Selective Deposition of Conducting Polymers on

Hydroxyl-Terminated Surfaces with Printed Monolayers of

Alkylsiloxanes as Templates
Zheyuan Huang, Pen-Cheng Wang, and Al an G. MacDi armi d
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104
Younan Xi a and George Whi tesi des*
Department of Chemistry and Chemical Biology, Harvard University,
Cambridge, Massachusetts 02138
Received May 23, 1997. I n Final Form: September 17, 1997
X
Thi s paper descri bes the use of patterned sel f-assembl ed monol ayers (SAMs)i n area-sel ecti ve deposi ti on
of conducti ng pol ymers (pol ypyrrol e and pol yani l i ne) on insulating, hydroxyl -termi nated surfaces such as
Si /Si O2 and gl ass. Patterned SAMs of octadecyl si l oxane were generated on the hydroxyl -termi nated surfaces
usi ng mi crocontact pri nti ng; they defi ned and di rected the deposi ti on of conducti ng pol ymers. The rate
of deposi ti on on the hydrophobi c surface i s hi gher than that on the hydrophi l i c surface: i mmersi on of a
substrate patterned wi th a methyl -termi nated SAMi n an appropri ate aqueous pol ymeri zati on bath produced
a posi ti ve pattern of the conducti ng pol ymer on the surface. The conducti ng pol ymer deposi ted on the
hydrophobi c regi on of a surface compl etel y covered by the pol ymer coul d be readi l y removed by transferri ng
i t to adhesi ve tape to form a posi ti ve pattern on the tape, l eavi ng a negati ve pattern on the surface
of the substrate. The conducti ng pol ymer deposi ted on the hydrophobi c surface had a more extended
conformati on, and thus a hi gher conducti vi ty (approxi matel y 3 orders of magni tude i n di fference), than
that formed on the hydrophi l i c surface. The smal l est features of conducti ng pol ymers generated usi ng
these procedures were 2 m i n l ateral di mensi on. The edge roughness of these patterns was 0.5 m.
These patterned mi crostructures of conducti ng pol ymers were conducti ve; they have been used as el ectrodes
i n di spl ay devi ces based on pol ymer di spersed l i qui d crystal s.
Introduction
Conjugated organi cpol ymers are i ncreasi ngl y i mportant
as acti ve materi al s i n optoel ectroni cs,
1
mi croel ectroni cs,
2
mi croel ectromechani cal systems (MEMS),
3
sensors,
4
and
rel ated areas.
5
For exampl e, the undoped, semi conducti ve
forms of conjugated pol ymers are used i n the fabri cati on
of mi croel ectroni c devi ces such as di odes, l i ght-emi tti ng
di odes (LEDs), and transi stors.
1,2
The doped, conducti ve
forms of conjugated pol ymers are bei ng eval uated as
potenti al al ternati ves to metal s as connecti ng wi res and
conducti ve channel s, si nce the conducti vi ty of these
materi al s can be tuned over a wi de range by changi ng the
dopant and/or dopi ng l evel . Fl exi bl e, al l -pl asti c, mi cro-
el ectroni c devi ces based on conjugated organi c pol ymers
are now appeari ng i n prototype forms.
6,7
Many of these appl i cati ons requi re the formati on of
patterns and structures of conjugated organi c pol ymers
wi th feature si zes e100 m. A number of techni ques have
been successful l y demonstrated for the formati on of
patterned mi crofeatures of these materi al s; for exampl e,
photol i thography,
8
e-beam wri ti ng,
9
l aser wri ti ng,
10
and
surface-templ ated deposi ti on.
11
Here we wi sh to report
another procedure for such appl i cati on that combi nes
mi crocontact pri nti ng (CP)
12
and area-sel ecti ve deposi -
ti on.
11
Mi crocontact pri nti ng i s a conveni ent, non-photol i tho-
graphi c techni que that has been used to form patterned
mi crofeatures of sel f-assembl ed monol ayers (SAMs) on
the surfaces of a vari ety of substrates.
12
Patterned
features as smal l as 0.5 m can be routi nel y generated on
both pl anar and nonpl anar surfaces.
13
The capabi l i ty of
patterni ng a surface wi th di fferent monol ayers al l ows us
to easi l y tai l or the physi cal and/or chemi cal properti es of
thi s surface and thus al l ows us to defi ne and control the
nucl eati on and deposi ti on of other materi al s on thi s
surface. For exampl e, we have been abl e to attach
mammal i an cel l s sel ecti vel y,
14
and Nuzzoand co-workers
X
Abstract publ i shed i n AdvanceACS Abstracts, November 1,
1997.
(1) See, for exampl e: (a) Braun, D.; Brown, A.; Stari ng, E.; Mei jer,
E. W. Synth. Met. 1994, 65, 85. (b)Berggren, M.; I nganas, O.; Gustafsson,
G.; Rasmusson, J.; Andersson, M. R.; Hjertberg, T.; Wennerstrom, O.
Nature1994, 372, 444. (c) Burroughes, J. H.; Bradl ey, D. D. C.; Brown,
A. R.; Marks, R. N.; Mackay, K.; Fri end, R. H.; Burns, P. L.; Hol mes,
A. B. Nature1990, 347, 539.
(2) See, for exampl e: (a) Dodadabal apour, A.; Torsi , L.; Katz, H. E.
Science1995, 268, 270. (b) Yang, Y.; Heeger, A. J. Nature1994, 372,
344. (c)Burroughes, J. H.; Jones, C. A.; Fri end, R. H. Nature1988, 335,
137.
(3) See, for exampl e: (a) Smel a, E.; I nganas, O.; Pei , Q.; Lundstrom,
I . Adv. Mater. 1993, 5, 630. (b) I nganas, O.; Pei , Q. Adv. Mater. 1992,
4, 277. (c)Baugman, R. H.; Shackl ette, L. W.; El senbaumer, R. L.; Pl i chta,
E. J.; Becht, C. I n Molecular Electronics; Lazarev, P. I ., Ed.; Kl uwer
Academi c Publ i shers: The Netherl ands, 1991; p 267.
(4) Lonergan, M. C.; Severi n, E. J.; Dol eman, B. J.; Beaber, S. A.;
Grubbs, R. H.; Lewi s, N. S. Chem. Mater. 1996, 8, 2298.
(5) Chen, L. H.; Ji n, S.; Ti efel , T. H. Appl. Phys. Lett. 1993, 62, 2440.
(6) Gustafsson, G.; Cao, Y.; Treacy, G. M.; Kl avetter, F.; Col aneri ,
N.; Heeger, A. J. Nature1992, 357, 477.
(7) Garni er, F.; Hajl aoui , R.; Yassar, A.; Sri vastava, F. Science1994,
265, 1684.
(8) See, for exampl e: (a) Schanze, K. S.; Bergstedt, T. S.; Hauser, B.
T. Adv. Mater. 1996, 8, 531. (b) Venugopal , G.; Quan, X.; Johnson, G.
E.; Houl i han, F. M.; Chi n, E.; Nal amasu, O. Chem. Mater. 1995, 7, 271.
(9) (a) Magnus Persson, S. H.; Dyrekl ev, P.; I nganas, O. Adv. Mater.
1996, 8, 405. (b) Angel opoul os, M.; Patel , N.; Shaw, J. M. Mater. Res.
Soc. Symp. Proc. 1994, 328, 173. (c) Cai , S. X.; Kanskar, M.; Nabi ty, J.
C.; Keana, J. F. W.; Wybourne, W. N. J . Vac. Sci. Technol., B 1992, 10
(6), 2589. (d) Angel opoul os, M.; Shaw, J. M.; Lee, K.-L.; Huang, W.-S.;
Lecorre, M.-A.; Ti ssi er, M. J . Vac. Sci. Technol., B 1991, 9 (6), 3428.
(10) Abdou, M. S. A.; Xi e, Z. W.; Leung, A. M. Synth. Met. 1992, 52,
159.
(11) See, for exampl e: (a)Rozsnyai , L. F.; Wri ghton, M. S. Langmuir
1995, 11, 3913. (b)Zheng, X.-Y.; Di ng, Y.; Bottoml ey, L. A. J . Electrochem.
Soc. 1995, 142, L226. (c) Gorman, C. B.; Bi ebuyck, H. A.; Whi tesi des,
G. M. Chem. Mater. 1995, 7, 526. (d) Rozsnyai , L. F.; Wri ghton, M. S.
J . Am. Chem. Soc. 1994, 116, 5993.
(12) A recent revi ew: Xi a, Y.; Zhao, X.-M.; Whi tesi des, G. M.
Microelectron. Eng. 1996, 32, 255.
(13) See, for exampl e: Jackman, R. J.; Wi l bur, J. L.; Whi tesi des, G.
M. Science1995, 264, 696.
6480 Langmuir 1997, 13, 6480-6484
S0743-7463(97)00537-4 CCC: $14.00 1997 Ameri can Chemi cal Soci ety
have deposi ted copper by chemi cal vapor deposi ti on (CVD),
excl usi vel y,
15
on certai n regi ons of a surface by patterni ng
thi s surface wi th appropri ate SAMs. Here we demon-
strated that patterned SAMs can serve as templ ates for
area-sel ecti ve deposi ti on to form patterned mi crostruc-
tures of conducti ng pol ymers on surfaces of i nsul ati ng
substrates termi nated wi th hydroxyl groups.
16
The SAMs used i n the present work were octadecyl -
si l oxanes on Si /Si O
2
or gl ass. Pol ypyrrol e (PPY) and
pol yani l i ne (PANI ) were chosen i n the present study for
thei r ease of preparati on and thei r excel l ent stabi l i ty i n
ai r. Thi s work demonstrates a conveni ent, l ow-cost
method for formi ng patterned mi crostructures of conduct-
i ng pol ymers on i nsul ati ng substrates and provi des a
potenti al protocol for fabri cati ng fl exi bl e, al l -pl asti c,
el ectroni c or optoel ectroni c devi ces.
Experimental Section
MaterialsandSubstrates. Octadecyl tri chl orosi l ane (OTS,
95%), anthraqui none-2-sul foni c aci d, sodi um sal t monohydrate
(97%), 5-sul fosal i cyl i caci d di hydrate (99+%), FeCl 36H2O(98%),
and pyrrol e (98%)were purchased from Al dri ch. Ani l i ne (99.9%),
(NH4)2S2O8 (99.4%), and hydrochl ori caci d (37.5%)were obtai ned
from Fi sher Sci enti fi c. Al l chemi cal s were used as recei ved unl ess
a puri fi cati on procedure i s menti oned i n the text. Mi croscope
sl i des (Gol d Seal , precl eaned) were obtai ned from Cl ay Adams
Co. The pol y(di methyl si l oxane)(PDMS)el astomer (Syl gard 184)
was obtai ned from Dow Corni ng (Mi dl and, MI ). Pol i shed Si (100)
wafers (Cz, N/phosphorus-doped, 1-10 cm, test grade, and
SEMI standard fl atness) covered by nati ve oxi de were obtai ned
from Si l i con Sense (Nashua, NH). Si /Si O2 substrates and gl ass
sl i des were cl eaned by heati ng at 70 C for 1 h i n a freshl y
prepared pi ranha sol uti on (a mi xture of 98% H2SO4 and 30%
H2O2, 7:3, v/v), fol l owed by extensi ve ri nsi ng wi th di sti l l ed water.
They were dri ed under a stream of ni trogen and were used
i mmedi atel y. Cauti on: piranhasolutionisanextremelystrong
oxidant and should behandled with care.
MicrocontactPrintingofOctadecyltrichlorosilane. The
stamps were fabri cated by casti ng a l i qui d prepol ymer of PDMS
agai nst appropri ate masters accordi ng to publ i shed proce-
dures.
12,17
The masters were patterned rel i ef structures i n thi n
fi l ms of ei ther photoresi st or wax and were fabri cated usi ng
photol i thography and mi cromachi ni ng, respecti vel y. The i nk
used for the present work was an 0.2% (w/w) sol uti on of OTS
i n hexane; i t was prepared and stored i n a ni trogen-fi l l ed gl ovebox
and coul d be used up to 2 months i f fi l tered through a nyl on
membrane (Spartan-25, 0.2 m pore si ze) each ti me before use.
The PDMS stamp was i nked wi th a Q-ti p cotton swab (Fi gure
1), and then brought i nto contact wi th the substrate for 15-30
s.
18
SAMs onl y formed on those areas of the surface that were
i n contact wi th the stamp duri ng pri nti ng.
Polymerization and Deposition of Conducting Poly-
mers. Pol ymeri zati on of PPY and PANI were carri ed out at
room temperature (23-25 C). I n general , two sol uti ons (one
contai ni ng the monomer and the other contai ni ng the oxi dant)
were prepared separatel y and then mi xed together to start the
pol ymeri zati on. The pol ymeri zati on ti me was regi stered rel ati ve
to the poi nt when the two sol uti ons were mi xed together. When
gl ass sl i de was used as the substrate, the si de that had not been
patterned wi th SAMs was covered wi th adhesi ve tape to bl ock
the pol ymeri zati on and deposi ti on of pol ymers on the surface of
thi s si de.
Polymerization and Deposition of Polypyrrole.
19
Anthraqui -
none-2-sul foni c aci d, sodi um sal t monohydrate (2.45 g), 5-sul fo-
sal i cyl i c aci d di hydrate (13.35 g), and FeCl
36H2O (8.75 g) were
di ssol ved i n 250 mL of di sti l l ed water. The substrates patterned
wi th SAMs were pl aced i n thi s sol uti on usi ng pl asti c cl amps and
were equal l y spaced. An aqueous sol uti on of pyrrol e (1.5 mL i n
250 mL of di sti l l ed water) was then added sl owl y wi th mi l d
magneti c sti rri ng. After di fferent peri ods of pol ymeri zati on, the
substrates were taken out, washed i n di sti l l ed water for 10
mi n, and then dri ed under a stream of ni trogen.
Polymerization and Deposition of Polyaniline.
20
The ani l i ne
was puri fi ed by di sti l l ati on i n vacuum. The substrates patterned
wi th SAMs were pl aced i n an aqueous sol uti on contai ni ng ani l i ne
(4 mL) and 1 M HCl (200 mL) sol uti on usi ng pl asti c cl amps and
were equal l y spaced. Another sol uti on contai ni ng (NH
4)2S2O8
(2.3 g)and 1 MHCl (100 mL)was added toi ni ti ate pol ymeri zati on.
The substrates were taken out after 5 mi n and pl aced i n an
aqueous sol uti on of ani l i ne (8 mL) i n 1 N HCl (200 mL) for 30
mi n to reduce the oxi dati on state of pol yani l i ne from the
perni grani l i ne to the emeral di ne.
20
The substrates were then
i mmersed i n 1 M HCl for 1 mi n and dri ed under a stream of
ni trogen.
AdhesiveTapeTestofDepositedFilms. Api ece of i nvi si bl e
tape (Hi ghl and, 3M) was pl aced on the deposi ted fi l m, pressed
gentl y to achi eve a homogeneous contact between the tape and
the fi l m, and then peel ed off qui ckl y.
Fabricationof Polymer LiquidCrystal (PDLC)Display
Devices. A di spl ay devi ce can be easi l y fabri cated by sandwi ch-
i ng a thi n l ayer of PDLC between two el ectrodes. I n our
experi ments, one el ectrode was a pi ece of gl ass sl i de coated wi th
an i nterdi gi tated array of pol ypyrrol e and the other was another
pi ece of gl ass sl i de covered wi th a thi n l ayer of i ndi um-ti n-oxi de
(I TO). The pattern of pol ypyrrol e was fabri cated usi ng area-
sel ecti ve deposi ti on wi th a pol ymeri zati on ti me of 10 mi n. Three
drops of E7 l i qui d crystal fl ui d (BDH Ltd.), seven drops of NOA-
65 opti cal adhesi ve (Norl ands Products, New Brunswi ck, NJ),
and 20 mg of 15 m pol ystyrene spacer (EM. I nd.) were mi xed
thoroughl y i n a watch gl ass. One or two drops of thi s homo-
geneous mi xture were spread ontothe gl ass sl i de patterned wi th
(14) Si nghvi , R.; Kumar, A.; Lopez, G. P.; Stephanopoul os, G. P.;
Wang, D. I . C.; Whi tesi des, G. M.; I ngber, D. E. Science1994, 264, 696.
(15) See, for exampl e: (a)Jeon, N.-L.; Nuzzo, R. G.; Xi a, Y.; Mrksi ch,
M.; Whi tesi des, G. M. Langmuir 1995, 11, 3024. (b) Jeon, N.-L.; Cl em,
P. G.; Payne, D. A.; Nuzzo, R. G. Langmuir 1996, 12, 5350.
(16) Huang, Z.; Wang, P-C.; Feng, J.; MacDi armi d, A. G.; Xi a, Y.;
Whi tesi des, G. M. Synth. Met. 1997, 85, 1375.
(17) Xi a, Y.; Zhuk, A.; Whi tesi des, G. M. Unpubl i shed resul ts.
(18) Xi a, Y.; Mrksi ch, M.; Ki m, E.; Whi tesi des, G. M. J . Am. Chem.
Soc. 1995, 117, 9576.
(19) See, for exampl e: (a) Gregory, R. B.; Ki mbrel l , W. C.; Kuhn, H.
H. Synth. Met. 1989, 28, C-823. (b) Manohar, S. K.; MacDi armi d, A. G.
Bull. Am. Phys. Soc. 1989, 34, 528.
(20) Manohar, S. K.; MacDi armi d, A. G.; Epstei n, A. J. Synth. Met.
1991, 41, 711.
Figure1. Schemati c i l l ustrati on of the procedure used for the
formati on of patterned mi crostructures of conducti ng pol ymers
wi th pri nted SAMs as templ ates.
SelectiveDeposition of Conducting Polymers Langmuir, Vol. 13, No. 24, 1997 6481
pol ypyrrol e and the I TO el ectrode was then careful l y pl aced on
the top of the l i qui d fi l m. After the fl ui d was sol i di fi ed by exposure
toa UV l i ght for 20 mi n, copper wi res were attached tothe pads
of the pattern of pol ypyrrol e usi ng si l ver paste (DuPont) and
these pads were subsequentl y covered wi th epoxy gl ue.
Instrumentation. Ul travi ol et-vi si bl e-near-i nfrared (UV-
vi s-near-I R) spectra were taken on a Perki n-El mer Lambda 9
spectrometer supported wi th 7700 computer software. Scanni ng
el ectron mi crographs were taken on a JEOL JSM-6400 (or JSM-
6300)scanni ng el ectron mi croscope. El l i psometry measurements
were done usi ng a thi n fi l m el l i psometer (Type 43603-200E,
Rudol ph Research, NJ) wi th Si /Si O
2 as the substrate.
Results and Discussion
Area-Selective Deposition of Conducting Poly-
mers. The success of area-sel ecti ve deposi ti on of a
conducti ng pol ymer usi ng a patterned templ ate depends
pri nci pal l y on the i nterfaci al properti es and the exposed
mol ecul ar functi onal i ty of the surface. Fi gure 1 outl i nes
the procedure that we have used. The SAM of octadecyl -
si l oxane changed the wettabi l i ty of a hydroxyl -termi nated
surface from hydrophi l i c to hydrophobi c: the change i n
water contact angl e was from 3 to 110. The pol y-
meri zati on and deposi ti on of pol ypyrrol e and pol y-
ani l i ne occurred more rapi dl y on the CH
3
-termi nated,
hydrophobi c regi ons than on the OH-termi nated, hydro-
phi l i c regi ons.
Fi gure 2 shows SEM i mages of patterned mi crostruc-
tures of PPY and PANI deposi ted on gl ass sl i des wi th
pri nted SAMs of OTS as templ ates. The smal l est feature
of the conducti ng pol ymer was 2 m i n l ateral di mensi on.
The qual i ty of these patterns i s obvi ousl y l ower than that
of patterns generated usi ng e-beam wri ti ng and photo-
l i thography.
8,9,21
The present procedure may, however,
be useful for i ts conveni ence and l ow cost and for i ts abi l i ty
toform mi cropatterns on nonpl anar surfaces
13
and/or over
l arge areas.
22
We al someasured quanti tati vel y the change of thi ckness
of pol ypyrrol e wi th the durati on of the pol ymeri zati on/
deposi ti on (Fi gure 3). Si /Si O
2
wafers (1 2 cm
2
) were
used as the substrate; hal f of the surface of each substrate
had been deri vati zed wi th a SAM of OTS by pri nti ng wi th
a fl at PDMS stamp. I mmedi atel y after i mmersi on i n the
pol ymeri zati on bath, deposi ti on occurred predomi nantl y
on the hydrophobi c regi on. The sel ecti vi ty decreased as
pol ymeri zati on proceeded. For exampl e, deposi ti on of
pol ypyrrol e on the hydrophobi c regi on was greater than
that on the hydrophi l i c regi on by a factor of 6 when the
deposi ti on ti me was 6 mi n, but was 2 for a deposi ti on
ti me of 15 mi n.
Electronic Structure of Polypyrrole Films De-
posited with SAMs as Templates. The el ectroni c
structure of thi n fi l ms of pol ypyrrol e deposi ted usi ng the
present procedure depends strongl y on the i nterfaci al
properti es of the surface. Fi gure 4 shows UV-vi s-near-
I R spectra of thi n fi l ms of pol ypyrrol e sel ecti vel y deposi ted
on the SAM-deri vati zed (hydrophobi c)regi on and the bare
(hydrophi l i c) regi on, respecti vel y. The substrates used
here were gl ass sl i des; hal f of the surface of each sl i de had
been deri vati zed wi th a SAM of OTS by pri nti ng wi th a
fl at PDMS stamp. The pol ymeri zati on/deposi ti on was
al l owed to proceed for 15 mi n. The UV-vi s-near-I R
spectrum (Fi gure 4A) of the thi n fi l m of pol ypyrrol e
deposi ted on the hydrophobi c regi on shows a steadi l y
i ncreasi ng free-carri er-tai l starti ng from 1000 nm to
the I R regi on; the UV-vi s-near-I R spectrum (Fi gure 4B)
of the thi n fi l m of pol ypyrrol e deposi ted on the hydrophi l i c
regi on shows a broad absorpti on band wi th a maxi mum
at 1182 nm.
(21) Thi s poor qual i ty may represent the i ntri nsi c characteri sti c of
the pol ymeri zati on procedure used here; i t coul d al so be caused by the
rel ati vel y poor qual i ty of si l oxane SAMs.
(22) Xi a, Y.; Qi n, D.; Whi tesi des, G. M. Adv. Mater. 1996, 8,1017.
Figure 2. SEM i mages of patterned mi crostructures of (A)
pol ypyrrol e and (B) pol yani l i ne deposi ted on gl ass sl i des wi th
pri nted SAMs as templ ates. The pol ymeri zati on ti me was 10.5
mi n for pol ypyrrol e and 5 mi n for pol yani l i ne. The dark regi ons
are conducti ng pol ymers sel ecti vel y deposi ted on the hydro-
phobi c, SAM-covered regi ons; the bri ght regi ons are hydrophi l i c,
bare regi ons. The stamps used for pol ypyrrol e and pol yani l i ne
had compl ementary rel i ef patterns on thei r surfaces.
6482 Langmuir, Vol. 13, No. 24, 1997 Huang et al.
The free-carri er-tai l i n the near-I R regi on i s charac-
teri sti c of mobi l i ty of conducti ve el ectrons.
23-25
We have
previ ousl y proposed from detai l ed studi es of pol yani l i ne
fi l ms deposi ted from good and poor sol vents that the
presence of a wel l -devel oped free-carri er-tai l i s associ ated
wi th an expanded coi l mol ecul ar conformati on whi l e i ts
absence and the appearance of a l ocal i zed pol aron peak
i s associ ated wi th a ti ght coi l mol ecul ar conformati on
whi ch reduces conjugati on al ong the pol ymer backbone
and hence conducti on el ectron mobi l i ty.
26
We bel i eve that
the presence of a free-carri er-tai l i n the UV-vi s-near-
I Rspectrum of the PPYdeposi ted on a hydrophobi csurface
may be associ ated wi th a more extended mol ecul ar
conformati on than the pol ymer deposi ted on a hydrophi l i c
surface whi ch onl y shows a l ocal i zed pol aron adsorpti on
at 1182 nm. The i nterfaci al properti es of a substrate
probabl y onl y di rectl y determi ne the properti es of pol ymer
chai ns wi thi n the fi rst several monol ayers i ni ti al l y pol y-
meri zed on the surface; these pol ymer chai ns may,
however, i nfl uence the conformati onal properti es of
pol ymer chai ns pol ymeri zed afterward.
Electrical Properties of Conducting Polymers
Deposited with SAMs as Templates. The most sur-
pri si ng and i nteresti ng feature of the present study (and
possi bl y a feature of si gni fi cant technol ogi cal i mportance)
was the di scovery of enormous di fference i n sheet resi st-
i vi ty of the pol ymer fi l ms deposi ted on hydrophobi cversus
hydrophi l i csurfaces. The sheet resi sti vi ty of a pol ypyrrol e
fi l m deposi ted (wi th a pol ymeri zati on ti me of 15 mi n)on
the CH
3
-termi nated, hydrophobi c surface was 1.6 10
3
/0(the correspondi ng conducti vi ty was 150 S/cm, based
on a fi l m thi ckness of 410 from Fi gure 3); the fi l m
deposi ted (wi th the same pol ymeri zati on ti me)on the OH-
termi nated, hydrophi l i c surface had a sheet resi sti vi ty
greater than the l i mi t of the ohmmeter empl oyed, i .e.,
>10
7
/0(the correspondi ng conducti vi ty was <0.5 S/cm,
based on a fi l m thi ckness of 20 from Fi gure 3). A
si mi l ar el ectri cal behavi or was al so observed for pol y-
ani l i ne fi l ms deposi ted wi th SAMs as templ ates: the sheet
resi sti vi ty of a pol yani l i ne fi l m deposi ted (wi th a pol y-
meri zati on ti me of 5.5 mi n) on the hydrophobi c surface
was 5 10
3
/0whereas that of a fi l m deposi ted on the
hydrophi l i c surface was >10
7
/0.
Li nes of PPY (1 cm i n l ength, 200 m i n wi dth,
deposi ted on the hydrophobi c regi ons of a SAM-patterned
surface wi th a pol ymeri zati on ti me of 15 mi n) were
prepared on gl ass sl i des and used for the measurement
of conducti vi ty. A conducti vi ty of 100 S/cm was meas-
ured usi ng the two-probe method. An i nterdi gi tated array
contai ni ng i sol ated l i nes (500 m i n wi dth, separated by
300 m)of PPY was al sofabri cated totest i sol ati on. The
measured resi stance across thi s array was >10 M
(beyond the measurabl e range of the i nstrument). Thi s
val ue i s more than 3 orders of magni tude hi gher than
that measured on conti nuous regi ons of PPY fi l ms,
confi rmi ng that PPYl i nes that are 300 m i n separati on
are el ectri cal l y i sol ated from each other by a medi um
havi ng much l ower conducti vi ty.
Adhesion Properties of Deposited Conducting
Polymers. The adhesi on between a deposi ted pol ymer
and a substrate i s mai nl y determi ned by the i nterfaci al
properti es of the substrate. I n many cases, the adhesi on
strength i s rel ated to the surface free energy of the
substrate.
27
As a resul t, the patterned SAMs used here
not onl y control l ed the nucl eati on and deposi ti on of a
conducti ng pol ymer but al so i nfl uenced the adhesi on
between the deposi ted fi l m of thi s pol ymer and the
substrate.
28
We found that the deposi ted thi n fi l ms of
pol ypyrrol e adhered more strongl y tothe hydrophi l i c, bare
regi on than to the hydrophobi c regi on deri vati zed wi th
SAMs of OTS. Thi s property has been used i n a di fferent
system tofabri cate both posi ti ve and negati ve patterns
of pol ypyrrol e usi ng a procedure si mi l ar to the adhesi ve
tape test.
29
For exampl e, we i mmersed a SAM-patterned
substrate i n the pol ymeri zati on bath for 18 mi n to cover
the enti re surface wi th a thi n l ayer of pol ypyrrol e, and
then we removed the fi l m on the hydrophobi c regi on by
transferri ng i t toadhesi ve tape toform a posi ti ve pattern
(that i s, the pattern of the SAM on the ori gi nal substrate)
on the tape and to l eave a compl ementary, negati ve
pattern on the surface of the substrate. Fi gure 5 shows
SEM i mages of the posi ti ve and negati ve patterns of
pol ypyrrol e prepared usi ng thi s procedure. The adhesi on
(23) Xi a, Y.; MacDi armi d, A. G.; Epstei n, A. J. Macromolecules1994,
27, 7212.
(24) Xi a, Y.; Wi esi nger, J. M.; MacDi armi d, A. G.; Epstei n, A. J. Chem.
Mater. 1995, 7, 443.
(25) Avl yanov, J. K.; Mi n, Y.; MacDi armi d, A. G.; Epstei n, A. J. Synth.
Met. 1995, 72, 65.
(26) MacDi armi d, A. G.; Epstei n, A. J. Synth. Met. 1995, 69, 85.
(27) Good, R. J.; Gupta, R. K. J . Adhes. 1988, 26, 13.
(28) Newby, Z. B.-M.; Chaudhury, M. K.; Brown, H. R. Science1995,
269, 1407.
(29) Rozsnyai , L. F.; Wri ghton, M. S. Chem. Mater. 1996, 8, 309.
Figure 3. Dependence of thi ckness of deposi ted pol ypyrrol e
on the ti me el apsed duri ng pol ymeri zati on/deposi ti on. The
thi ckness of pol ypyrrol e was measured usi ng an el l i psometer.
Si wafers covered wi th nati ve oxi de were used as the substrates;
hal f of the surface of each substrate was pri nted wi th SAMs
usi ng a fl at PDMS stamp.
Figure4. UV-vi s-near-I R spectra of thi n fi l ms of pol ypyrrol e
deposi ted (wi th a pol ymeri zati on ti me of 15 mi n) on di fferent
regi ons of a patterned surface: (A) hydrophobi c regi on; (B)
hydrophi l i c regi on.
SelectiveDeposition of Conducting Polymers Langmuir, Vol. 13, No. 24, 1997 6483
between pol ypyrrol e and the bare, hydrophi l i c regi on was
strong enough topass the adhesi ve tape test. The adhesi on
between the pol ymer and the SAM-deri vati zed regi on was
rel ati vel y weak, and the fi l m was easi l y removed by usi ng
adhesi ve tape.
PatternedThinFilmsofPolypyrroleasElectrodes
in Liquid Crystal Display Devices. The surface
resi sti vi ty of thi n fi l ms of PPY deposi ted on the hydro-
phobi cregi ons was more than 3 orders of magni tude l ower
than that of fi l ms deposi ted on the hydrophi l i c regi ons.
As a resul t, we coul d di rectl y fabri cate di spl ay devi ces
usi ng as-deposi ted mi crostructures of PPY as the el ec-
trodes. Fi gure 6 shows photographs of a di spl ay devi ce
based on pol ymer di spersed l i qui d crystal s (PDLC).
30
The
i nterdi gi tated array of pol ypyrrol e was deposi ted on the
hydrophobi c regi on of a gl ass sl i de wi th a pol ymeri zati on
ti me of 10 mi n. Thi s pol ymeri zati on ti me, and therefore
the thi ckness of the deposi ted fi l m of pol ypyrrol e, was
chosen such that the opti cal transparency i n the vi si bl e
regi on and the resi stance of the formed fi l m were both
opti mi zed. A mi xture of PDLC was sandwi ched between
two gl ass sl i des; one of them had been covered wi th the
i nterdi gi tated array of pol ypyrrol e and the other one had
been coated wi th a thi n fi l m of i ndi um-ti n-oxi de (I TO). A
thi n l ayer of PDLC i s opaque because the i nci dent l i ght
i s scattered from the submi crometer-si zed dropl ets of
PDLC. Thi s l ayer becomes transparent when a vol tage
i s appl i ed between the two el ectrodes and the dropl ets
are ori ented i n the el ectri c fi el d to an ori entati on where
thei r refl ecti ve i ndex matches that of the pol ymer matri x.
The procedure demonstrated here coul d al so be extended
toform patterned mi crostructures of conducti ng pol ymers
on i nsul ati ng, pol ymeri c fi l ms that coul d be subsequentl y
used tofabri cate fl exi bl e, al l -pl asti c el ectroni c and opti cal
devi ces.
Summary
I n summary, we have demonstrated a si mpl e, conve-
ni ent, and l ow-cost method for formi ng mi cropatterns and
mi crostructures of conducti ng pol ymers (pol ypyrrol e and
pol yani l i ne) on i nsul ati ng substrates. The i nterfaci al
properti es of a surface control the pol ymeri zati on, deposi -
ti on, and adhesi on of conducti ng pol ymers on a substrate.
The rate of deposi ti on on the hydrophobi c surface i s
somewhat hi gher than that on the hydrophi l i c surface;
the sheet resi sti vi ty of the fi l m deposi ted on the hydro-
phobi c surface i s several orders of l ower than that of the
fi l m deposi ted on the hydrophi l i csurface. Usi ng patterned
SAMs of octadecyl si l oxane (formed by CP)as templ ates,
we have been abl e to form patterned mi crostructures of
conducti ng on hydroxyl -termi nated surfaces wi th a mi ni -
mum feature si ze of 2 m. The substrates used here
coul d be i nsul ators and semi conductors (for exampl e, gl ass
sl i des, pl asma-treated pol ymer fi l ms, and Si /Si O
2
). The
patterned mi crostructures of conducti ng pol ymers formed
thi s way coul d be di rectl y used as el ectrodes i n di spl ay
devi ces or sensors
31
and as connecti ng wi res i n mi cro-
el ectroni c ci rcui ts. As a prototype exampl e, we have
fabri cated PDLC di spl ay devi ces usi ng patterned mi cro-
structures of PPY as the el ectrodes.
Acknowledgment. Thi s work was supported i n part
by ONR (N00014-92-J-1369) and ARPA. Thi s work al so
made use of MRSEC shared Faci l i ti es at Harvard and at
the Uni versi ty of Pennsyl vani a supported by the Nati onal
Sci ence Foundati on under award numbers DMR-94-00396
and DMR-96-32598, respecti vel y.
LA970537Z
(30) Crawford, G. P.; Doane, J. W. Condensed Matter News 1992, 1
(6), 5.
(31) I mi si des, M. D.; John, R.; Wal l ace, G. G. CHEMTECH 1996,
May, 19.
Figure 5. SEM i mages of a posi ti ve pattern (that i s,
pol ypyrrol e deposi ted on the hydrophobi cregi on)of pol ypyrrol e
and the correspondi ng negati ve pattern (that i s, pol ypyrrol e
deposi ted on the hydrophi l i c regi on).
Figure6. Photographs of a PLCD devi ce wi th a mi cropattern
of i nterdi gi tated pai r: (A) no vol tage was appl i ed; (B) the l eft-
hal f of the pai r was turned on; (C)the ri ght-hal f of the pai r was
turned on; (D) the whol e pattern was turned on. The appl i ed
ac vol tage was 110 V, 60 Hz. The bottom hal f i n each smal l
fi gure i s Cu wi res attached to the pads of the PPY pattern.
6484 Langmuir, Vol. 13, No. 24, 1997 Huang et al.