, and a *a9s capping la%er. he thic,nesses of these la%ers are labeled as ts,l, tb,l, tc, tb,r, and ts,r, respectivel%. he thic,ness of each la%er is intended to be thin to minimi5e the formation and propagation of dislocations. he thic,ness of the deposited In9s la%er is intended to be just large enough to produce a Strans,i$Frastanov morphological change from a t#o$dimensional epita.ial$la%er to a threedimensional la%er of quantum dots. he band gaps of the *a9s la%er and *a9sSb la%ers are labeled as =),s and =),b, respectivel%. he conduction$band discontinuit% and valenceband discontinuit% at the interface bet#een the *a9s and *a9sSb la%ers are labeled as W=E,s$b and W)E,s$b, respectivel%. he conduction$band discontinuit% at the interface bet#een the *a9sSb and In9s la%ers is labeled as W=E,b$c. he valence$band discontinuit% at this interface is intended to be negligible. 9 collection of bound electronic states #ill be present in the potential #ell defined b% the conduction$band discontinuit% W=E,b$c. he minimum energetic separation bet#een the collection of bound states and the valence$band continuum is labeled as I,), #here I,) % =),bW=E,b$c. he minimum energetic separation bet#een the collection of bound states and the conduction$band continuum is labeled as =I, #here 0 % =I % W=E,b$c. he difference bet#een the energ% of the bound state #ith the largest energ% and the bound state #ith smallest energ% is labeled as WIE, #here 0 % WIE % W=E,b$c. 1ig*re 31/ Schematic band structure for the In9sR*a9s0 .33Sb0.12R*a9s quantum dot absorber.

..3." Predi'!ion o0 Ele'!roni' S!r*'!*re Eased on the band parameters of the technologicall% important III$) semiconductors and their ternar% allo%s ;1/4<, the author calculates the bandgaps =),s and =),b as 1./ e) and 1.2 e), respectivel%L and the discontinuities W=E,s$b, W)E,s$b, and W=E,b$c as "0 me), 210 me), and 3"0 me), respectivel%. he calculations of the above values include the temperature$related )arshni coefficients but e.clude the strain$ related elastic coefficients. he inclusion of the strain$related coefficients significantl% reduces the value of W=E,b$c, so that it ma% be of order /00 me) ;104<. he locations of the bound electronic states that are predicted from the band parameters of the technologicall% important III$) semiconductors and their ternar% allo%s roughl% conforms to the locations of the bound states derived from an atomistic pseudopotential method ;100<. he application of an atomistic pseudopotential method to a protot%pical In9sR*a9s s%stem predicts that the ground energ% of the bound level is "00 me) less than the lo#er edge of the conduction$band continuum ;100<. 8.4 E)"erimentation 0ith the !(sor(er #o absorbers are gro#n on *a9s60 0 17 epi$read% substrates b% molecular$beam epita.%. One is a quantum$dot absorber and the other is a control that has a structure similar to that depicted in :igure "1, e.cept that the la%er of In9s quantum dots is e.cluded. Sra% diffractometr% is used to characteri5e the la%er compositions and la%er thic,nesses of both absorbers 6section 4./.17. Eoth transmission$electron microscop% and atomic$force microscop% are used to characteri5e the morphological structure of the quantum dot

absorber 6section 4./.27. +hotoreflectent spectroscop% is used to characteri5e changes in the optical constants of both absorbers 6section 4./."7. +hotoreluminescent spectroscop% is used to characteri5e the photo$emission of both absorbers 6section 4././7. ..+.1 B-Ray 6i00ra'!o%e!ry S$ra% diffractometr% is used to characteri5e the la%er compositions and la%er thic,nesses b% fitting double$ cr%stal and triple$cr%stal roc,ing curves 6both * and */2E roc,ing curves7. he fitting of the roc,ing curves associated #ith the quantum$dot absorber implies that the thic,ness of the *a9s buffer la%er is "?0 nm, the thic,ness of first *a9s1/Sb/ la%er is 1? nm, the thic,ness of the In9s la%er is 0." nm, the thic,ness of second *a9s1/Sb/ la%er is 10 nm, the thic,ness of the *a9s capping la%er is /8 nm, and the molar concentration of antimonide, /, in the first and second *a9sSb la%er is 0.1/ and 0.11, respectivel%. he fitting of the roc,ing curves associated #ith the control absorber implies that the thic,ness of the *a9s buffer la%er is "30 nm, the thic,ness of the single *a9s1 /Sb/ la%er is "/ nm, the thic,ness of the *a9s capping la%er is ?/ nm, and the molar concentration of antimonide, /, is 0.12. ..+." Tran#%i##ion-Ele'!ron 2i'ro#'o-y and A!o%i'-1or'e 2i'ro#'o-y Eoth transmission$electron microscop% and atomic$force microscop% are used to characteri5e the morphological structure of the quantum dots. Images obtained from contact$mode atomic$force microscop% performed in both height mode and deflection mode suggest that the quantum dots form into elongated lenses. he t%pical length along the major a.is is of order /0 nm. he t%pical length along the minor a.is is of order 20 nm. Images obtained from transmission$electron microscop% suggest that the t%pical diameter of a quantum dot is of order 20 nm and that the t%pical height of a quantum dot is of order / nm. In the follo#ing section, the author describes the characteri5ation of the absorbers b% photoreflectent spectroscop%. ..+.3 P&o!ore0le'!en! S-e'!ro#'o-y In this section, section 4./.", the author describes the apparatus used to acquire the photoreflectent spectra, and presents a time$integrated photoreflectent spectrum of the control absorber and the quantum$dot absorber. 8.4.3.1 -escri"tion o the !""aratus ime$integrated photoreflectent measurements are conducted #ith t#o beams of light. he pump beam is a Oe$Te laser that operates at 10 mW and emits photons #ith a #avelength of 4"2 nm 61.?4 e)7 #ithin a spot si5e of 1 mm2. he probe beam is a 280 W quart5tungsten halogen lamp that operates at 128 W and is suitable for measuring #ithin the visible and near$infrared regimes of the electromagnetic spectrum. he probe beam is first passed through a monochrometer and ne.t, passed through a lens to enhance the po#er densit% #ithin a spot si5e of 1 mm2, #hich matches that of the laser. he photoreflectance is modulated b% chopping the laser beam at 0?0 O5. he signal at the photodetector is integrated over a period of one second. 9 *e detector operating at room temperature is used to detect photons #ith #avelengths bet#een 300 nm 61.88 e)7 and 1400 nm 60.03 e)7. 8.4.3.2 *resentation o the %ime-Integrated *hotore lectance he photoreflectent spectrum of the control absorber and the photoreflectent spectrum of the quantum$dot absorber are presented in :igure "2. he photoreflectent spectrum of the control absorber implies that its optical constant changes starting at 1.2 e) and again at 1."0 e). he change at 1.2 e) results from the *a9sSb matri. and the change at 1."0 e) results from the *a9s matri.. he photoreflectent spectrum of the quantum$dot absorber is qualitativel% similar to that of the control absorber. he author emphasi5es that, similar to the photoreflectent spectrum of the control absorber, the photoreflectent spectrum of the quantum$ dot absorber is unchanging bet#een 0.03 e) and 1.2 e). In the follo#ing section, the author describes the characteri5ation of the absorbers b% photoluminescent spectroscop%. 1ig*re 3"/ ime$integrated photoreflectent spectra of the quantum$dot absorber and the control absorber. hough probed, no change in optical constant is discernable in either absorber bet#een the energies 0.03 e) and 1.2 e).

..+.+ P&o!ol*%ine#'en! S-e'!ro#'o-y In this section, section 4././, the author describes the apparatus used to acquire the photoluminescent spectra, presents a time$integrated photoluminescent spectrum of the control absorber and of the quantum$ dot absorber, and discusses time$resolved photoluminescent data of the control absorber and the quantum$ dot absorber. 8.4.4.1 -escri"tion o the !""aratus he photoluminescent apparatus is described in reference ;103<. ime$integrated photoluminescent 6+'7 and time$resolved photoluminescent 6 N+'7 measurements are conducted #ith the sample mounted in a Oe$flo# cr%ostat operating from /./ to "00 F. he e.citation source #as a tunable i&sapphire laser #ith operating #avelength fi.ed at 080 nm 61.48 e)7, #hich delivers 1"0 fs long pulses #ith a po#er densit% of 1."4 WRcm2 and #ith a repetition rate of 04 AO5. he luminescence is dispersed into a 0."2 m spectrometer and is detected b% a liquid nitrogen cooled In*a9s detector or b% a =/""/ strea, camera for +' and N+', respectivel%. he In*a9s detector is used to detect photons #ith #avelengths bet#een 000 nm 61.00 e)7 and 1400 nm 60.03 e)7. he time resolution of the setup is less than 30 ps. he author no# offers the time$ integrated photoluminescent spectra. 8.4.4.2 *resentation o the %ime-Integrated *hotoluminescence :igure "" presents time$integrated photoluminescent spectra of the control absorber and the quantum$dot absorber, #here each spectrum is normali5ed #ith respect to its pea, intensit%. he spectrum of the control absorber 6dashed line of :igure ""7, #hich is obtained #hile the absorber is maintained at / F, indicates strong luminescence #ithin t#o spectral bands. hese spectral bands are labeled +'= ,I and +'= ,II. In spectral band +'= ,I, photoluminescence is apparent for photons #ith energ% in the range 61.1? e) 610/0 nm7 %% 1."8 e) 6?1? nm77, #ith a pea, occurring at 1."2 e) 6?"? nm7. In spectral band +'= ,II, photoluminescence is apparent for photons #ith energ% in the range 61."4 e) 6?12 nm7 % % 1.82 e) 6314 nm77, #ith a pea, occurring at 1./0 e) 63// nm7. he spectrum of the quantum dot absorber 6solid line of :igure ""7, #hich is obtained #hile the absorber is maintained at 00 F, indicates strong luminescence #ithin t#o spectral bands. hese spectral bands are labeled +'-(,I and +'-(,II. In spectral band +'-(,I, photoluminescence is apparent for photons #ith energ% 612/0 nm7 % +'-(,II, photoluminescence is apparent for photons #ith energ% in the range 61.0" e) % 1.22 e) 61020 nm77, #ith a pea, occurring at 1.1/ e) 610?0 nm7. In spectral band in the range 61.2? e) 6?40 nm7 %

% 1./0 e) 6334 nm77, #ith a pea, occurring at 1."8 e) 6?1? nm7. In :igure "", the author emphasi5es that the spectral band +'-(,I ma% be characteri5ed b% its full #idths. he full$#idth at half$ma.imum, :Wa, the full$#idth at tenth$ma.imum, :Wb, and the full$#idth at hundredth$ma.imum, :Wc, are 88 me), 120 me), and 140 me), respectivel%. 1ig*re 33/ ime$integrated photoluminescent spectra of the quantum$dot absober 6solid7 and the control absorber 6dashed7. Cach spectrum is normali5ed #ith respect to its pea, intensit%. hough probed, no photons #ith energies bet#een 0.03 e) to 1.0" e) are detected from sample E.

he photoluminescent response of the control absorber #ithin the spectral bands labeled +'= ,I and +'= ,II results from its *a9s0 .?0Sb0.10 matri. and its *a9s matri., respectivel%. he photoluminescent response of the quantum dot absorber #ithin the spectral band labeled +'-(,II is highl% correlated #ith the photoluminescent response of the control absorber #ithin the spectral band labeled +'= ,I. herefore, photoluminescence of the quantum dot absorber #ithin the spectral band labeled +'-(,II ma% be attributed to the *a9s0.33Sb0.12 barrier la%er. he presents author no# discusses the time$integrated photoluminescent spectra. 8.4.4.3 -iscussion o the %ime-&esolved *hotoluminescence ime$resolved photoluminescent spectroscop% is performed on the control absorber and the quantum$dot absorber #hile the% are maintained at 00 F. :or the control absorber, the tunable laser is set to ?// nm 61."1 e)7, #hich corresponds to the pea, of the spectral band labeled +'= ,I 6see :igure ""7. he fit to the time$ resolved data indicates a lifetime of ".3 ns at this #avelength. :or the quantum dot absorber, t#o time$ resolved measurements are made. :irst, the tunable laser is set to ?20 nm 61."8 e)7, #hich corresponds to the pea, of the spectral band labeled +'-(,II 6see :igure ""7. Second, the tunable laser is set to 10?1 nm 61.1/ e)7, #hich corresponds to the pea, of the spectral band labeled +'-(,I 6see :igure ""7. he fit to the time$resolved data indicates a lifetime of 10 ns and 1./ ns at these #avelengths, respectivel%. he author no# offers a discussion of the theoretical and e.perimental components presented thus far. 8.# -iscussion o the &esults In Section 4.8 the author discusses the e.perimental results #ithin the conte.t of the three$transition solar cell. Specificall%, in Section 4.8.1, the author infers the electronic structure of the quantum$dot absorber from e.perimental results and in Section 4.8.2, the author discusses the failure to match the e.perimental photoluminescent spectrum of the quantum$dot absorber #ith the photoluminescent signature of a three$ transition absorber. In Section 4.8.", the author discusses #h% a photoreflectent signal associated #ith the bound states of the quantum$dot heterojunctions is not apparent. ..,.1 In0eren'e Regarding A$#or$erA# Ele'!roni' S!r*'!*re he author dra#s three inferences regarding the absorber!s electronic structure. he author infers that the In9sR*a9s1/Sb/ 6/ D 0.127 heterojunctions e.ists at or near a t%pe$I to t%pe$II heterojunctions. he author infers that the bandgap of the *a9s1/Sb/ 6/ D 0.127 is roughl% 1.22 e) and 1.1? e) at room temperature and at / F, respectivel%. he author infers that the conduction band discontinuit% in the In9sR*a9s1 /Sb/ heterojunctions is roughl% 200 e)$"00 me). he author infers that the band alignment of the In9sR*a9s1/Sb/ heterojunctions #ithin the quantum$dot absorber e.ist at or near the transition bet#een a t%pe$I heterojunctions and a t%pe$II heterojunctions. %pe$II heterojunctions are theoreticall% predicted ;1/"< and e.perimentall% verified ;1//< as having relativel% long radiative lifetimes resulting from the spatial division of confined electrons and holes. 9 ver% long lifetime 610 ns7 is e.trapolated from the time$resolved photoluminescent data that is ta,en at a #avelength associated #ith the pea, of the photoluminescent spectrum #ithin the spectral band labeled +'= ,I in :igure "". his lifetime is one order of magnitude greater than the lifetimes associated #ith the bound states in t%pe$I In9sR*a9s heterojunctions, #hich are t%picall% of the order 1 ns #hen the In9sR*a9s absorber is maintained at temperatures bet#een 10 F and 38 F ;10?<. he author infers that the bandgap of the *a9s1 /Sb/ 6/ D 0.127 matri., =),b, is roughl% 1.22 e) VR$ 0.01 e) at room temperature and 1.1? e)VR$ 0.02 e) at / F. he former inference is dra#n from the photoreflectent spectrum that sho#s a change in the photoreflectance beginning roughl% at 1.22 e). he latter inference is dra#n from the timeintegrated photoluminescent data #ithin the spectral band labeled +'= ,I 6see :igure ""7, #hich has an emission onset at 1.1? e). he author infers that the conduction$band

discontinuit% at the interface bet#een the *a9sSb matri. and In9s matri., W=E,b$c, is bet#een 210 me) and "20 me). his inference is dra#n from the time$integrated photoluminescent spectrum of the quantum dot absorber. he smaller of the t#o values corresponds to the energetic difference bet#een the pea, of spectral band +'-(,II, and the pea, of spectral band +'-(,I, #hich is 210 e). he larger of the t#o values corresponds to the energetic difference bet#een the pea, of spectral band +'-(,II, and the onset of spectral band +'-(,I, #hich is "20 e). he author no# discusses the photoluminescent spectrum of the quantum$dot absorber in relation to the photoluminescent signature of a three$transition absorber. ..,." Non-a--aren'e o0 P&o!ol*%ine#'en! Signa!*re he author no# discusses the failure to observe the photoluminescent signature of a threetransition solar cell #ithin the photoluminescent spectrum of the In9sR*a9s1 /Sb/ 6/ D0.127 quantum$dot absorber. he photoluminescent spectrum of the quantum$dot absorber, #hich is illustrated in :igure "", sho#s significant photoluminescent intensit% #ithin t#o #ell$separated spectral bands. his, as opposed to the photoluminescent signature of the three$transition absorber that is theori5ed to have significant intensit% #ithin three ;/1, 3"< or four ;?3< #ell$separated spectral bands. he author infers #here these non$apparent photoluminescent features #ould be visible, #ere the% to e.ist. he author discusses the need for infrared detection, to determine #hether or not the% are visible. +hotoluminescent features #ill result from radiativel%$ coupled transitions bet#een an% t#o states in the collection of bound states 6hereafter referred to as I6I,I7 transitionsJ7. he onset of the photoluminescent features associated #ith the 6I,I7 transitions should be apparent, beginning just above 0 me). he offset of the photoluminescent features associated #ith the 6I,I7 transitions should be apparent at an energ% less than or equal to WIE 6see :igure "17 ;?3<. Eased on the inferred electronic structure, the offset of the photoluminescent features associated #ith 6I,I7 transitions should be detected from photons #ith energ% #here 0 me) & % "20 me) 6".? m7. If the energetic e.tent of the collection of bound states is infinitesimall% small, then the offset should occur at 0 me). If the energetic e.tent of the collection of bound states is equal to the potential depth of the In9sR*a9s0.33Sb0.12, W=E,b$c, then the onset should occur nearer to "20 me). he higher the temperature at #hich the absorber is maintained, the nearer the offset #ill be to WIE ;?3<. he author emphasi5es that if the photoluminescent features resulting from the 6=,I7 transitions and the 6I,I7 transitions of the In9sR*a9s1/Sb/ 6/ D 0.127 absorber #ere to be vie#able, then the% #ould li,el% appear #ithin one spectral band. he shallo#ness of the conduction$band discontinuit% and the broadness of the spectrum of the electronic levels ;100< justif% this. :urthermore, the photoluminescent features associated #ith the 6=,I7 transitions might or might not be distinguishable from the photoluminescent features associated #ith the 6I,I7 transitions ;130<. he failure to detect photoluminescence #ithin the remaining one or t#o spectral bands ma% be attributed to the absence of infrared photodetection in the e.perimental apparatus 6see section 4././.17. In addition, because of the failure to detect photons #ithin the infrared regime of the electromagnetic spectrum, it is impossible to irrefutabl% assert that the In9sR*a9s1 /Sb/ 6/ D 0.127 quantum$dot absorber is, in fact, a three$transition absorber. In the ne.t subsection, the author no# discusses the absence of a photoreflectent signal associated #ith the bound states of the quantum$dot absorber. ..,.3 Non-a--earan'e o0 P&o!ore0le'!en! Signal In this subsection, the author discusses the failure to observe a photoreflectent signal associated #ith the collection of bound electronic states. he author presents four possible reasons for this non$apparent photoreflectent signal and ne.t evaluates each of the reasons. 9 correspondence bet#een the time$ integrated photoluminescent spectra and time$integrated photoreflectent spectra of an absorber is generall% e.pected. Eoth an appreciable photoluminescent intensit% and an appreciable change in the photoreflectance are apparent #ithin the domain from 1 e) to 1.2 e) in In9sR*a9s quantum$dot heterojunctions ;131, 132, 13", 13/, 138<. he features #ithin this domain, similar to the features of the In9sR*a9sSb of :igure "2, are attributed to electronic transitions at bound states introduced b% the quantum$ dot heterojunctions ;131, 132, 13", 13/, 138<. Oo#ever, in some instances the correspondence bet#een time$resolved photoluminescent spectra and time$resolved photoreflectent spectra of an absorber are not apparent. 9n appreciable photoluminescence is apparent and an appreciable change in the photoreflectance is not apparent #ithin the domain from 1 e) to 1.2 e) in In9sR*a9s quantum$dot heterojunctions ;134, 13", 138<. here are four potential reasons as to #h% a photoreflectent signal #ould not appear #ithin this domain. :irst, if the modulated pump beam is comprised of photons #ith energies belo# the bandgap of the barrier material, then a photoreflectent signal ma% not appear ;13"<. Second, if the total volume of the quantum dots is small and the si5e distribution of the quantum dots is largel% inhomogeneous, then a photoreflectent signal ma% not appear ;138<. hird, if the oscillator strength is reduced because of the transition from a t%pe$I heterojunctions, then a photoreflectent signal ma% not appear ;130<. :ourth, if the signal$to$noise ratio is lo#, then a photoreflectent signal ma% not appear. he first reason is not plausible in e.plaining the e.perimental results because the pump beam is comprised of photons #ith energies larger than both the *a9sSb matri. and *a9s matri.. he second reason is plausible in e.plaining the results because the quantum$dot absorber presented here is composed of a single quantum$dot la%er #ith a qualitativel% large inhomogeneit% in the si5e of the quantum dots Hthis is indicated b% atomic$force

microscopic images, #hich are not illustrated. he third reason is plausible in e.plaining the results because the quantum$dot absorber presented here is not composed of quantum$dot heterojunctions #ith a t%pe$I band alignment. he fourth reason is plausible in e.plaining the results because, #hen the signal appears #ithin this domain, the amplitude of the photoreflectent signal ma% be of the order 1 108 or less ;131, 13"<. he signal$tonoise ratio in the photoreflectance apparatus emplo%ed b% the author is too large to discern a signal #ith an amplitude that is of the order 1 108 6see :igure "2 on page 1187. he author no# offers concluding remar,s. 8.8 Conclusions C.perimentation on the In9sR*a9s1 /Sb/ 6/ D 0.127 quantum$dot absorber offers significant insight regarding the research and development of a three$transition solar cell. he band alignment of the In9sR*a9s1/Sb/ 6/ D 0.127 heterojunctions occurs at the transition bet#een a t%pe$I and t%pe$II heterojunctions, #hich abates the difficult% in interpreting empirical data from inter$band, optical e.perimental methods. he plausibilit% that the In9sR*a9s1 /Sb/ 6/ D 0.127 quantum$dot absorber is, in fact, a three$ transition absorber remains an open question. his remains so because the author does not detect photoreflectance nor photoluminescence associated #ith each of the three distinct photoinduced interband electronic transitions of a three$transition absorber. he author detects one change in the photoreflectent signal and detects photoluminescent intensit% #ithin t#o #ell$separated spectral bands. 9ll of these are detected #ithin the visible regime of the electromagnetic spectrum. he author infers that one of the three distinct photo$induced interband electronic transitions of the In9sR*a9s1 /Sb/ 6/ D 0.127 is onl% vie#able in the infrared regime of the electromagnetic spectrum. he author concludes that #hen using optical e.perimental methods, detecting photons #ithin the infrared regime of the electromagnetic spectrum is necessar% to confirm that the In9sR*a9s1 /Sb/ 6/ D 0.127 absorber is, in fact, a three$transition absorber and, more generall%, that an% absorber is a three$transition absorber that is appropriate for a three$ transition solar cell. he general conclusion is derived from the fact that the domain of high solar irradiance is roughl% centered around 300 me) 61.88 m7 and the related fact that the optimal band structure of a three$ transition solar cell!s absorber has a bandgap at roughl% 000 me) 61.00 m7. herefore, as long as researchers intend to reali5e three$transition absorbers appropriate for three$transition solar cells, researchers must include infrared photodetection in their optical e.perimental apparati. APPEN6IB A - RAPI6 AN6 PRECISE CALC@LATION O1 1L@B !.1 !""endi) Introduction he central problem addressed in this appendi. is the rapid and precise calculation of the energ% and particle flu. for detailed$balance photovoltaic applications. he calculation of energ% and particle flu. is essential to modeling the efficiencies and efficienc% limits of solar energ% conversion devices. =omputing flu. #ith the canonical Eose$Cinstein integral, #hich has no closed$form solution, is time consuming and, #ithout due care, prone to error. he novel numerical approach presented here transforms the Eose$Cinstein integral into a linear combination of incomplete Niemann 5eta integrals. he numerical method is benchmar,ed b% comparisons #ith the Niemann 5eta functions. he rapidit% of the numerical pac,age is gauged b% comparing the duration of flu. calculations to other calculation methods. he organi5ation of this appendi. is as follo#s& the ne.t section presents the details of this method, the third section sho#s the means b% #hich the precision of the method has been verified, the fourth section presents evidence that this method is highl% precise, and the fifth section presents evidence that this method, in most cases, is faster than other methods. !.2 Calculation o lu) o calculate flu. rapidl% and precisel% an integral is sought such that its integrand is a function of a single dumm% variable and its limits of integration allo# it to be a proper definite integral. In order to avoid accruing numerical error, the limitations of the computer arithmetic must be considered #ith respect to the integrands. In regions #here there is large floating$point error, appropriate limiting functions must be emplo%ed to appro.imate the integrands. :inall%, consideration must be given to the generation of the 'K . A.".1 1or% #*i!a$le 0or n*%eri'al 'o%-*!a!ion# he integral describing photon flu., FB , derives from the emissivit% of the matter that the photons are interacting #ith, the densit% of photon modes, and the Eose$Cinstein statistics. he canonical form of the flu. is given as

#here EG and E@ are the upper and lo#er energ% limits of the photon emission from the solid, respectivel%, is the equilibrium chemical potential of the radiation, T is the surface temperature of the matter, c is the speed of light, 5 is +lanc,!s constant, A is Eolt5mann!s constant, and B ta,es the values 2 or " for the calculation of particle flu. or energ% flu., respectivel% ;10/<. In future e.pressions for flu., it is understood that the inequalities given in Cquation 6247 are satisfied so that that the flu. is non$5ero. he first step in creating loo,$up$tables, #hich e.pedite the rapidit% and precision of flu. calculations, is to transform

Cquation 6247 into a form #hose integrands are functions of unitless, dumm% variables. E% the follo#ing substitution, . > 6E7/A T, Cquation 6247 is re#ritten as a linear combination of INUI

#here ap1 ma% be determined from carr%ing through the algebra. hough the integrands of Cquation 6207 are a function of a unitless dumm% variable, the form of Cquation 6207 is not al#a%s suitable. Such is the case #hen the upper limit of the emissivit% tends to#ard infinit%, #hich is the case in the majorit% of detailed$ balance efficienc% calculations. In such circumstances, the forms given b% Cquation 6247 and Cquation 6207 become improper integrals. hus, the numerical integration tends to become arbitrar%, as the follo#ing question must be ans#ered& Bust ho# large is infinit%[ 9ccording to some some authors ;10<, it is 4 e). o surmount this problem, the substitution / > 1/. is emplo%ed and thus flu. is re$#ritten as

he form of Cquation 6237 is superior to the t#o previous forms because it allo#s for the construction of 'K and avoids the difficult% of evaluating improper integrals. 9n additional benefit of Cquation 6207 and Cquation 6237 is that the individual integrals 6for p a positive integer greater than one7 ma% be compared #ith closed$ form e.pressions of the Niemann 5eta functions, thus allo#ing chec,s on the precision of the method. A."." Li%i!a!ion# o0 'o%-*!er ari!&%e!i' =omputer arithmetic further complicates the precise computation of flu.. When / is small, one must guard against underflo# errors #hen evaluating the Niemann 5eta integrands. :or comparison, #hen E of Cquation 6247 is large, one must guard against both underflo# and round$off errors. :urther, #hen / is large, the floating$point error caused b% the subtraction in the denominator causes the integrands to oscillate #ith /, until finall% one$over$5ero errors occur. his ma% be seen clearl% b% plotting the relative error bet#een the integrands and a limiting appro.imation to the integrands. :igure "/ illustrates for the case p > " that the Niemann integrand of Cquation 6237 begins to oscillate #ith /, but that the integrand ma% be appro.imated b% a limiting e.pression given in Cquation 6"07. :or comparison, #hen nears E@, the same phenomenon is observed for the Eose$Cinstein integrands. 9s sho#n in :igure "8, #hen / increases a bit be%ond 1 100, the relative error bet#een the t#o integrands stops decreasing and begins to oscillate #ith larger and larger amplitude. hus, for all the Niemann integrals, there is a fi.ed domain of /, D/, such that the integrands are both computable and stable. he limits of this domain largel% depend upon the machine precision of the microprocessor, %et some judgment is necessar% as to the location of the upper cutoff of the domain. It is found ;122< that for a machine precision of order 11014, D/ > ;1./1 10", 1.00 100<is suitable for all the orders of the INUI that are of interest 6p > 1, 2, ", /7. he limits of this numerical domain derive purel% from the constraints of the computer arithmetic, as opposed to considerations regarding the spectrum of a given radiation of interest. In those cases #here there is a contribution to the flu. from outside the boundaries of D/, limiting e.pressions must be used to calculate that contribution. he author recommends the use of \ Flo# B and \ Fhigh B to calculate that contribution if A T/6EG 7 & min6D/7 and if A T/6E@ 7 H ma.6D/7 respectivel%, #here

1ig*re 3+/ :or large /, evaluation of Niemann 5eta integrands is subject to round$off errors that are caused b% the denominator terms. In these cases, the integrands ma% be appro.imated b% limiting functions such as those given in Cquation 6"07. his figure sho#s the integrand of Cquation 6207, 6 /pV1 ;e.p 61//7 1<71, and that of Cquation 6"07, /p, for the case p > "

Tote that Cquation 62?7 and Cquation 6"07 are both anal%tic and thus can be e.pressed in a closed form, #hich further augments both the precision and the speed of computation, as numerical integration is unnecessar%. In addition to their utilit% in appro.imating flu. outside the bounds of D/, Cquation 62?7 and Cquation 6"07 ma% be used to gauge the accurac% of computations #hile debugging soft#are and even, in some cases, to appro.imate the flu. across the #hole limit of integration, E@ to EG, as #ill be seen in Section 9.". A.".3 Loo(-*--!a$le# 0or Rie%ann ze!a in!egral# Cach of the Niemann integrals is associated #ith t#o 'K & one containing increasing values of /, beginning #ith min6D/7 and ending #ith ma.6 D/7L and a second recording the computed values of the INUI bet#een t#o successive entries in the first 'K . :or e.ample, in calculating the particle flu. in a situation such that min 6D/7 & E@ & EG & ma. 6D/7, the operations given in Cquation 6"17 are performed. Oere /6p7 n is the smallest value in the first 'K associated #ith the pth Niemann 5eta integral greater than A T/6EG 7, /6p7 $ is the largest value in the first 'K associated #ith the p th Niemann 5eta integral less than A T/6E@ 7. In addition, and all the integrals in the inner summation are pre$computed and recorded in the second 'K associated #ith the pth Niemann 5eta integral.

1ig*re 3,/ 9s / increases be%ond 1 100, the relative error bet#een the integrands of Cquation 6237 and Cquation 6"07 begins to oscillate #ith increasing amplitude. his is true for p > 1, 2, ", /. his figure sho#s p > ".

:or the special case #here n > 1, the last integral in Cquation 6"17 is appro.imated b% the limiting e.pression given in Cquation 62?7. Similarl%, for the special case #here /$ >ma. 6D/7, the first integral in Cquation 6"17 is appro.imated b% the limiting e.pression given in Cq 6"07. +re$computing 'K in the manner of Cquation 6"17 not onl% speeds up calculations during run time but, in general, provides more precise results. he reason is that numerical integration routines are almost e.clusivel% based upon interpolation pol%nomials and the integrands of the Niemann 5eta integrals must be interpolated #ith pol%nomials of ver% large order. hus, in general, numerical integration routines #ill have a difficult time maintaining both precision and rapidit%, especiall% over large intervals ;133<. herefore, the method that the author adopts is to generate 'K b% composite integration across D/. In performing the composite integrations, the author first performs E$form least$squares spline appro.imations of order si. to the integrand functions using A9 '9E!s spap2 function. he spline appro.imations are performed b% logarithmicall% sampling the integrand functions five thousand times. Te.t, A9 '9E!s ne#,nt function is emplo%ed to choose a ,not sequence that divides the numerical range into five intervals. he ,not sequence obtained b% this procedure is sho#n in :igure "4 for the case p > 2. Te.t, each interval is logarithmicall% partitioned into sub$intervals. he number of sub$intervals in a given interval is increased until the integral across the interval converges. able 0 gives the intervals! brea,points for the cases p > 1, 2, ", and /. :or each of these, to obtain convergence, the first interval 6small /7 is bro,en into 30 sub$intervals, the last interval is bro,en into 400 sub$intervals, and the remaining three intervals are bro,en into ten sub$intervals. 1ig*re 3./ Integrand of the Niemann 5eta integral of order t#o #ithin the numerical domain D/. he circles indicate the interval demarcations as obtained b% the spline appro.imation.

he ne.t section provides evidence that the method developed in this section has a high degree of precision. Ta$le ;/ he value of / that demarcates the ith brea,point of the integrand of the pth INUI. hese demarcations are obtained b% a spline appro.imation to the integrands.

!.3 3eri ication o high-"recision he numerical soft#are that implements this method is benchmar,ed for precision b% a number of means. hese include comparisons bet#een the Niemann 5eta functions, and previousl% recorded values for solar cell limiting efficiencies from the literature. Aost importantl%, the fact that the complete Niemann 5eta integrals for positive integers greater than one are given in closed form allo#s for a comparison that provides conclusive indication of the precision of the combination of 'K and limiting e.pressions. :or p > 2, ", and / the simulator %ields an absolute error of order 1 101/ such that the computed value #as greater than the closed$form e.pression. he computational pac,age is also benchmar,ed against a number of efficienc% limit results for the single p-n junction solar cell and the IES=. o further judge the precision of the numerical pac,age, results are compared #ith previous results obtained b% the literature. Knder ma.imum solar concentration, a solar surface temperature, Ts, of 8042 F, and a planetar% surface temperature, Tp of 233 F, the efficienc% limit of the single junction solar cell 6SBS=7 is calculated as /0.01. his efficienc% occurs #hen the lo#er limit of the emissivit%, #hich is equal to the band$gap Eg, is 1.04 e) and the upper limit of the emissivit% tends to#ards infinit%. his compares favorabl% to the results of (e )os 6/0.31 for Eg > 1.18 e)7 ;10/<. It is #orth noting that under these conditions if Cquation 62?7 is used to appro.imate the solar cell flu. over the complete limit of integration, / > ;0, ATs/Eg< 6#here > Eg61Tp/Ts7 ;10/<7H#hich is justified because for Eg > E@ of order 1 e) the integrand of Cquation 6237 is dominated b% the e.ponential termHthen the solar cell particle flu. ma% be appro.imated anal%ticall%. he resultant value #ill be slightl% larger than #hat #ould be obtained from numerical calculations using Cquation 6237 because, for all values of /, the denominator of Cquation 62?7 is greater than the denominator of Cquation 6237 . hus a ceiling is obtained, #hereb% an% computed efficienc% above this ceiling is patentl% invalid. he efficienc% limit computed in this manner, for the identical conditions stated in the beginning of this paragraph, establishes a ceiling of /0.31. Ksing the same temperatures as listed above, but #ith a solar concentration of 1., the optimum efficienc% is computed as "1.01 #hen Eg > 1.24 e). hese results compare favorabl% #ith the #or, of (e )os, #ho records the identical efficienc% #hen Eg > 1."0 e) ;10/<. he numerical pac,age is also benchmar,ed on the efficienc% limit of a SBS= at full concentration but #ith Ts > 808? F and Tp > "00 F. he results of such calculations provide an efficienc% limit of /0.41 at Eg > 1.04 e), #hich compares favorabl% to the previousl% reported result under identical conditions& /0.01 at Eg > 1.04 e) ;13?<. :inall%, the soft#are pac,age is benchmar,ed against previous calculations of the IES=. he numerical soft#are obtains a conversion efficienc% of 4".21, #hich is obtained #hen the effective band$ gap bet#een the conduction band and valence band is 1.?8 e) and the band$gap bet#een the intermediate band and valence band is 0.01 e). his result compares e.actl% #ith the efficienc% limit as defined here ;"8<. 9dditionall%, under 1$sun illumination the simulator calculates an optimum efficienc% of /4.31, #hich is obtained #hen the effective band$gap bet#een the conduction band and valence band is 2./0 e) and the effective bandgap bet#een the intermediate band and valence band is 0.?2 e). his result again compares favorabl% #ith the previousl% reported optimi5ed efficienc% of /4.01, #hich is reported to occur #hen the effective band$gap bet#een the conduction band and valence band is 2./" e) and the effective band$gap bet#een the intermediate band and valence band is 0.?" e) ;10<. he ne.t section presents a verification of the rapidit% of the method formulated herein. !.4 3eri ication o ra"idity o gauge the rapidit% of the method, it must be compared to other methods of calculating flu.. he method is benchmar,ed b% comparing the average durations of flu. calculations as per the e.pressions given b% Cquation 6247, Cquation 6207, Cquation 6237, and Cquation 6237 . Oere Cquation 6237 signifies the use of Cquation 6237 #ith the incorporation of the 'K as #ell as the limiting functions given in Cquation 62?7 and Cquation 6"07. able 3 sho#s ho# these different methods of calculation compare for t#elve unique cases, all of #hich are performed #ith a numerical tolerance of 1 101/. hese specific cases are chosen because the% are t%pical for detailed$balance applications #ith internall% biased operating points and applications #ith multiple absorbers. o minimi5e the temporal variabilit% #ith respect to the evaluation of the t#elve cases, for each case, the duration is given as the average of 800 identical calculations. he data of able 3, #hich is

obtained #ith a ".4 *O5 processor, indicate that for nine of the t#elve cases, the method that is developed herein is roughl% bet#een five times and a hundred times faster than the ne.t fastest method. he gains in speed tend to increase as the value of approaches its as%mptote E@. Knder most circumstances, the method developed herein requires that a numerical integration routine be called 2 6B V17 times, #hich is compared to a single call if using the Eose$Cinstein integral of Cquation 6247. Oo#ever, the duration is never three times slo#er #hen compared to the calculations using Cquation 6247. :urther, in onl% t#o of the t#elve cases is the method developed herein more than three times slo#er than the fastest method. 2et, in applications that require the determination of the internall% biased operating points, man% more flu. calculations must be made for greater than 5ero as compared #ith onl% a small number of flu. calculations #here is equal to 5ero. herefore, for these detailed$balance applications, significant time saving ma% be achieved b% adopting the method presented herein. Ta$le </ 9verage duration of 800 identical flu. computations for t#elve unique input conditions, each of #hich are computed b% four different methods. hese conditions are selected because the% are t%pical for detailed$balance efficienc% calculations. he values of E@, EG and are given in electron$)olts

!.# !""endi) Conclusions 9 method is formulated to rapidl% and precisel% calculate particle flu. and energ% flu. for detailed$balance efficienc% calculations. he method transforms the canonical Eose$ Cinstein integral into a linear combination of incomplete Niemann 5eta integrals. E% use of this transformation, loo,$up$tables are generated that record the results of pre$computed composite integration. he precision of the method is established b% comparing the numericall% computed values of the Niemann 5eta integrals #ith the closed$form e.pressions for these integrals. 9n absolute error of 1 101/ is obtained bet#een the t#o. he rapidit% is gauged b% comparing the duration of various flu. calculations using several different methods. It is found that, under most circumstances, the formulated method is bet#een five times and one hundred times faster than other methods. APPEN6IB 7 - A7SORPTION COE11ICIENTS 7ASE6 ON PARA7OLIC-7AN6 APPROBI2ATIONS In this appendi., the author generali5es the procedure of Nosencher and )inter ;102< is to render the absorption coefficients of the si. momentum$conserving transitions. :or photons in the range the absorption coefficients, 46S,27 states ;121<, IJ,6S,27 and :ermi$(irac statistics, f6S,27 are given in terms of the joint densities of and f6S,27 as

#here /6S,27 are the matri. elements of the optical interactions under the supposition that the% are independent of the #avevector, K is the permittivit% of free space, nop is the optical inde. of refraction, q is the elementar% =oulomb charge, * is the radian frequenc% of the photons, and c is the speed of light. he joint densities of states and :ermi$(irac statistics are e.pressed as

Oere, <9,6S,27 are the reduced effective masses, AE is Eolt5mann!s constant, and Tc is the temperature of the absorber. he upper and lo#er bounds of the inequalities of Cquation "" are given in able ?. Cquation "/ is #ritten in terms of the three quasi$:ermi levels 6see :igure 227. It is understood from the introduction that the carriers in the t#o intermediate subbands are in electro$chemical equilibrium, so that :,IO is equal to :,I'. Ta$le =/ Optical absorption edges, for each element 6S,27 in the set T of si. allo#ed momentum$ conserving transitions, #here the absorption coefficients are non$5ero. he onsets and offsets of absorption are labeled as

APPEN6IB C - A7SOL@TE LOCATION O1 THE )@ASI-1ER2I LEVELS In this appendi., the author details the method used to identif% the quasi$:ermi levels. his method hinges upon t#o balance equations and the capabilit% to calculate the carrier statistics in each of the bands. he latter is done #ith a numerical method ;1?0< to calculate both the complete and the incomplete :ermi$(irac integrals. C.1 /alance E5uations he location of the quasi$:ermi levels ma% be found b% simultaneousl% solving t#o balance equations& a charge$neutralit% condition and a charge current densit% condition. he chargeneutralit% of an IE absorber is enforced b% a balance of the electronic charge in the absorber. his balance is #ritten in terms of the concentrations of electrons in the =E, n=, holes in the IE, pI, electrons in the IE, nI, and holes in the valence band, p), as 9dditionall%, #hile operating in stead% state, the charge current densit% through the IE is in balance ;"8<. Including the effect of nonradiative recombination the net charge current densit% is in balance as ;//<

#here @$p,I) ;m2s1< and @$s,I) ;m2s1< are, respectivel%, the photons flu.ed absorbed and emitted due to photo$induced electronic transition bet#een the IE and )E continuaL @ $p,=I ;m2s1< and @$s,=I ;m2s1< are, respectivel%, the photons flu.ed absorbed and emitted due to photo$induced electronic

transition bet#een the =E and IE continuaL ;m"s1< and ;m"s1< are the average net rates of nonradiative recombination per volume from the IE to the )E and =E to the IE, respectivel%L and - is the length of the absorbing medium. he simplif%ing assumption of parabolic bands allo#s for a direct numerical computation of the carrier concentrations using the :ermi$(irac integral. his is no# sho#n belo#. C.2 Carrier Concentrations Solving the charge$neutralit% balance equation 6Cquation "47 requires the computation of the carrier concentrations. In the case of parabolic bands, the carrier concentrations are #ritten as ;100<

and

he carrier concentrations are given in terms of the effective densities of states, $S, #hich are given as

the incomplete :ermi$(irac function, FJ6/, b7, #hich is given as ;1?0<

and the follo#ing unitless variables&

he carrier concentrations %ield the follo#ing equation for the concentration of intermediate states in the IE, CI ;m"<, #hich is used e.tensivel% in section 8.2./. his is given as the sum of the concentration of electrons and holes in the IE, and ma% be #ritten in closed form as

RE1ERENCES ;1< +. W]urfel, I hermod%namic limitations to solar energ% conversion,J +h%sica C,vol. 1/, no. 1$2, pp. 13H24, 2002. ;2< +. W]urfel, I hermod%namics of solar energ% converters,J in Te.t *enerations +hotovoltaics, 9. AartPQ and 9. 'uque, Cds. Eristol and +hiladelphia& Institute of +h%sics +ublishing, 200/, ch. ", p. 80. ;"< +. . 'andsberg and *. onge, I hermod%namic energ% conversion efficiencies,J Bournal of 9pplied +h%sics, vol. 81, p. N1, 1?30. ;/< 9. (e )os, Cndoreversible hermod%namics of Solar Cnerg% =onversion. O.ford&O.ford Kniversit% +ress, 1??2, pp. /, 0, 13, 00, ?/H4, 120H12", 12/H128,128H12?. ;8< W. Shoc,le% and O. B. -ueisser, ICfficienc% of p-n junction solar cells,J Bournal of 9pplied +h%sics, vol. "2, p. 810, 1?41. ;4< 9. (e )os, I(etailed balance limit of the efficienc% of tandem solar cells.J Bournal of +h%sics (, vol. 1", no. 8, pp. 3"?H/4, 1?30. ;0< B. Werner, N. Erendel, and O. Oueisser, ITe# upper efficienc% limits for semiconductor solar cells,J in 1??/ ICCC :irst World =onference on +hotovoltaic Cnerg% =onversion. =onference Necord of the #ent%

:ourth ICCC +hotovoltaic Specialists =onference$1??/ 6=at.To.?/=O""48$/7, vol. vol.2, Wai,oloa, OI, KS9, 1??/, pp.10/2H8. ;3< 9. AartPQ and *. '. 9raPujo, I'imiting efficiencies for photovoltaic energ% conversion in multigap s%stem,J Solar Cnerg% Aaterials and Solar =ells, vol. /", pp. 20"H222, 1??4. ;?< 9. de )os and E. (esoete, IOn the ideal performance of solar cells #ith larger$thanunit% quantum efficienc%,J Solar Cnerg% Aaterials and Solar =ells, vol. 81, no. "$/, pp. /1" H 2/, 1??3. ;10< 9. 'uque and 9. AartPQ, I9 metallic intermediate band high efficienc% solar cell,J +rogress in +hotovoltaics, vol. ?, no. 2, pp. 0"H34, 2001. ;11< 9. S. Ero#n and A. 9. *reen, I(etailed balance limit for the series constrained t#o terminal tandem solar cell,J +h%sica C, vol. 1/, pp. ?4H100, 2002. ;12< 9. Ero#n and A. *reen, IImpurit% photovoltaic effect& :undamental energ% conversion efficienc% limits,J Bournal of 9pplied +h%sics, vol. ?2, no. ", pp. 1"2?H"4, 2002. ;1"< A. 'ev% and =. Oonsberg, IAinimum effect of non$infinitesmal intermediate band #idth on the detailed balance efficienc% of an intermediate band solar cell,J in / th World =onference on +hotovoltaic Cnerg% =onversion, Wai,oloa, OI, KS9, 2004, pp. 01H0/. ;1/< S.+. Eremner, A.2. 'ev%, and =.E. Oonsberg, I9nal%sis of tandem solar cell efficiencies under 9m1.8* spectrum using a rapid flu. calculation method,J +rogress in +hotovoltaics, vol. $, pp. H, 2003, accepted for publication. ;18< N. +etela, IC.erg% of heat radiation,J 9SAC Bournal of Oeat ransfer, vol. 34, pp.130H?2, 1?4/. ;14< 9. (e)os, =. =. *rosjean, and O. +au#els, IOn the formula for the upper limit of photovoltaic solar energ% conversion efficienc%,J Bournal of +h%sics (, vol. 18, no. 10, pp. 200"H18, 1?32. ;10< *. 9raPujo and 9. AartPQ, I9bsolute limiting efficiencies for photovoltaic energ% conversion,J Solar Cnerg% Aaterials and Solar =ells, vol. "", no. 2, pp. 21" H /0, 1??/. ;13< 9. 'uque and 9. AartPQ, I'imiting efficienc% of coupled thermal and photovoltaic converters,J Solar Cnerg% Aaterials and Solar =ells, vol. 83, no. 2, pp. 1/0 H 48, 1???. ;1?< C. Bac,son, I9reas for improvement of the semiconductor solar energ% converter,J in +roceedings of the =onference on the Kse of Solar Cnerg%, ucson, 9ri5ona, 1?88, pp. 122H4. ;20< A. Wolf, I'imitations and possibilities for improvement of photovoltaic solar energ% converters. +art I& =onsiderations for Carth!s surface operation,J in +roceedings of the Institute of Nadio Cngineers, vol. /3, no. 0, 1?40, pp. 12/4H4". ;21< T. 9lvi, =. Eac,us, and *. Aasden, I he potential for increasing the efficienc% of photovoltaic s%stems b% using multiple cell concepts,J in #elfth ICCC +hotovoltaic Specialists =onference 1?04, Eaton Nouge, '9, KS9, 1?04, pp. ?/3H84. ;22< B. 'ofers,i, I andem photovoltaic solar cells and increased solar energ% conversion efficienc%,J in #elfth ICCC +hotovoltaic Specialists =onference 1?04, Eaton Nouge, '9, KS9, 1?04, pp. ?80H41. ;2"< 9. (e )os and (. )%nc,e, ISolar energ% conversion& +hotovoltaic versus photothermal conversion.J in :ifth C. =. +hotovoltaic Solar Cnerg% =onference, +roceedings of the International =onference, 9thens, *reece, 1?3/, pp. 134H?0. ;2/< +. W]urfel, I he chemical potential of radiation,J Bournal of +h%sics =, vol. 18, pp."340H38, 1?32. ;28< . Aar,vart, I hermod%namics of losses in photovoltaic conversion,J 9pplied +h%sics 'etters, vol. ?1, no. 4, pp. 04/ 102 H, 2000. ;24< T. *. 9nderson, IOn quantum #ell solar cell efficiencies,J +h%sica C, vol. 1/, no. 1$2, pp. 124H"1, 2002. ;20< N. Fing, (. 'a#, F. Cdmondson, =. :et5er, *. Finse%, O. 2oon, N. Sherif, and T. Faram, I/01 efficient metamorphic *aIn+R*aIn9sR*e multijunction solar cells,J 9pplied +h%sics 'etters, vol. ?0, no. 13, pp. 13" 814 H 1, 2000. ;23< 9. Earnett, =. Oonsberg, (. Fir,patric,, S. Furt5, (. Aoore, (. Sal5man, N. Sch#art5, B. *ra%, S. Eo#den, F. *oossen, A. Oane%, (. 9i,en, A. Wanlass, and F. Cmer%, I801 efficient solar cell architectures and designs,J in =onference Necord of the 2004 ICCC /th World =onference on +hotovoltaic Cnerg% =onversion 6ICCC =at. To. 04=O"00/07, Wai,oloa, OI, KS9, 2004, pp. 2840H/. ;2?< 9. Imenes and (. Aills, ISpectral beam splitting technolog% for increased conversion efficienc% in solar concentrating s%stems& a revie#,J Solar Cnerg% Aaterials and Solar =ells, vol. 3/, no. 1$/, pp. 1?H4?, 200/. ;"0< +. 'andsberg, O. Tussbaumer, and *. Wille,e, IEand$band impact ioni5ation and solar cell efficienc%,J Bournal of 9pplied +h%sics, vol. 0/, no. 2, p. 1/81, 1??". ;"1< B. Werner, S. Folodins,i, and O. -ueisser, ITovel optimi5ation principles and efficienc% limits for semiconductor solar cells,J +h%sical Nevie# 'etters, vol. 02, no. 2/, pp. "381H/, 1??/. ;"2< S. Folodins,i, B. Werner, . Wittchen, and O. -ueisser, I-uantum efficiencies e.ceeding unit% due to impact ioni5ation in silicon solar cells,J 9pplied +h%sics 'etters, vol. 4", no. 10, pp. 2/08H0, 1??". ;""< N. Noss, ICfficienc% of hot$carrier solar energ% converters,J Bournal of 9pplied +h%sics, vol. 8", no. 8, pp. "31"H3, 1?32. ;"/< +. W]urfel, 9. Ero#n, . Oumphre%, and A. *reen, I+article conservation in the hot$carrier solar cell,J +rogress in +hotovoltaics, vol. 1", no. /, pp. 200H38, 2008. ;"8< 9. 'uque and 9. AartPQ, IIncreasing the efficienc% of ideal solar cells b% photon induced transitions at intermediate levels,J +h%sical Nevie# 'etters, vol. 03, p. 801/, 1??0.

;"4< 9. S. Ero#n, A. 9. *reen, and N. +. =or,ish, I'imiting efficienc% for a multi$band solar cell containing three and four bands,J +h%sica C, vol. 1/, pp. 121H8, 2002. ;"0< A. 'ev% and =. Oonsberg, ISolar cell #ith an intermediate band of finite #idth,J in process for +h%sical Nevie# E, 2003. ;"3< 9. S. Ero#n and A. 9. *reen, IIntermediate band solar cell #ith man% bands& Ideal performance,J Bournal of 9pplied +h%sics, vol. ?/, pp. 4180H3, 200". ;"?< A. *reen, IAultiple band and impurit% photovoltaic solar cells& general theor% and comparison to tandem cells,J +rogress in +hotovoltaics, vol. ?, no. 2, pp. 1"0H//, 2001. ;/0< +. W]urfel, IEasic principles of solar cells and the possible impact of nano$structures,J in +roceedings of the "rd World =onference on +hotovoltaic Cnerg% =onversion, vol. =, Osa,a, Bapan, 200", pp. 2402H8. ;/1< 9. 'uque, 9. AartPQ, =. Stanle%, T. 'Pope5, '. =uadra, (. Uhou, B. '. +earson, and 9. AcFee, I*eneral equivalent circuit for intermediate band devices& potentials, currents and electroluminescence,J Bournal of 9pplied +h%sics, vol. ?4, no. 1, pp. ?0"H?, 200/. ;/2< . rup,e and +.W]urfel, IImproved spectral robustness of triple tandem solar cells b% combined seriesRparallel interconnection,J Bournal of 9pplied +h%sics, vol. ?4, no. /, pp. 2"/0H81, 200/. ;/"< W. Shoc,le% and W. . Nead Br., IStatistics of the recombinations of holes and electrons,J +h%sical Nevie#, vol. 30, pp. 3"8H3/2, 1?82. ;//< A. 2. 'ev% and =. Oonsberg, IIntraband absorption in solar cells #ith an intermediate band,J submitted to ICCC Clectron (evice 'etters, 2000. ;/8< C. :. Schubert, I=ambridge studies in semiconductor ph%sics and microelectronic engineering&1,J in (oping in III$) Semiconductors, O. 9hmed, A. +epper, and 9. Eroers, Cds. =ambridge, KF& =ambridge Kniversit% +ress, 1??", ch. 1, pp. /1H//. ;/4< +. WahnPon and =. ablero, I @b initi electronic structure calculations for metallic intermediate band formation in photovoltaic materials,J +h%sical Nevie# E, vol. 48, no. 14, pp. 148 118 H 1, 2002. ;/0< =. ablero and +. WahnPon, I9nal%sis of metallic intermediate$band formation in photovoltaic materials,J 9pplied +h%sics 'etters, vol. 32, no. 1, pp. 181H", 200". ;/3< F. 2u, W. Walu,ie#ic5, B. Wu, W. Shan, B. Eeeman, A. Scarpulla, O. (ubon, and +. Eecla, I(iluted II$)I o.ide semiconductors #ith multiple band gaps,J +h%sical Nevie# 'etters, vol. ?1, no. 2/, pp. 2/4 /0"H1, 200". ;/?< =. ablero, IClectronic and magnetic properties of 5ns doped #ith cr,J +h%sical Nevie# E, vol. 0/, no. 1?, pp. 1?8 20"H1, 2004. ;80< +. +alacios, B. :ernande5, F. Sanche5, B. =onesa, and +. Wahnon, I:irst$principles investigation of isolated band formation in half$metallic ti/ga1/p 6/>0."128$0.287,J +h%sical Nevie# E, vol. 0", no. 3, pp. 38 204 H 1, 2004. ;81< =. ablero, I=orrelation effects and electronic properties of =r$substituted SUn #ith an intermediate band,J Bournal of =hemical +h%sics, vol. 12", no. 11, p. 11/00?, 2008. ;82< (. Ne%nolds and S. =5%5a,, IAechanism for photovoltaic and photoconductivit% effects in activated =dS cr%stals,J +h%sical Nevie#, vol. ?4, no. 4, p. 1008, 1?8/. ;8"< *. *uettler and O.B. -ueisser, IImpurit% photovoltaic effect in silicon,J Cnerg% =onversion, vol. 10, no. 2, pp. 81H8, 1?00. ;8/< B. Eruns, W. Seifert, +. Wa#er, O. Winnic,e, (. Eraunig, and O. Wagemann, IImproved efficienc% of cr%stalline silicon solar cells due to heV implantation,J 9pplied +h%sics 'etters, vol. 4/, no. 20, pp. 2000H2, 1??/. ;88< O. Fasai, . Sato, and O. Aatsumura, IImpurit% photovoltaic effect in cr%stalline silicon solar cells,J in =onference Necord of the #ent% Si.th ICCC +hotovoltaic Specialists =onference $ 1??0 6=at. To.?0=E"40247, 1??0, pp. 218H13. ;84< S. +. Eremner, N. =or,ish, and =. E. Oonsberg, I(etailed balance efficienc% limits #ith quasi$fermi level variations,J ICCC ransactions on Clectron (evices, vol. /4, no. 10, pp. 1?"2H?, 1???. ;80< A. *reen, I+rospects for photovoltaic efficienc% enhancement using lo#$dimensional structures,J Tanotechnolog%, vol. 11, no. /, pp. /01H8, 2000. ;83< F. Earnham, E. Eraun, B. Telson, A. +a.man, =. Eutton, B. Noberts, and =. :o.on, IShort$circuit current and energ% efficienc% enhancement in a lo#$dimensional structure photovoltaic device,J 9pplied +h%sics 'etters, vol. 8?, no. 1, pp. 1"8H0, 1??1. ;8?< 9. AartPQ, '. =uadra, and 9. 'uque, I-uantum dot intermediate band solar cell,J in =onference Necord of the #ent%$Cighth ICCC +hotovoltaic Specialists =onference, 9nchorage, 9F, KS9, 2000, pp. ?/0H". ;40< 9. AartPQ, '. =uadra, and 9. 'uque, I+artial filling of a quantum dot intermediate band for solar cells,J ICCC ransactions on Clectron (evices, vol. /3, no. 10, pp. 2"?/H?, 2001. ;41< 9. AartPQ, '. =uadra, and 9. 'uque, IIntermediate band solar cells,J in Te.t *enerations +hotovoltaicsL Oigh Cfficienc% through :ull Spectrum Ktili5ation, 9. AartPQ and 9. 'uque, Cds. Eristol& Institute of +h%sics +ublishing, 200/, ch. 0, pp. 180H140. ;42< 9. 'uque, 9. AartPQ, T. 'Pope5, C. 9ntolin, C. =Panovas, =. Stanle%, =. :armer, '. B. =aballero, '. =uadra, and B. '. Ealen5ategui, IC.perimental anal%sis of the quasi$fermi level split in quantum dot intermediate$band solar cells,J 9pplied +h%sics 'etters, vol. 30, no. 3, p. 03"808, 2008.

;4"< 9. 'uque, 9. AartPQ, T. 'Pope5, C. 9ntolin, C. =Panovas, =. Stanle%, =. :armer, and +. (ia5, IOperation of the intermediate band solar cell under nonideal space charge region conditions and half filling of the intermediate band,J Bournal of 9pplied +h%sics, vol. ??, no. ?, pp. ?/ 80"H1H?, 2004. ;4/< 9. AartPQ, C. 9ntolPQn, =. Stanle%, =.:armer, T. 'Pope5, +. (PQa5, C. =Panovas, +. 'inares, and 9. 'uque, I+roduction of photocurrent due to intermediate$to$conduction$band transitions& 9 demonstration of a ,e% operating principle of the intermediate$band solar cell,J +h%sical Nevie# 'etters, vol. ?0, no. 2/, pp. 2/0 001R1H/, 2004. ;48< 9. *. Torman, A. =. Oanna, +. (ippo, (. O. 'evi, N. =. Need%, B. S.Ward, and A.A. 9l$Bassim, IIn*a9sR*a9s -( superlattices& AO)+C gro#th, structural and optical characteri5ation, and application in intermediate$band solar cells,J in =onference Necord of the "1st ICCC +hotovoltaic Specialists =onference, Orlando, :', KS9, 2008, pp. /"H3. ;44< A. 2. 'ev% and =. Oonsberg, ITanostructured absorbers for multiple transition solar cells,J ICCC ransactions on Clectron (evices, vol. $, no. $, p. in print, 2003. ;40< 9. AartPQ, T. 'Pope5, C. 9ntolPQn, C. =Panovas, 9. 'uque, =. Stanle%, =. :armer, and +. (PQa5, ICmitter degradation in quantum dot intermediate band solar cells,J 9pplied +h%sics 'etters, vol. ?0, no. 2", pp. 2"" 810 H 1, 2000. ;43< =. ablero, 9. B. *arcia, B. B.:ernande5, +. +alacios, and +.WahnPon, I:irst principles characteri5ation of direct transitions for high efficienc% ne# photovoltaic materials,J =omputational Aaterials Science, vol. 20, no. 1$2, p. 83, 200". ;4?< =. ablero, +. +alacios, B. :ernande5, and +. Wahnon, I+roperties of intermediate band materials,J Solar Cnerg% Aaterials and Solar =ells, vol. 30, no. 1$/, pp. "2"H"1, 2008. ;00< =. ablero, I9nal%sis of the electronic properties of intermediate band materials as a function of impurit% concentration,J +h%sical Nevie# E, vol. 02, no. ", pp. "8 21" H 1, 2008. ;01< =. ablero, IClectronic and magnetic properties of UnS doped #ith =r,J +h%sical Nevie# E, vol. 0/, no. 1?, pp. 1?8 20" H 1, 2004. ;02< =. ablero, ISurve% of intermediate band materials based on UnS and Un e semiconductors,J Solar Cnerg% Aaterials and Solar =ells, vol. ?0, no. 8, pp. 833H8?4, 2004. ;0"< +. +alacios, F. Sanche5, B. =onesa, and +. Wahnon, I:irst principles calculation of isolated intermediate bands formation in a transition metal$doped chalcop%rite$t%pe semiconductor,J +h%sica Status Solidi 9, vol. 20", no. 4, pp. 1"?8H/01, 2004. ;0/< W. Fohn and '. Sham, ISelf$consistent equations including e.change and correlation effects,J +h%sical Nevie#, vol. 1/0, no. 9, p. 11"", 1?48. ;08< O. *unnarsson and E. 'undqvist, IC.change and correlation in atoms, molecules, and solids b% the spin$densit% formalism,J +h%sical Nevie# E, vol. 1", no. 10, pp. /20/H?3, 1?04. ;04< B. +erde#, C. AcAullen, and 9. Uunger, I(ensit%$functional theor% of the correlation energ% in atoms and ions& a simple anal%tic model and a challenge,J +h%sical Nevie# 9 6*eneral +h%sics7, vol. 2", no. 4, pp. 2038 H ?, 1?31. ;00< W. Walu,ie#ic5, F. 2u, B. Wu, B.W. 9ger III, W. Shan, A. Scrapulla, O. (ubon, and +. Eecla, IOighl% mismatched allo%s for intermediate band solar cells,J hin$:ilm =ompound Semiconductor +hotovoltaics. S%mposium 6Aaterials Nesearch Societ% S%mposium +roceedings )ol.3487, pp. 128H"0, 2008. ;03< F. 2u, W. Walu,ie#ic5, B.W. 9ger III, (. Eour, N. :arshchi, O. (ubon, S. 'i, I. Sharp, and C. Oaller, IAultiband *aT9s+ quaternar% allo%s,J 9pplied +h%sics 'etters, vol. 33, no. ?, p. 0?2110, 2004. ;0?< W. Shan, W. Walu,ie#ic5, B.W. 9ger III, C. Oaller, B. *eis5, (. :riedman, B. Olson, and S. Furt5, IEand anticrossing in gainnas allo%s,J +h%sical Nevie# 'etters, vol. 32, no. 4, pp. 1221 H /, 1???. ;30< W.Walu,ie#ic5, W. Shan, B.W. 9ger III, (. =hamberlin, C. Oaller, B. *eis5, (. :riedman, B. Olson, and S. Furt5, ITitrogen$induced modification of the electronic structure of group III$T$) allo%s,J in +hotovoltaics for the 21st =entur%. +roceedings of the International S%mposium. 6Clectrochem. Soc. +roceedings )ol.??$ 117 , Seattle, W9, KS9, 1???, pp. 1?0H?. ;31< W. Walu,ie#ic5, W. Shan, F. 2u, B.W. 9ger III, C. Oaller, I. Aiot,o#s,i, A. Seong, O. 9la#adhi, and 9. Namdas, IInteraction of locali5ed electronic states #ith the conduction band& band anticrossing in II$)I semiconductor ternaries,J +h%sical Nevie# 'etters, vol. 38, no. 0, pp. 1882H8, 2000. ;32< B. Wu, W. Shan, and W. Walu,ie#ic5, IEand anticrossing in highl% mismatched III) semiconductor allo%s,J Semiconductor Science and echnolog%, vol. 10, no. 3, pp. 340H?, 2002. ;3"< T. C,ins$(au,es, =. Oonsberg, and A. 2amaguchi, ISignature of intermediate band materials from luminescence measurements,J in =onference Necord of the hirt%$:irst ICCC +hotovoltaic Specialist =onference 6ICCC =at. To. 08=O"04037, 'a,e Euena )ista, :', KS9, 2008, pp. /?H8/. ;3/< '. =uadra, 9. AartPQ, and 9. 'uque, IInfluence of the overlap bet#een the absorption coefficients on the efficienc% of the intermediate band solar cell,J ICCC ransactions on Clectron (evices, vol. 81, no. 4, pp. 1002H0, 200/. ;38< A. Uundel, W. =sas5ar, and 9. Cndr]os, I(etailed e.perimental investigation of a local defect la%er used for si solar cells,J 9pplied +h%sics 'etters, vol. 40, no. 24, pp. "?/8 H 0, 1??8.

;34< F. 2u, W. Walu,ie#ic5, A. Scarpulla, O. (ubon, W. Shan, B. Wu, B. Eeeman, and +. Eecla, IS%nthesis and properties of highl% mismatched ii$o$vi allo%s,J ICC +roceedings$Optoelectronics, vol. 181, no. 8, pp. /82 H ?, 200/. ;30< B. I. +an,ove, Optical processes in semiconductors, ser. +rentice$Oall electrical engineering series. Solid state ph%sical electronics series. Cngle#ood =liffs, Te# Berse%& +rentice$Oall, 1?01, vol. 11, pp. ?"H/. ;33< A. =ardona, Aodulation Spectroscop%, ser. Solid State +h%sics& 9dvances in Nesearch and 9pplications. Te# 2or, and 'ondon& 9cademic +ress, 1?4?, vol. 11. ;3?< (. 9spnes, I hird$derivative modulation spectroscop% #ith lo#$field electrore$flectance,J Surface Science, vol. "0, pp. /13 H /2, 1?0". ;?0< :. +olla, and O. Shen, IAodulation spectroscop% of semiconductors& bul,Rthin film, microstructures, surfacesRinterfaces and devices,J Aaterials Science ^ Cngineering N& Neports, vol. N10, no. 0$3, pp. 208 H "0/, 1??". ;?1< :. Naga%, B. Wolter, 9. AartPQ, and *. 9raPujo, IC.perimental anal%sis of *a9s$In*a9s A-W solar cells,J in 1??/ ICCC :irst World =onference on +hotovoltaic Cnerg% =onversion. =onference Necord of the #ent% :ourth ICCC +hotovoltaic Specialists =onference$1??/ 6=at.To.?/=O""48$/7, vol. 2, Wai,oloa, OI, KS9, 1??/, pp. 108/H3. ;?2< T. C,ins$Fau,es, B. Earnes, F. Earnham, B. =onnoll%, A. Aa55er, B. =lar,, N. *re%, *. Oill, A. +ate, and B. Noberts, IStrained and strain$balanced quantum #ell devices for high$efficienc% tandem solar cells,J Solar Cnerg% Aaterials and Solar =ells, vol. 43, no. 1, pp. 01H30, 2001. ;?"< T. C,ins$(au,es, F. Earnham, B. =onnoll%, B. Noberts, B. =lar,, *. Oill, and A. Aa55er, IStrain$balanced *a9s+RIn*a9s quantum #ell solar cells,J 9pplied +h%sics 'etters, vol. 08, no. 24, pp. /1?8H0, 1???. ;?/< F. Earnham, I. Eallard, B. =onnoll%, T. C,ins$(au,es, E. Fluftinger, B. Telson, =. Nohr, and A. Aa55er, INecent results on quantum #ell solar cells,J Bournal of Aaterials Science& Aaterials in Clectronics, vol. 11, no. 0, pp. 8"1 H 4, 2000. ;?8< T. 'Pope5, 9. AartPQ, 9. 'uque, =. Stanle%, =. :armer, and +. (PQa5, IC.perimental anal%sis of the operation of quantum dot intermediate band solar cells,J Bournal of Solar Cnerg% Cngineering, ransactions of the 9SAC, vol. 12?, no. ", pp. "1?H"22, 2000. ;?4< A. 2. 'ev% and =. Oonsberg, IAodeling of nanostructured materialsL photoabsorption based on parabolic band appro.imations 6contract S9 $8$//200$017,J Tational Nene#able Cnerg% 'aborator%, *olden, =O, KS9, ech. Nep., 9ug. " 2000. ;?0< A. 2. 'ev% and =. Oonsberg, I9bsorption coefficients of an intermediate band absorbing medium under parabolic band appro.imations,J in process for +h%sical Nevie# E, 2003. ;?3< A. 2. 'ev%, T. B. C,ins$(au,es, and =. Oonsberg, I+hotoluminescent signature of absorbing medium #ith deep levels based upon absorption coefficients derived from parabolic$band appro.imations,J in +roc. CK+)SC= 22, Ailan, Ital%, 2000, pp. H. ;??< C. sui, B. Telson, F. Earnham, =. Eutton, and B. Noberts, I(etermination of the quasi$fermi$level separation in single$quantum$#ell p-i-n diodes,J Bournal of 9pplied +h%sics, vol. 30, no. 3, pp. /8??H40", 1??4. ;100< B. Telson, B. Earnes, T. C,ins$(au,es, E. Fluftinger, C. sui, F. Earnham, =. . :o.on, . =heng, and B. S. Noberts, IObservation of suppressed radiative recombination in single quantum #ell p$i$n photodiodes,J Bournal of 9pplied +h%sics, vol. 32, no. 12, pp. 42/0H4, 1??0. ;101< T. C,ins$(au,es, B. Telson, B. Earnes, F. Earnham, E. Fluftinger, C. sui, =. :o.on, . =heng, and B. Noberts, INadiative currents in quantum$#ell solar cells,J +h%sica C, vol. 2, no. 1$/, pp. 101H4, 1??3. ;102< E. Fluftinger, F. Earnham, B. Telson, . :o.on, and . =heng, I emperaturedependent stud% of the quasi$fermi level separation in double quantum #ell p$i$n structures,J in Aicroelectronic Cngineering, vol. 81$ 82, no. 1$/, 9ntal%a, ur,e%, 2000, pp. 248H0/. ;10"< E. Fluftinger, F. Earnham, B. Telson, . :o.on, and . =heng, I emperaturedependent stud% of the radiative losses in double$quantum #ell solar cells,J Solar Cnerg% Aaterials and Solar =ells, vol. 44, no. 1$/, pp. 801H?, 2001. ;10/< F. Earnham, I. Eallard, B. =onnoll%, T. C,ins$(au,es, E. Fluftinger, B. Telson, and =. Nohr, I-uantum #ell solar cells,J +h%sica C, vol. 1/, no. 1$2, pp. 20 H "4, 2002. ;108< F. Earnham, +. 9bbott, I. Eallard, (. Eushnell, B. =onnoll%, T. C,ins$(au,es, A. Aa55er, B. Telson, =. Nohr, . ibbits, N. 9ire%, *. Oill, and B. Noberts, INecent results on quantum #ell solar cells,J in +roceedings of "rd World =onference on +hotovoltaic Cnerg% =onversion 6ICCC =at. To.0"=O"0/?07, vol. )ol. 1, Osa,a, Bapan, 200", pp. 404 H 11. ;104< T. C,ins$(au,es, =. =alder, I. Eallard, F. Earnham, B. Telson, B. Noberts, and *. Oill, I-uantum #ell and bul, quasi$fermi level behaviour under illuminated conditions,J in +roceedings of "rd World =onference on +hotovoltaic Cnerg% =onversion 6ICCC =at. To.0"=O"0/?07, vol. )ol.", 200", pp. 2002 H 8. ;100< =. Summonte, A. Eiavati, C. *abilli, N. *alloni, S. *uerri, N. Ni55oli, and :. Uignani, ISpectral behavior of solar cells based on the _junction near local defect la%er! design,J 9pplied +h%sics 'etters, vol. 4", no. 4, pp. 038H0, 1??". ;103< A. Feevers and A. *reen, IC.tended infrared response of silicon solar cells and the impurit% photovoltaic effect,J Solar Cnerg% Aaterials and Solar =ells, vol. /1$/2, pp.1?8H20/, 1??4.

;10?< O. Fasai and O. Aatsumura, IStud% for improvement of solar cell efficienc% b% impurit% photovoltaic effect,J in Solar Cnerg% Aaterials and Solar =ells, vol. /3, no. 1$/,1??0, pp. ?"H100. ;110< T. C,ins$(au,es, I. Eallard, =. =alder, F. Earnham, *. Oill, and B. Noberts, I+hotovoltaic efficienc% enhancement through thermal up$conversion,J 9pplied +h%sics 'etters, vol. 32, no. 12, pp. 1?0/ H 4, 200". ;111< F. Earnham, B. =onnoll%, +. *riffin, *. Oaarpaintner, B. Telson, C. sui, 9. Uachariou, B. Osborne, =. Eutton, *. Oill, A. Oop,inson, A. +ate, B. Noberts, and . :o.on, I)oltage enhancement in quantum #ell solar cells,J Bournal of 9pplied +h%sics, vol. 30, no. 2, pp. 1201H4, 1??4. ;112< E. Fochman, 9. (. Stiff$Noberts, S. =ha,rabarti, B. (. +hillips, S. Frishna, B. Singh, and +. Ehattachar%a, I9bsorption, carrier lifetime, and gain in In9s$*a9s quantumdot infrared photodetectors,J ICCC Bournal of -uantum Clectronics, vol. "?, no. ",pp. /8?H40, 200". ;11"< S. Fettemann and B.$F. *uillemoles, I'imiting efficienc% of '(S solar cells,J in 1" th Curopean +hotovoltaic Solar Cnerg% =onference, Tice, :rance, 1??8, pp. 11?H21. ;11/< +. *ibart, :. 9u5el, B.$=. *uillaume, and F. Uahraman, IEelo# band$gap IN response of substrate$free *a9s solar cells using t#o$photon up$conversion,J Bapanese Bournal of 9pplied +h%sics 1, vol. "8, no. 3, pp. //01H2, 1??4. ;118< . rup,e, A. 9. *reen, and +. W]urfel, IImproving solar cell efficiencies b% do#nconversion of high$ energ% photons,J Bounal of 9pplied +h%sics, vol. ?2, pp. 1443H0/, 2002. ;114< :. Oatami, W. Aasselin,, and B. Oarris, I=olour$tunable light$emitting diodes based on In+R*a+ nanostructures,J Tanotechnolog%, vol. 10, no. 18, pp. "00"H4, 2004. ;110< S.$(. =hen, 2.$2. =hen, and S.$=. 'ee, I ransverse$electric$field$enhanced response in In9sR9l*a9sR*a9s quantum$dot infrared photodetectors,J 9pplied +h%sics 'etters, vol. 34, no. 28, p. 28"10/, 2008. ;113< 9. (e )os and E. (esoete, IOn the ideal performance of solar cells #ith larger$thanunit% quantum efficienc%,J Solar Cnerg% Aaterials and Solar =ells, vol. 81, no. "$/, pp. /1"H2/, 1??3. ;11?< 9. 'uque, 9. AartPQ, and '. =uadra, I hermod%namic consistenc% of sub$bandgap absorbing solar cell proposals,J ICCC ransactions on Clectron (evices, vol. /3, no. ?, pp. 2113H2/, 2001. ;120< . rup,e, A. 9. *reen, and +. W]urfel, Bournal of 9pplied +h%sics, vol. ?2, p. 1443, 2002. ;121< +. Eardeen, :. B. Elatt, and '. O. Oall, IIndirect transitions from the valence to the conduction bands,J in +hotoconductivit% =onference, N. *. Erec,enridge, Cd.,9tlantic =it%, TB, KS9, 1?8/, pp. 1/4H18/. ;122< A. 2. 'ev% and =. Oonsberg, INapid and precise calculations of energ% and particle flu. for detailed$ balance photovoltaic applications,J Solid$State Clectronics, vol. 80, pp. 1/00H8, 2004. ;12"< N. =. 9lig, S. Eloom, and =. W. Stuc,, IScattering b% ioni5ation and phonon emission in semiconductors,J +h%sical Nevie# E, vol. 22, no. 12, pp. 8848H32, 1?30. ;12/< N. Schaller and ). Flimov, IOigh efficienc% carrier multiplication in +bSe nanocr%stals& Implications for solar energ% conversion,J +h%sical Nevie# 'etters, vol. ?2, no. 13, pp. 134 401H1, 200/. ;128< A. =. Eeard, F. +. Fnutsen, +. 2u, B. A. 'uther, -. Song, W. F. Aet5ger, N. B. Cllingson, and 9. B. To5i,, IAultiple e.citon generation in colloidal silicon nanocr%stals,J Tano 'etters, vol. 0, no. 3, pp. 2804H12, 2000. ;124< O. Aadelung, Introduction to Solid$State heor%. Oeidelberg& Springer$)erlag, 1?03, pp. 230,"32,/"8H //0. ;120< O. '. 'a5aren,ova and 9. 9. Ealandin, IAiniband formation in a quantum dot cr%stal,J Bournal of 9pplied +h%sics, vol. 3?, pp. 880?H18, 2001. ;123< 9. AartPQ, '. =uadra, and 9. 'uque, I(esign constraints of the quantum$dot intermediate band solar cell,J +h%sica C, vol. 1/, no. 1$2, pp. 180H0, 2002. ;12?< A. 2. 'ev%, 9. AartPQ, =. Oonsberg, and 9. 'uque, I=alculation of the band properties of quantum dot intermediate band solar cells #ith h%drogenic impurities,J in 1? th Curopean +hotovoltaic Cnerg% =onference, +aris, :rance, 200/, pp. ""2H8. ;1"0< 9. Sibille, IAiniband transport,J in Semiconductor SuperlatticesL *ro#th and Clectronic +roperties, O. . *rahn, Cd. Singapore& World Scientific, 1??8, ch. 2, p. "0. ;1"1< A. 'ev%, =. Oonsberg, 9. Aarti, and 9. 'uque, I-uantum dot intermediate band solar cell material s%stems #ith negligible valence band offsets,J in =onference Necord of the hirt%$:irst ICCC +hotovoltaic Specialist =onference 6ICCC =at. To. 08=O"04037, 'a,e buena )ista, :', KS9, 2008, pp. ?0H". ;1"2< 2. Sugi%ama, 2. Ta,ata, F. Imamura, S. Auto, and T. 2o,o%ama, IStac,ed In9s selfassembled quantum dots on 60017 *a9s gro#n b% molecular beam epita.%,J Bapanese Bournal of 9pplied +h%sics, +art 1 6Negular +apers ^ Short Totes7, vol. "8, no. 2E, pp. 1"20H/, 1??4. ;1""< F. Shiramine, 2. Oorisa,i, (. Su5u,i, S. Itoh, 2. Cbi,o, S. Auto, 2. Ta,ata, and T. 2o,o%ama, I CA observation of threading dislocations in In9s self$assembled quantum dot structure,J Bournal of =r%stal *ro#th, vol. 208, no. /, pp. /41H4, 1???. ;1"/< =. O. Noh, 2. B. +ar,, F. A. Fim, 2. A. +ar,, :. F. Fim, and F. E. Shim, I(efect generation in multi$ stac,ed In9s quantum dotR*a9s structures,J Bournal of =r%stal *ro#th, vol. 224, no. 1, pp. 1H0, 2001. ;1"8< F. Ste#art, A. Euda, B. Wong$'eung, '. :u, =. Bagadish, 9. Stiff$Noberts, and +. Ehattachar%a, IInfluence of rapid thermal annealing on a "0 stac, In9sR*a9s quantum dot infrared photodetector,J Bournal of 9pplied +h%sics, vol. ?/, no. 3, pp.823"H?, 200".

;1"4< A. *utiPerre5, A. Oop,inson, O. 2. 'iu, B. S. Tg, A. Oerrera, (. *on5Pale5, N. *arcia,and N. Eeanland, IStrain interactions and defect formation in stac,ed In*a9s quantum dot and dot$in$#ell structures,J +h%sica C, vol. 24, no. 1$/, pp. 2/8H281, 2008. ;1"0< F. 9,ahane, T. Ohtani, 2. O,ada, and A. Fa#abe, I:abrication of ultra$high densit% In9s$stac,ed quantum dots b% strain$controlled gro#th on In+6"117E substrate,J Bournal of =r%stal *ro#th, vol. 2/8, pp. "1H"4, 2002. ;1"3< +. 'ever, O. O. an, and =. Bagadish, IIn*a9s quantum dots gro#n #ith *a+ strain compensation la%ers,J Bournal of 9pplied +h%sics, vol. ?8, no. 10, pp. 8010H/, 200/. ;1"?< U. O. Uhang, =. :. Su, F. =. Osieh, and F. 2. =heng, I(efect$free 80$la%er strainbalanced In9s quantum dots gro#n on In9l*a9sRIn+ for infrared photodetector applications,J Bournal of =r%stal *ro#th, vol. 203, no. 1$/, pp. 41H4, 2008. ;1/0< F. 9,ahane, T. 2amamoto, and T. Ohtani, I'ong$#avelength light emission from In9s quantum dots covered b% *a9sSb gro#n on *a9s substrates,J +h%sica C, vol. 21, pp. 2?8H2??, 200/. ;1/1< U. O. Uhang, F. 2. =heng, =. :. Su, and F. =. Osieh, I(efect$free 100$la%er strainbalanced In9s quantum dot structure gro#n on In+ substrate,J 9pplied +h%sics 'etters, vol. 3?, no. 4, p. 4"118, 2008. ;1/2< . rup,e, A. 9. *reen, and +. W]urfel, IImproving solar cell efficiencies b% upconversion of sub$band$ gap light,J Bournal of 9pplied +h%sics, vol. ?2, p. /110, 2002. ;1/"< K. 'aheld, :. +edersen, and +. Oemmer, IC.citons in t%pe$II quantum dots& finite offsets,J +h%sical Nevie# E, vol. 82, no. /, pp. 24?0H00", 1??8. ;1//< =.$F. Sun, 9. Wang, B. Eo#ers, E. Erar, O.$N. Elan,, O. Froemer, and A. +il,uhn, IOptical investigations of the d%namic behavior of *aSbR*a9s quantum dots,J 9pplied +h%sics 'etters, vol. 43, no. 11, pp. 18/"H8, 1??4. ;1/8< O. Aune,ata, . Smith, III, :. :ang, '. Csa,i, and '. =hang, IClectrons and holes in In9s$*a69l7Sb69s7 quantum #ells,J Bournal de +h%sique =olloque, vol. /3, no. =$8, pp. 181H/, 1?30. ;1/4< I. )urgaftman, B. N. Ae%er, and '. N. Nam$Aohan, IEand parameters for III$) compound semiconductors and their allo%s,J Bournal of 9pplied +h%sics, vol. 3?, no. 11, pp. 8318H8308, 2001. ;1/0< T. C,ins$(au,es, F. Fa#aguchi, and B. Uhang, IStrain$balanced criteria for multiple quantum #ell structures and its signature in S$ra% roc,ing curves,J =r%stal *ro#th ^ (esign, vol. 2, no. /, pp. 230H?2, 2002. ;1/3< T. Tunta#ong, S. Eirudavolu, =. Oains, S. Ouang, O. Su, and (. Ouffa,er, ICffect of strain$ compensation in stac,ed 1." m In9sR*a9s quantum dot active regions gro#n b% metalorganic chemical vapor deposition,J 9pplied +h%sics 'etters, vol. 38, no. 18, pp. "080H2, 200/. ;1/?< C. Nibeiro, N. Aalte5, W. =arvalho, (. Kgarte, and *. Aedeiros$Nibeiro, IOptical and structural properties of In9s+ ternar% self$assembled quantum dots embedded in *a9s,J 9pplied +h%sics 'etters, vol. 31, no. 14, pp. 2?8"H8, 2002. ;180< N. '. Aalte5, C. Nibeiro, W. =arvalho Br., (. Kgarte, and *. Aedeiros$Nibeiro, I=ontrolling allo% composition of In9s+ self$assembled quantum dots embedded in *a9s,J Bournal of 9pplied +h%sics, vol. ?/, no. 8, pp. "081H4, 200". ;181< O. 2. 'iu, A. B. Steer, . B. Eadcoc,, (. B. Ao#bra%, A. S. S,olnic,, +. Tavaretti, F. A. *room, A. Oop,inson, and N. 9. Oogg, I'ong$#avelength light emission and lasing from In9sR*a9s quantum dots covered b% a *a9sSb strain$reducing la%er,J 9pplied +h%sics 'etters, vol. 34, p. 1/"103, 2008. ;182< O. 2. 'iu, A. B. Steer, . B. Eadcoc,, (. B. Ao#bra%, A. S. S,olnic,, :. Suare5, B. Tg, A. Oop,inson, and B. +. N. (avid, INoom$temperature 1.4 m light emission from In9sR*a9s quantum dots #ith a thin *a9sSb cap la%er,J Bournal of 9pplied +h%sics, vol. ??, p. /410/, 2004. ;18"< A. =opel, A. =. Neuter, C. Fa.iras, and N. A. romp, ISurfactants in epita.ial gro#th,J +h%sical Nevie# 'etters, vol. 4", no. 4, pp. 4"2H8, 1?3?. ;18/< A. 'arsson, W. Ti, F. Boelsson, and *. Oansson, I*ro#th of high qualit% *e films on Si6l l l7 using Sb as surfactant,J 9pplied +h%sics 'etters, vol. 48, no. 11, pp. 1/0?H11,1??/. ;188< O. Shimi5u and S. Saravanan, IEuffer$material dependence of In9s quantum dots on *a9s substrate,J 9pplied +h%sics 'etters, vol. 33, no. /, p. /111?, 2004. ;184< =. ablero, IOptical properties for *a"2+"1=r and *a"1 +"2=r intermediate band materials,J Solar Cnerg% Aaterials and Solar =ells, vol. ?0, no. 2, pp. 20"H12, 2004. ;180< (. '. (e.ter, I9bsorption near the edge in insulators,J in +hotoconductivit% =onference, N. *. Erec,enridge, Cd., 9tlantic =it%, TB, KS9, 1?8/, pp. 188H3". ;183< O. 2. :an, A. '. Shepherd, and W. Spit5er, IInfrared absorption and energ%$band structure of germanium and silicon,J in +hotoconductivit% =onference, N. *. Erec,enridge, Cd., 9tlantic =it%, TB, KS9, 1?8/, pp. 13/H202. ;18?< O. :an, IInfra$red absorption in semiconductors,J Neports on +rogress in +h%sics,vol. 1?, pp. 100H18/, 1?84. ;140< S. +antelides and =. Sah, I heor% of locali5ed states in semiconductors. i. ne# results using an old method,J +h%sical Nevie# E, vol. 10, no. 2, pp. 421H"0, 1?0/. ;141< C. B. Bohnson, I9bsorption near the fundamental edge,J in Semiconductors and Semimetals, N. F. Willardon and 9. =. Eeer, Cds. Te# 2or,& 9cademic +ress, 1?40, vol. ", ch. 4, p. 20".

;142< A. 9sada, 2. Ai%amoto, and 2.Suematsu, I*ain and the threshold of three dimensional quantum$bo. lasers,J ICCC Bournal of -uantum Clectronics, vol. -C$22, no. ?,pp. 1?18H21, 1?34. ;14"< W.$2. Wu, B. Schulman, . Osu, and K. Cfron, ICffect of si5e nonuniformit% on the absorption spectrum of a semiconductor quantum dot s%stem,J 9pplied +h%sics 'etters, vol. 81, no. 10, pp. 010H2, 1?30. ;14/< F. Fang, E. Ac*innis, Sandalphon, 2. Ou, S. Foch, T. +e%ghambarian, 9. A%s%ro#ic5, '. 'iu, and S. Nisbud, I=onfinement$induced valance$band mi.ing in cds quantum dots observed b% t#o$photon spectroscop%,J +h%sical Nevie# E, vol. /8, no. 0, pp. "/48H3, 1??2. ;148< . rup,e, A. 9. *reen, and +. W]urfel, IImproving solar cell efficiencies b% upconversion of sub$band$ gap light,J Bounal of 9pplied +h%sics, vol. ?2, pp. /110H22, 2002. ;144< F. =hoi, E. 'evine, =. Eethea, B. Wal,er, and N. Aali,, IInfrared photoelectron tunneling spectroscop% of strongl% coupled quantum #ells,J +h%sical Nevie# E, vol. "?, no. 11, pp. 302?H"2, 1?3?. ;140< C. Aartinet, C. Nosencher, :. 'uc, +. Eois, C. =ostard, and S. (ela\Qtre, IS#itchable bicolor 68.8$?.0 m7 infrared detector using as%mmetric *a9sR9l*a9s multiquantum #ell,J 9pplied +h%sics 'etters, vol. 41, no. ", pp. 2/4H3, 1??2. ;143< S. =ha,rabarti, S. Su, +. Ehattachar%a, *. 9ri%a#ansa, and 9. +erera, I=haracteristics of a multicolor In*a9s$*a9s quantum$dot infrared photodetector,J ICCC +hotonics echnolog% 'etters, vol. 10, no. 1, pp. 103H130, 2008. ;14?< 9. A. Stoneham, heor% of (efects in Solids& Clectronic Structure of (efects in Insulators and Semiconductors. O.ford& =larendon +ress, 1?08, p. 20/. ;100< A. 2. 'ev% and T. A. Cl#a,il, I-uarterl% revie#,J Tational Nene#able Cnerg% 'aborator%, *olden, =O, KS9, ech. Nep., Bune 2004. ;101< A. 2. 'ev% and =. Oonsberg, I-uarterl% revie#& Salient features of intermediate band absorbing media,J Tational Nene#able Cnerg% 'aborator%, *olden, =O, KS9, ech. Nep., Bul% 2000. ;102< C. Nosencher and E. )inter, Optoelectronics, english edition ed. =ambidge, KF& =ambridge Kniversit% +ress, 2002, chapter 0, pp. "00, "01H/. ;10"< 9. B. To5i,, I-uantum dot solar cells,J +h%sica C, vol. 1/, pp. 118H20, 2002. ;10/< 9. (e)os, Cndoreversible hermod%namics of Solar Cnerg% =onversion. O.ford& O.ford Kniversit% +ress, 1??2, pp. 1H12,10,21,?2,?4,??,120,121H1"1. ;108< C. 9ntolPQn, 9. AartPQ, and 9. 'uque, ICnerg% conversion efficienc% limit of series connected intermediate band solar cells,J in 21th Curopean +hotovoltaic Solar Cnerg% =onference, (resden, *erman%, 2004, pp. /12H8. ;104< S. (ahal, I, 3p method for band structure calculation of intermediate band solar cell,J Knpublished, annotated draft of a poster presentation, Tov. 2000, personal communication. ;100< *. Tarvae5 and 9. Uunger, I=alculation of conduction$to$conduction and valence$tovalence transitions bet#een bound states in 6In,*a79sR*a9s quantum dots,J +h%sical Nevie# E, vol. 08, no. 3, pp. 38 "04 H 1, 2000. ;103< 2. Uhang, 9. +ancholi, and ). Stoleru, ISi5e$dependent radiative lifetime in verticall% stac,ed 6In,*a79s quantum dot structures,J 9pplied +h%sics 'etters, vol. ?0, no. 13, pp. 13" 10/H1, 2000. ;10?< O. 2u, S. '%cett, =. Noberts, and N. Aurra%, I ime resolved stud% of self$assembled In9s quantum dots,J 9pplied +h%sics 'etters, vol. 4?, no. 24, pp. /030 H ?, 1??4. ;130< 9. AartPQ, T. 'Pope5, C. 9ntolPQn, C. =Panovas, =. Stanle%, =. :armer, '. =uadra, and 9. 'uque, ITovel semiconductor solar cell structures& he quantum dot intermediate band solar cell,J hin Solid :ilms, vol. 811$812, pp. 4"3 H //, 2004. ;131< *. No#land, . Oosea, S. Aali,, (. =hilds, and N. Aurra%, I9 photomodulated reflectance stud% of In9sR*a9s self$assembled quantum dots,J 9pplied +h%sics 'etters, vol. 0", no. 22, pp. "243 H 00, 1??3. ;132< B. Nojas$Namire5, 9. +ul5ara$Aora, C. =ru5$Oernande5, 9. +ere5$=enteno, A. Aelende5$'ira, ). Aende5$*arcia, and A. 'ope5$'ope5, I+hotoreflectance stud% of In9s quantum dots on *a9s6 n117 substrates,J +h%sica C, vol. "2, no. 1$2, pp. 1"? H /", 2004. ;13"< A. Aot%,a, *. Se,, N. Fudra#iec, B. Aisie#ic5, '. 'i, and 9. :iore, IOn the modulation mechanisms in photoreflectance of an ensemble of self$assembled In9sR*a9s quantum dots,J Bournal of 9pplied +h%sics, vol. 100, no. 0, pp. 00" 802 H, 2004. ;13/< *. Se,, F. N%c5,o, A. Aot%,a, B. 9ndr5eje#s,i, F. W%soc,a, B. Aisie#ic5, '. 'i, 9. :iore, and *. +atriarche, IWetting la%er states of In9sR*a9s self$assembled quantum dot structures& effect of intermi.ing and capping la%er,J Bournal of 9pplied +h%sics, vol. 101, no. 4, pp. 4" 8"? H 1, 2000. ;138< W. Nudno$Nud5iPns,i, *. Se,, B. Aisie#ic5, . 'amas, and 9. -uiv%, I he formation of self$assembled In9sR*a9s quantum dots emitting at 1." m follo#ed b% photore$flectance spectroscop%,J Bournal of 9pplied +h%sics, vol. 101, no. 0, p. 00"813, 2000. ;134< B.$N. 'ee, =.$N. 'u, W.$I. 'ee, and S.$=. 'ee, IInvestigation of populated In9sR*a9s quantum dots b% photoluminescence and photoreflectance,J +h%sica C, vol. 28, no. /, pp. 842 H3, 2008. ;130< B. +rieto, *. 9rmelles, . Kt5meier, :. Eriones, B. :errer, :. +eirPo, 9. =ornet, and B. Aorante, IStrain$ induced quenching of optical transitions in capped self$assembled quantum dot structures,J +h%sical Nevie# 'etters, vol. 30, no. 8, pp. 10?/ H 0, 1??3.

;133< N. Eurden and B. (. :aires, Tumerical 9nal%sis, Si.th Cdition. O.ford& Eroo,sR=ole +ublishing =ompan%, 1??0, p. 1??. ;13?< *. '. 9raPujo and 9. AartPQ, I*enerali5ed detailed balance theor% to calculate the ma.imum efficienc% of solar cells,J in +roceedings of the 11th C= +)SC=,Aontreau., S#it5erland, 1??2, pp. 1/2H8. ;1?0< A. *oano, I9lgorithm 0/8& computation of the complete and incomplete :ermi$(irac integral,J 9=A ransactions on Aathematical Soft#are, vol. 21, no. ", pp. 221H"2, 1??8.