Vol. 32, No.5 Journal of Semiconductors May 2011 Physical properties of sprayed antimony doped tin oxide thin films: The role of thickness A.R. Babar', S. S. Shinde’, A.V. Moholkar!, C. H. Bhosale!, J. H. Kim?, and K. Y. Rajpure!’* ‘ectrochemical Materials Laboratory, Department of Physics, Shivaji Univesity, Kolhapur-416 004, Indie 2Department of Materials Science and Engineering, Chonnam Nationsl University, 300 Yongboug-Dong, Buk-Gu, ‘Gwangiu, 300-757, Soute Korea Abstract: Transparent conducting antimony doped tin oxide (Sb:SnO,) thin films have been deposited onto pre- heated glass substrates using a spray pyrolysis technique by varying the quantity of spraying solution. The struc- tural, morphological, X-ray photocleciron spectroscopy, opticel, photoluminescence and clectrieal properties ‘these films have been studied. Is found thatthe films are polyerystalline in nature with a tetragonal erystal struc- ture having orientation along the (211) and (112) planes. Polyhodrons like grains appear in the FE-SEM images ‘The average grain size increases with inereasing spraying quantity. The compositional analysis and electron be- haviour of Sb:SnO> thin films were studied using X-ray photoelectron spectroscopy. The binding enerey of Sn3dsj2 for all samples shows the Sn** bonding stat from SnOz. An intensive violet luminescence peak near 395 nm is ‘observed at room temperature due to oxygen vacancies or donor levels formed by Sb** ions. The film deposited with 20 ce solution shows 70 % transmittance at 550 nm leading to the highest figure of merit (2.11 x 10? 8~) ‘The resistivity and carrer concentration vary over 1,22 x 107 t0 0,89 x 10-® Stem and 5.19% 102° to 8.52 102° cm, respectively. Key words: semiconductors; microstructure; optical properties; electrical properties Do 2 10.1088/1674-4926/32/5/053001 1, Introduction, Electrically conductive materials with high optical trans- rmittance are key elements for thin film solar eells and display devices. Amongst them, transparent conductive oxides (TCO), based on high band gap, degenerate semiconductors are me- chanivally hard and can withstand high temperatures. Along with this, wide and direct band gap semiconductor materials are ‘of much interest for blue and ultraviolet (UV) optical devices, such as light-emitting diodes and laser diodes"). As wide band {gap semiconductors, SnO, and doped Sn0 are known to have 1 wide range of technological applications, such as transpar- cent conducting electrodes, dye-sensitized solar cells?) and chemical sensors, and now they seem to be more attrac- tive for their luminescence properties", Antimony doped tin oxide (Sb:SnO,) thin films are deposited by various methods, viz. sputtering”), chemical vapour deposition®), DC glow ischarge!"4, dip coating!*4, sol-gel!) and spray pyroly- sist), Spray pyrolysis sa promising technique for produc- ing sufficiently conductive end adherent Sb:Sn0, thin films in a cost-effective way. Kaneko et af investigated the physical properties of SbiSnO, thick films (4000-14000 A) deposited onto fused {quart borosilicate and soda lime glasses. They showed that the electrical resistivity and optical band gap are independent of film thickness deposited on fused quartz and borosilicate Ma et all reported the dependence of film thickness on the physical properties of Sn0:$b films deposited on flexible sub- strates by RF magnetron sputtering. They observed that mabil- ity increases with thickness and resistivity decreases. Agashe 1 Coresponding author, Email raipure@yahoo.com Received 25 October 2010, rovised manuscript received 8 December 2010 EEACC: 2520 et all) studied the competitive eects of film thickness and srowth rate in spray pyrolytically deposited fluorine-doped tin oxide films. The thickness evolution involved textured growth along the [200] orientation followed by a secondary promi- renee of [110] and [101] orientations. The growth rate induced effects avcelerated this change. The carier concentration and carrier mobility showed that the [200] oriented growth is tech- nologically advantageous and can be obtained using a wider ‘growth rate range of ~ 50-130 nm/min. Yannopoulos!”! stud ied the use of stannic oxide thick films that incorporate ant- ‘mony as a structural dopant for sensing combustible gases in ‘oxidizing and fixed water vapour-containing atmospheres. In the present investigation, we have studied the effect of| thickness on the physicochemical properties of Sb:SnO thin films synthesized by spray pyrolysis. The growth mechanism has been correlated to use these Films in gas sensor and opto- electronic devices. 2, Experimental ‘Stannie chloride (Thomas Baker) and antimony trichloride (ed. fine), respectively, were used as precursors for tin and an- timony. The glass substrates (75 x 25 x 1.2 mm*) supplied by [Blue Star, Mumbai, were used. The required amount of SbCly, dissolved in IM HCI was added to 2M aqueous SnCly-SH20 solution to obtain 2 at% Sb doping in the starting solution!" ‘This was taken as the stock solution, fen millilitres of propan- 2-01 was added to the ten millilitres of stock solution before spraying. The amount of SbCl; was kept fixed at 2 at% for an- timony doping, which has been found to be optimal for good © 2011 Chinese insite of Electronics 053001-1Semicond, 2011, 3245 AR Babar ef al Table 1. Various parameters estimated for sprayed Sb:SnO, thin film resistivity, n = carier concentration, e = mobility, = figure of mer 8 with various quantities of spraying solution (Ry = sheet resistance, p it, Ey = Fermi energy, ! = mean fee path, r= thickness, CS = crystallite size, ay = plasma frequency, %7 = transmittance ofthe films). Spans kp w = = FT TT solution (2) (10> Mem) (10®% mm) femPAV9) COA) (VY (A) fom) (am) (HOS Ha) 2.= 550mm quantity (eo) 20 Sar Ta sy oa ZT Ta 1607 To 19ST TT 30 165 13 63 875 oz TL 1526 969 245 3.65 31 0 S84 O89 852 749 ots Lm 14as tos 2756424 41 264 Ly — & is] vw] oi yy » 0 OOD so SS wD 29 deer) ‘Quantity oFspeaying sluion ce) Fig. 1. XRD patters ofthe Sh:Sa0> thin films deposited for vations Fig 2. Variation in average exystallite size of sprayed Sb:SuO, thin amounts of spraying olution. ‘quality films obtained earlier. The quantity of spraying solution ‘was varied from 10 to 40 cubic centimetres (ce). The substrates ‘were maintained at 475 °C optimal temperature for forma- tion of pyrolytically decomposed good quality Sb:SaO, films. TThese films were then allowed to cool at rooms temperature and, further used for structural, optical, electrical characterizations tc, The structural properties were studied by a powder X-ray diffractometer (Bruker D8 Advance, France) using Cu-Karra- diation in the span of 20°-80°, The morphology of the films ‘was observed by field emission scanning electron microscopy (FE-SEM, Model: JSM-6701F, Japan), XPS studies were car- tied out using model PHI-5400 type X-ray photoelectron spe troscopy (XPS, physical clectronics PHI 5400, USA) with a ‘monochromatic Mg-Ka' (1254 eV) radiation souree. An opti- cal absorption study was carried out in the wavelength range ‘of 200-1 100 nm using a double beam spectrophotometer (SHI- MADZU UV-1700, Japan). The electrical properties were stud- ied by using a Hall effect setup (Scientific Instruments, DHE- 21, India) i the Van der Pauw configuration. 3, Results and discussion 3.1. Structural analysis Table 1 shows the variation in film thickness as a fune- tion of the quantity of spraying solution, from which itis seen that the film thickness inereases with the quantity of spraying. solution. The expected reason for this isthe supply of more in- agredient ions with an increasing quantity of spraying solution. ‘The XRD patterns for the Sb:SnQa thin films grown on glass fms for different quantities of spraying solution substrates were studied in the 28 range of 20°80" shown in Fig. [Its seen that the material deposited is polyerystallineir- respective ofthe quantity of spraying solution, The presence of 4 tetragonal crystal structure has beca confirmed from match- ing of observed and standard d (inter planer spacing) values. [No other extra phases (such as SnO, Sn03 and S203) are ob- served inthe deposited thin films, Iti found that the film tends to grow in specific (211) and (112) crystallographic directions. However, as the quantity of solution is increased, the intensity ‘of the (211) peak decreases and the intensity of tae (112) peak increases, indicating a slight erystal reorientation effect. The variation in preferred orientation with respect to the quantity of spraying solution may be attributed to the change in film thickness! Above 40 ce, milky and powdery films resulted ‘The crystallite size D’is caleulated using Scherrer's for- mule, 0.98 Feast Where D is the erystallite size, f is the broadening of the diffraction line measured at half ofits maximum intensity (rad.) FWHM and is the X-ray wavelength (1.5406 A), The vari= ation in average crystallite size with the quantity of spraying solution for Sb:SnO> thin films is shown in Fig, 2, It is seen that the erystallite size inereases with an increase in spraying. solution, The analysis reveals that the quantities of spraying solution strongly influence the crystallite size as well as the thickness of the thi films. ‘The reflection intensities from cach XRD pattern contain mation related to the preferential or random growth of o inf 0530012,Semicond, 2011, 3215) 50. 40. © 30. — 101) bas — =o on > un) Fis 10. os oS 0 8 Quang of spaying slain (ce) ig. 3 Variation n TC (101), TC (211) and TC (112) of $b:S20, thin films for diferent quantities of spraying solution. ». » oS oS Quantity oF paying solution (ee) Fig. 4 Variation in standard deviation for quantities of spraying solu tion for Sb:Sn0 thin fils polycrystalline thin films, whichis studied by calculating the texture cooticient TCgq forall planes exing™) Fey Toinkry TOK) ~ TANS Faun] loan 2 where Zit is the measured intensity of X-ray reflection, Toya is the corresponding standard intensity from the JCPDS data card No-01-0625 and NV is the number of reflections ob- served inthe XRD patter, Figure 3 depts the variation inthe texture coefficient with the quantity of spraying solution forthe (101), (211) and (112) planes. For 20 ce solution, TCaaxa has a relatively higher value than the other planes (101) and (211) Ciara slightly dereases for 30 cc and further increases fora higher solution quantity (40 ce). This confirms the erystl re crientation effet. In order to understand the growth mechanism involved in spray deposited S:Sn0> films at various quantities of spraying solution, the standard deviation (0) was estimated by using the equation 8 AR Babar ef al Fig. 5. FE-SEM micrographs of Sb:SnO, thin films prepared for (2) 20, (6) 30, (¢) 40 ce spraying solution, Magnification: 20000 x, ‘where J stands for the relative intensity ofthe (hk!) plane. The variation in standard deviation with the quantity of spraying so- lution is shown in Fig. 4. Initially at 20 cc, the nucleation and adsorption-desorption phenomenon seems to be predominant, aa result of hoterogencous nucleation resulting in relatively higher o values. A decrease in o values with further increase in spraying solution suggests the onset of homogeneous nucle 3.2. Morphological study Figures 5(@)-S(e) show scanning electon micrographs (SEM) of Sb:Sn0, films deposited on glass substrates. Iris ob- served thatthe surface morphology ofthe films was strongly dependent upon the quantity of spraying solution. It is soen that the layers ate made up of grains with polyhedron like shapes. The presence of big and faceting nanocrystals observed inthese images present the fat tha the polyhedron crystallites are formed by coalescence. The average grain size increases 0530013,Semicond, 2011, 3215) AR Babar ef al ces, 10 "sho soa Binding cnorsy (eV) Fig. 6, XPS survey sean spectra of Sb:SnO2 thin films deposited for ferent quantities of spraying solution. (a) 20 ec. (6) 30 ee. (c) 40, sis se Saws Binding enrsy (eV) Fig. 7.SaXd narrow scan XPS spectra ofSb-SnO> thin films deposited for various quanties of spraying soltion, ‘with increasing spraying quantity. At 20 ce solution quantity, ‘small polyhedrons like grains are observed, As the quantity in- creased further, the polyhedron-like grains dwindled and were hardly distinguished from the small grains. The grains are ran- domly grown giving rise to scattering effec, thereby reducing, transmittance. 43.3. X-ray photoelectron spectroscopy Figure 6 shows the X-ray photoclectron spectroscopy (PS) survey sean of thin films deposited with various solu tion quantities (20, 30, 40 cc). The sample contains Sn, Sb, O and traces of C having a SnMNI auger peak with Sn3p, Sn34, Sn core levels. The presence of a Cs peak in the spectra can be attrbuted to contamination which resulted from the samples being exposed to air before the XPS measurements?" ‘Narrow sean XPS spectra of Sn3dstat forthe samples are shown in Fig. 7. The spectra show well-esolved doublets due to the Sn35j2 and 3éy/2 components corresponding to bind- ing energies of 486 86, 486.78, 486.73 eV and 495.29, 495.22, 495.19 eV for 20, 30,40 ce, respectively. The binding energy of Sn3dlsa is atributed to the Sn** bonding state, which agrees a, wis So Ss os Binding energy (eV) Fig. 8. Sb3d narrow sean XPS spectra of Sb:SnOp tin flms deposited at various quantities of spraying solution, wel withthe previous report. The gap between the Sibdy2 and Sida levels (= 8.45 eV) closely comesponds tothe O in SaO and Sn in S00, respectively), Figure 8 shows the narrow sean XPS spectra of Sh3d state for the samples de- posited with various solution quantities. Ata low doping con- entation of Sb, we observe the lower intensity peak of the Sb3dyya state, Terror etal reported thatthe major Sb ox- idation states existed for Sb°* state at a lower doping level and a Sb** state at higher doping level, They showed that the ‘Sb5+ and Sb** peak position was located at binding energies of $40.1 eV and 539.2 eV, respectively. In our study, all of the Samples show the binding energy of Sh3ds/s (shown in Fig. 8) in the region of 530.6-530.9 . indicating thet all antimony detected was in a pentavalent state (Sb5*)*), \Nartow scan XPS spectra ofthe Ols state for samples de- posited with various solution quantities (20-80 ce) ae shown {nFigs.9(a)-9(0). Gaussian curve iting ilustates tht the O1s peti has «doublet component; sich a phenomenon is common for oxides containing oxygen in multiple valence states!" The binding energies of Oi are $30.55, $52.02; 530.45, 531.72 and 530,37, 531.70 eV for 20, 30 and 40 ce, respectively. Gener- ally, the O1s peak observed inthe region 528530 eV hasbeen attributed to lattice oxygen. Ghuang et ai.) attributed the peak around 530.7-531.6 eV to oxygen in non-stoichiometic ‘Oxides inthe surface region, They observed chemisorbed O3 ‘on the metal surface jn 530-530.9 eV and surface oxides and hydroxides in 529,6-531.0 eV and $33.3 eV binding energy te- sions, respectively. Sharma etal have assigned the 532.€V peak to absorbed hydroxyl ions. Srinivasan et al 2! have at- tributed the peak at $31.7 eV to chemisorbed oxygen. On the basis of the above, the Ols peak observed inthe region 5$30,45-830.37 eV for SbiSnOp thin film prepared by spray pyrolysis in the present work canbe attributed to chemisorbed ‘oxygen. The peak appeared around $32 eV attributed tothe O11 _roup linked to Sn. This has been observed forall samples, i thin films deposited with a solu- tion quantity between 20 to 40 cv ata fixed substrate temper- ature of 7, = 475 °C. It is sen that transmittance decreases ‘with increasing solution quantity. The low transmittance is at tributed to increasing thickness, which causes surface darken- ing, At higher (30, 40 cc) solution quantities, it consists of more Sn! ions; therefore, films prepared with this solution 0. : 2». a a Wivelengh (om) 100 ig. 10. Variation of transmitance with wavelength for Sb:SnO> thin films deposited fr various quantities of spraying solution. 25«10 aon \\ sow | \ =3: alo” 300 abo” sto” ato” bo” wl” 900 Wavelength (am) Lost soaot Fig. [1. PL emission specira of Sb:SiO thin films for various quan tities of spraying solution, are thicker and consequenily less transparent, At higher thick- ness, the films tend to be powdery in nature and whitish in appearance. However, there isa slight shift in the absorption bband edge. The shift in the absorption edge can be accounted for by the inerease in carier concentration and blocking of low energy transitions! The transmittance of al of the films de- thin films deposited with 20, 30, 40 ce solution quantities is 16.07, 15.56, 14.44 A, respec- tively Since the values are considerably shorter shan the grain size (as seen in FE-SEM images), the Hall mobility is limited by the ionized impurity scattering rather than the grain bound- ary scattering. The film degenerae confirmed by evaluating the Fermi 053001-6Semicond, 2011, 3245 AR Babar ef al ‘energy using the relation oe=(25)(2)" © ‘The value of the effective mass (m* = 0.19m,) is eval- uated from the plasma frequency for antimoay doped SAO. films. The calculated value ofthe Fermi energy lis in the range of 1.24-1.72 eV (Table 1). Fermi energy values of Sb:Sn0; films are higher compared to kT’ at room temperature, which is evidence for the degenerate nature of the material, For optoelectronic device applications, the figure of meri (@) plays an important role, The device performance is deter- ‘mined from ¢ and is caleulated by using the formula), -= 6) POR ° where 7 the transmittance at 5$0 nm and Rsy is the sheet re- sistance. “The sheet resistance Rey is a main factor fr the Figure of ‘merit, which is calculated by the Van der Pauw technique. The variation inthe figure of merit wit solution quantity is shown in Table 1. The figure of merit decreases with respect to so- lution quantity. The obtained highest figure of merit is about 2.11 x 10727? for the film deposited with a 20 ce solution quantity 4, Conclusions The growth kinetics and physical properties of Sb:SnO thin films with the quantity of spraying solution have been successfully investigated by spray pyrolysis. These films are polycrystalline in nature, highly textured and have a tetrago- nal erystal structure with (211) and (112) reflections. The big and faceting polyhedron like nanocrystals are observed in the FE-SEM images. The analysis of core levels of the prepared films has been undertaken with the help of X-ray photoclec tron spectroscopy. Strong violet emission has been seen in the luminescence spectra, The highest figure of merit is achieved atabout2.11 x 10-* 2 ata 20 cc quantity of solution, These films are highly applicable to short wavelength optoelectronic devices and gas sensors, Acknowledgement One of the authors (A. R. Babar) is highly grateful to the University Grants Commission, New Delhi, for its support through a UGC meritorious fellowship, References [1] Vaufrey D, Khalife MB, Besland MP etal. Reatve ion etching of sol gel-processed transparent conductive oxide asa new ma organic light emitting diodes. Synthetic Metals, 2002, [2] Fl-Rire AY, Reda S M. 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