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Macromolecules 2010, 43, 811–820 811

DOI: 10.1021/ma902241b

Donor-Acceptor Polymers Incorporating Alkylated
Dithienylbenzothiadiazole for Bulk Heterojunction Solar Cells:
Pronounced Effect of Positioning Alkyl Chains
Huaxing Zhou,† Liqiang Yang,‡ Shengqiang Xiao,†,§ Shubin Liu,^ and Wei You*,†

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina
27599-3290, ‡Curriculum in Applied Sciences and Engineering, University of North Carolina at Chapel Hill,
Chapel Hill, North Carolina 27599-3287, §State Key Lab of Advanced Technology for Materials Synthesis
and Processing, Wuhan University of Technology, Wuhan, P. R. China 430070, and ^Research Computing Center,
University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 25599-3420
Received October 8, 2009; Revised Manuscript Received November 24, 2009

ABSTRACT: 4,7-Di(thiophen-2-yl)benzothiadiazole (DTBT) has been used to construct a number of
donor-acceptor low band gap polymers for bulk heterojunction (BHJ) photovoltaics with high efficiency
numbers. Its strong tendency to π-stack often leads to polymers with low molecular weight and poor solubility,
which could potentially be alleviated by anchoring solubilizing chains onto the DTBT unit. A systematic study of
the effect of positioning alkyl chains on DTBT on properties of polymers was implemented by investigating a
small library of structurally related polymers with identical conjugated backbone. This series of donor-
acceptor polymers employed a common donor unit, benzo[2,1-b:3,4-b0 ]dithiophene (BDT), and modified DTBT
as the acceptor unit. Three variations of modified DTBT units were prepared with alkyl side chains at (a) the 5-
and 6-positions of 2,1,3-benzothiadiazole (DTsolBT), (b) 3-positions of the flanking thienyl groups (3DTBT),
and (c) 4-positions (4DTBT), in addition to the unmodified DTBT. Contrary to results from previous studies,
optical and electrochemical studies disclosed almost identical band gap and energy levels between
PBDT-4DTBT and PBDT-DTBT. These results indicated that anchoring solubilizing alkyl chains on the
4-positions of DTBT only introduced a minimum steric hindrance within BDT-DTBT, maintaining the
extended conjugation of the fundamental structural unit (BDT-DTBT). More importantly, the additional
high molecular weight and excellent solubility of PBDT-4DTBT led to a more uniform mixture with PCBM,
with better control on the film morphology. All these features of PBDT-4DTBT led to a significantly improved
efficiency of related BHJ solar cells (up to 2.2% has been observed), triple the efficiency obtained from BHJ
devices fabricated from the “conventional” PBDT-DTBT (0.72%). Our discovery reinforced the importance of
high molecular weight and good solubility of donor polymers for BHJ solar cells, in addition to a low band gap
and a low HOMO energy level, in order to further enhance the device efficiencies.

Introduction low band gap polymers have been demonstrated with decent
In recent years there has been tremendous progress in the field of efficiencies (3-6%) when they were blended with PCBM or
[6,6]-phenyl C70-butyric acid methyl ester (PC70BM) in typical
bulk heterojunction (BHJ) polymer solar cells since its inception in
BHJ devices.8-28 For example, PCDTBT, a low band gap polymer
1995.1 The overall energy conversion efficiency has been steadily
synthesized from a copolymerization of alkylated carbazole and
improving from an initial 1% via a blend of poly[2-methoxy-
4,7-di-2-thienyl-2,1,3-benzothiadiazole (DTBT), recently demon-
5-(30 ,70 -dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV)
strated a record high efficiency of 6.1% when it was blended in a
with [6,6]-phenyl C60-butyric acid methyl ester (PCBM)2 to an BHJ composite with PC70BM.17
impressive ∼5% achieved by poly(3-hexylthiophene) (P3HT): One common feature of these successful low band gap polymers is
PCBM via extensive morphology optimization.3-5 In order to the predominant employment of 2,1,3-benzothiadiazole (BT)12,14,24
further improve the efficiency of BHJ polymer solar cells, the or di-2-thienyl-2,1,3-benzothiadiazole (DTBT)8-10,15-17,23 as the
research community is enthusiastically searching for new poly- acceptor units. Compared with the BT unit, DTBT has a few
mers. From the materials perspective, these donor polymers advantages. First, the two flanking thienyl units relieve the otherwise
should not only have a low band gap (to increase the short circuit possibly severe steric hindrance between the acceptor BT unit and
current, Jsc) but also bear a low energy level of the highest oc- donor aromatic units (especially when benzene-based aromatics are
cupied molecular orbital (HOMO) (to improve the open circuit used). Thus, the synthesized donor-acceptor polymers would adopt
voltage, Voc).6 Typically, a low band gap polymer is designed via a a more planar structure, thereby reducing the band gap by enhancing
“donor-acceptor” (D-A) approach, which is to incorporate the D-A conjugation. In addition, a more planar conjugated
electron-rich and electron-deficient moieties in the polymer back- backbone would facilitate the chain-chain interactions among
bone. The low band gap is mainly caused by the intramolecular polymers, improving the charge carrier (usually hole) mobility.
charge transfer between donor and acceptor units.7 Indeed, several Second, while the electron accepting BT unit maintains the low band
gap, the two electron rich, flanking thienyl units would help improve
*To whom all correspondence should be addressed. E-mail: wyou@ the hole mobility, since thiophene-based polymers (such as P3HT) have shown very high hole mobility.29 Because of these advantages,
r 2009 American Chemical Society Published on Web 12/29/2009

2.35 cells. the steric hindrance introduced devices fabricated from either PBDT-DTBT (0.9 in spite of a lower band gap DTBT) was also synthesized.6% was obtained for PBDT-BT. mainly due to the lower Jsc in the minimum steric hindrance within BDT-DTBT. prepared the homopolymers HOMO energy level inherited from PBDT-DTBT. and better solubility compared pared: alkyl side chains at (a) the 5.812 Macromolecules.30 This low solubility can lead to low molecular weight of the polymer and unnecessary difficulty in processing the polymer.30. prepared polymers incorporating a DTBT unit better solubility in processing solvents were observed for all three modified with either alkyl chains on the 4-position of these polymers with alkylated DTBT units than those of PBDT- thienyl units or alkoxy chains on the 3-position. mainly due to a in a polymer with much higher molecular weight (number. such modification of DTBT units should also have observed from these reported polymers that incorporated modi- minimum impact on the band gap and energy levels one would fied DTBT units.6%).2  10-6 cm2/(V 3 s) than that of the polymers incorporating such modified DTBT units were PBDT-DTBT (3. 68 kg/mol) and better solubility36 hole mobility (4.41 Though relatively high molecular 2. the polymer with unmodified DTBT (PBDT- the original PF-DBT (up to 3.30 However. obtain from “conventional” polymers incorporating unmodified Previously. PBDT-4DTBT.30.23. resulting ciency of only 0. Chemical structures of PBDT-DTBT. small Jsc of 2. acceptor unit was envisioned and synthesized (Figure 1). Three variations of modified DTBT units were pre- gap. Furthermore.4-b0 ]dithiophene.1. which accounted for a smaller Jsc in the former case. and a similar HOMO energy level of PFO-M3. leads to a of alkylated DTBT by varying alkyl chains on either 3. Alkyl Wang et al. (BT). attempted to add additional alkylated thiophene chains. together with its low band gap and relatively low earlier study. These results indicate that anchoring solubilizing were lower than that of the corresponding DTBT-based polymer alkyl chains on the 4-positions of DTBT only introduces a without alkoxy/alkyl chains.benzothiadiazole on the DTBT unit in order to enhance both the solubility and molecular weight of resulting polymers. were used to mitigate the units to extend the DTBT unit. the overall tical band gap and energy levels between PBDT-4DTBT and BHJ device efficiencies of polymers with such modified DTBT PBDT-DTBT.and 6-positions of 2. the additional thiophene rings could result in polymers that are poorly soluble. which have been shown to help enhance the efficiency of related BHJ devices. Interestingly. Jayakannan et al. no improvements on BHJ devices efficiency were addition. an effi- alkoxy chains on the 3-position of these thienyl units.42 All of structurally related polymers unveils a complete picture of the these studies acknowledged the advantage of employing DTBT influence of alkyl chains on different positions of DTBT units on . donor. these modified ones were more soluble. This noticeably higher mobility of PBDT- unit.39 Compared DTBT (9 kg/mol).43 However. As expected. 2010 Zhou et al. contrary to results from previous with polymers incorporating DTBT without any decorated studies. presumably by improved inter-polymer interaction to enhance the current.1- There have been attempts to incorporate alkyl or alkoxy chains b:3. the strong stacking ability of polymers incor- porating the DTBT unit also introduces several concomitant technical difficulties. it is important to search for new strategies to modify molecular weight and good solubility of resulting polymers.21  noticeably lower than that of polymers with unmodified DTBT 10-6 cm2/(V 3 s)). BDT). and (c) 4-positions (4DTBT).15-17.21  10-6 cm2/(V 3 s)) and a low molecular than those of original polymers without any soluble chains on the weight (Mn: 10.5%).20.40 In an 4DTBT. triple the efficiency obtained from BHJ weight polymers were obtained. No. the excessive stacking may result in Figure 1. For of this new polymer (PFO-M3) was smaller (2.2% has been observed). the overall efficiency thienyl groups (3DTBT). This PBDT-3DTBT and PBDT-DTsolBT.or significantly improved efficiency of related BHJ solar cells (up to 4-positions of thienyl groups. For example. a library of poly- on the DTBT unit caused the HOMO level of the resulting mers incorporating BDT as the donor and modified DTBT as the polymer to increase. In another study. shows an such modified DTBT units. separated phases of donor polymers and fullerenes. Thus.40 Therefore. higher molecular weight. the structure of DTBT so as to improve the solubility and which should lead to PV devices with higher efficiencies.and an acceptor.72%) or by these alkyl chains in these polymers led to much larger band PBDT-BT (0. thereby main- former case. these electron-donating alkoxy groups introducing the modified DTBT units. high molecular weight polymers are desirable. Computational simulation revealed that a severe taining the extended conjugation of the fundamental structural steric hindrance was introduced by these alkyl/alkoxy chains. This low current was ascribed to a low average molecular weight.06 mA/cm2. PBDT-4DTBT. much higher molecular weights (∼30 kg/mol) and Song et al. the hole mobilities of improved hole mobility of 9. the widespread usage of the DTBT unit has resulted in a number of polymers with high BHJ solar cell efficiencies.43 A thorough investigation of this library gaps than that of the homopolymer of unmodified DTBT.a low band gap polymer (PBDT-BT) was obtained copolymerized alkylated fluorene with DTBT modified with together with a low HOMO energy level. in contrast to the desired morphology: nanometer units in constructing D-A low band gap polymers for BHJ solar sized. which led to a lower Voc. the polymer containing the leading to a twisted conjugated backbone in both polymers with “properly” modified DTBT unit. More recently. 43.8-10. unit (BDT-DTBT). Mn. More importantly.63%) than that of comparison.bithiophene fused with a benzene moiety (benzo[2.38 Unfortunately. aggregation of polymers upon spin-casting of the film.37 The resulting D-A polymer possible elevation of the HOMO energy levels of the resulting with alkylated fluorene as the donor unit showed a smaller band polymers. these previous studies underscored the In order to fully utilize the aforementioned merits of DTBT importance of the functionalization of DTBT units to reach high units.32-34 Even if one could manage to obtain high molecular weight polymers.31 Unfortunately.1 kg/mol). Shi et al.3- with the original copolymer that incorporated alkylated fluorene benzothiadiazole (DTsolBT). we have demonstrated that by incorporating a DTBT units. both of which would be alleviated by DTBT unit. In one study. For BHJ solar cells. (b) 3-positions of the flanking and DTBT (PF-DBT). rather than alkoxy chains. In fortunately. Again. aggregation leads to polymer-only domains on a micrometer scale. Un- molecular weight of polymers incorporating DTBT units. Vol.9  10-6 cm2/(V 3 s)) or PBDT-BT (4. optical and electrochemical studies disclose almost iden- chains.

Four polymers were therefore pre- mide with overall yield of >60%. the bro. solution genations and coupling reaction to monomer A1. 2010 813 Scheme 1. Synthetic Route for A2 and A3 (Brominated 3DTBT and 4DTBT) the optical.44. processable polymer. and photovoltaic properties of resulting selectively occurred at the more acidic 5-position.45 portion was discarded since it would not be solution proces- It is worth noting that the deprotonation of 3-octylthiophene sable.46 was prepared from commercially available 2-ethylhexyl bro. branched alkyl which was subsequently quenched by (n-Bu)3SnCl to yield the chains were attached at the central BT unit during the 2-stannylated (8). and afforded compound (6). Only the chloroform-soluble portion was (solBT). with tributyltin anchored at the 2-position. 4-Ethyloct-1-yne synthesized following a literature report. stopped after 18 h when precipitation was observed. distannane (D0) with brominated DTBT and its derivatives benzene (1). long. Vol. hexane. yielding alkylated diaminobenzene (5). The neously via Pd/H2. mained in the extraction thimble after the extraction with Synthesis of A2 and A3 is depicted in Scheme 2. This presumably high molecular weight synthesized via slightly modified literature procedures. A noticeable amount of residue re- minated DTsolBT. stannylation to yield (7).2-dibromo.5-dinitrobenzene (2) obtained by nitration of 1. The polymerization of PBDT-DTBT was Both triple bonds and nitro groups were reduced simulta. collected in order to obtain a high molecular weight. The other isomer (8). the alkylated benzothiadiazole finally chloroform. which then underwent several conventional halo. electrical. A Sonogashira coupling pared by a palladium-catalyzed Stille cross-coupling poly- was employed to attach the 4-ethyloct-1-yne to 1. No. Polymer Synthesis.Article Macromolecules.4-b0 ]dithiophene (BDT) 4. Synthesis of Monomer A1 (Brominated DTsolBT) Scheme 2. They were chloroform.2-dibromo. condensation of benzo[2. weight polymer with good solubility.1-b:3. The unmodified DTBT monomer was synthesis of DTsolBT (M1 in Scheme 1). leading to the alkylated dinitrobenzene (3).41. crude polymer was then precipitated from methanol and Treating (5) with thionyl chloride under basic conditions extracted via a Soxhlet apparatus with acetone. 2. since the bromination via NBS was selective at the more nucleophilic 2-position. followed by polymers. 43. was obtained via 2-bromo-3- Results and Discussion octylthiophene as the intermediate. which consequently led to a relatively low yield (51%) . (Scheme 3). Then Monomer Synthesis. In order to obtain a high molecular halogen exchange with n-BuLi led to the lithiated 2-position.

jugated backbone of PBDT-DTBT. The positioning of of the 2. 2. Please note that microwave-assisted on the 4-positions of the thienyl groups (i. while an appreciable red shift in thin the unsubstituted PBDT-DTBT has a strong tendency to film was still observed for PBDT-3DTBT. It is surprising to discover that anchoring these the conjugated backbone) is introduced when alkyl chains alkyl chains on the 4-positions of these thienyl groups on are located at the central BT unit. Not surprisingly. and the weight-average [%] mol] mol] PDIa [C] (Mw) is 12 kg/mol.. However. solubility.e.3-benzothiadiazole (DTsolBT). both . Large band gaps were observed for these two polymers effects were observed on the optical and electrochemical (2. standards. dramatic (BT).48 eV for PBDT- properties of polymers incorporating alkylated DTBT units. the central BT unit. partly due to its low molecular weight and polymers. The even larger band gap of PBDT-DTsolBT depending upon where these alkyl chains are attached on the implies much stronger steric hindrance (thereby twisting of DTBT units. tions of the thienyl groups (3DTBT) or the 5.44 440 resulting polymers and improves their solubility in com. The structures of these purified polymers were from about 550 nm. high molecular weight and good weight loss determined by TGA at a heating rate of 10 C/min. adding solubilizing chains to the DTBT PBDT-3DTBT 88 37 84 3. drance is introduced between the flanking thienyl groups and mingly has little impact on the molecular weight and solubi. These results suggest that anchoring alkyl chains more rigid backbone. The twisting of the the DTBT unit have negligible impact on the absorption backbone due to the DTsolBT unit also explains the fact and band gap of PBDT-4DTBT compared with those that nearly negligible stacking was observed for PBDT- of PBDT-DTBT in solution (Figure 2a). mainly due to the poor solubility of PBDT-DTBT. 2010 Zhou et al. No. extending up to almost 800 nm.7 eV) have been observed for both PBDT-DTBT. also explain the high yields of these polymeriza- tions even after crude polymers were extensively purified π-stack: a pronounced absorption increase was observed (Table 1). compared with that of PBDT-DTBT (735 nm vs 761 nm) indicating the amorphous nature of these polymers. Finally. severe steric hin- attached solubilizing alkyl chains on the DTBT unit see.80 420 On the other hand. Neither glass transition nor melting transition stacking. maintaining the elec- arable to that of PBDT-3DTBT or PBDT-DTsolBT) tron delocalization from D-A structures. Polymerization Results for Polymers molecular weight of PBDT-DTBT is low: the number. a Determined by GPC in tetrahydrofuran (THF) using polystyrene monly employed solvents such as THF and chloroform. Scheme 3.814 Macromolecules. DTsolBT). similarly visible melting transition at ∼190 C were obtained for small band gaps (<1. 43. 4DTBT) polymerization47-49 was employed in synthesizing PBDT. Polymerization by Stille Coupling Reaction of the polymerization. indicative of a slight steric hindrance from these slightly observable glass transition at ∼125 C and a barely extra alkyl chains in the solid state.31 270 PBDT-4DTBT 75 27 54 1. The confirmed by 1H NMR and elemental analysis (Supporting alkylated PBDT-4DTBT shows similar behavior of strong Information).1. yield Mna [kg/ Mwa [kg/ Tdb average (Mn) is only 9 kg/mol. the measured Table 1. obtained in much shorter time (half an hour compared with When these alkyl chains are located at either the 3-posi- days in conventional heating). In thin films.and 6-positions Optical and Electrochemical Properties. though the absorption edge is slightly blue-shifted was observed for all three polymers with alkylated DTBT.21 eV for PBDT-3DTBT and 2. b The temperature of degradation corresponding to a 5% Both of these features. Nevertheless. A (Table 2). Vol. DTsolBT in thin film. with satisfactorily high molecular weight (comp.07 436 unit significantly increases the molecular weight of the PBDT-DTsolBT 87 30 92 2. The conjugated backbone is thereby lity of related polymers: high molecular weight and good twisted at the D-A linkage. PBDT-DTBT 51 9 12 1. significantly affecting the solubility have been unanimously obtained for polymers effective conjugation between the donor and the acceptor incorporating alkylated DTBT units. introduces minimum steric hindrance to the original con- 4DTBT.

a very low HOMO level of -5. Thus. 2. and their electron density distributions were calculated at the B3LYP/6-311þG* level of theory50.98 -5. Computational study of this series of polymers provides insightful information to account for the observed difference of optical and electrochemical prop- erties.43 backbone via cyclic voltammetry provides direct evidence on Shifting these alkyl chains to the 3-positions of thienyl how the difference in positioning these alkyl chains affects groups (PBDT-3DTBT) leads to an appreciable conjuga- the energy levels of these related polymers.34 eV).21 -1.82/-2.58/-5. To simplify the calculation. which explains similar HOMO levels of PBDT-DTsolBT and HMPBDT.01 -5. All three dihedral angles for PBDT-DTBT are small (Table 3). HOMO and LUMO energy levels. only one repeating unit of each polymer was subject to the calculation.35 580 0.89/-5. PBDT-4DTBT. the eV was observed.67/-3.69 619 0. PBDT-3DTBT. -5. No.51 using density functional theory and Gaussian 03 package (Figure 4). the HOMO is essentially localized at the BDT unit (and partially on thienyls).43 This apparent HOMO energy levels of PBDT-4DTBT and PBDT-DTBT coincidence implies that the severe steric hindrance from differ only slightly (.69 LUMO energy levels (Figure 3 and Table 2).41/-5. Cyclic voltammograms of the oxidation and reduction beha- solid film (dash line) and (b) PBDT-DTsolBT and PBDT-3DTBT vior of thin films of PBDT-DTBT.27 eV vs .52 The dihedral angles between two thienyl groups with central BT unit as well as the donor BDT unit quantita- tively measure the steric hindrance introduced by these alkyl chains.5. The lowest tion twisting at the linkage of thienyl groups with the central unoccupied molecular orbital (LUMO) is essentially domi.68 666 761 1. 2010 815 PBDT-DTBT and PBDT-4DTBT are much more absorp.70 641 735 1. with alkyl chains replaced by CH3 groups.33 PBDT-DTsolBT 425 500 2. Optical and Electrochemical Data of All Polymers UV-vis absorption PL CHCl3 solution film CHCl3 solution cyclic voltammetry DFT λmax λonset Ega λmax Ega λmax Eox onest Ered onest calcd polymer [nm] [nm] [eV] [nm] λonset [nm] [eV] [nm] (V)/HOMO [eV] (V)/LUMO [eV] HOMO [eV] PBDT-DTBT 550 738 1. 43.5  10-5 cm-1 for the former two polymers at their maxi.97 654 0. which explains renders a lowered HOMO energy level of -5.47/-5.21 eV). of the latter two (up to 0. .5.27 -1.5. electron rich thienyl groups to the original PBDT-BT mum absorption wavelength.19 PBDT-3DTBT 475 560 2. Computational Study.70 eV).Article Macromolecules. significantly greater than those increases the electron density of the conjugated backbone.21 520 628 1.38 eV. and PBDT-DTsolBT. indicative of complete conjugation of all Figure 2. The optimized geometry. Vol. strikingly similar to that of the homopo- HOMO energy levels disclose dramatic differences. UV-vis spectra of all the polymers: (a) PBDT-DTBT and PBDT-4DTBT polymers in chloroform solution (solid line) and in Figure 3.13 -5.43 a Calculated from the intersection of the tangent on the low energetic edge of the absorption spectrum with the baseline.64/-3. BT unit.63 628 0.16 -5. that anchoring alkyl chains at the 4-positions of thienyl tive in the solid state than either PBDT-3DTBT or groups has almost negligible influence on the extended PBDT-DTsolBT: similar absorption coefficients of about conjugation of the D-A polymer.22 PBDT-4DTBT 567 726 1.69 -1. The introduction of two 1. further indicating DTsolBT may disrupt the conjugation between the “donor” and the “acceptor” in PBDT-DTsolBT.38 -1.48 435 528 2.9  10-5 cm-1) at their maxima. The lymer of BDT (HMPBDT. leading to an elevated HOMO energy level of PBDT-DTBT Probing this library of polymers with identical conjugated (. Table 2.5. The apparently reduced electron delocalization nated by the common acceptor unit (BT).79/-3. In the why all four polymers show similar reduction potential and case of PBDT-DTsolBT. However.21 eV) compared with that of PBDT-BT (. polymers in chloroform solution (solid line) and in solid film (dash line).

levels. greater steric hindrance is formed explains why the measured HOMO energy level of . The electron density PBDT-DTsolBT 58.1 PBDT-4DTBT 5. recovering small numbers on dihedral angle 3 all three polymers incorporating modified DTBT unit clearly (Table 3). supporting observed similar LUMO energy conjugation at the linkages between thienyl groups and BT. This severe steric hindrance essentially breaks the DTBT unit.0 55. All these similarities contribute to the similar UV-vis thereby rendering the HOMO of PBDT-DTsolBT localized absorptions and band gaps of PBDT-DTBT and PBDT. Compared with PBDT-DTsolBT. 4DTBT. The electron density is well Table 3. Comparing the isophases of BDT unit. example.7 hindrance introduced by the 4DTBT. 43. over 50 angles have been calculated for the the electron density of LUMO energy levels of both PBDT.9 14. 2010 Zhou et al. These very similar.3 30. the unit in the case of PBDT-3DTBT and PBDT-DTsolBT electron density is slightly extended to the BT unit in the relieves the steric hindrance between substituted DTBT and HOMO of PBDT-3DTBT. at the donor BDT unit. of PBDT-DTBT. There is only a slight increase of the dihedral angle between the 4-substituted thienyl group and BDT PBDT-DTBT 4.06 eV) was observed for the HOMO energy dramatic numerical increase in dihedral angles 1 and 2.7 36.9 is also delocalized in the HOMO of PBDT-4DTBT. smaller torsional angles between thienyl groups and BT unit Moving these alkyl chains away from the vicinity of BDT are calculated in the case of PBDT-3DTBT. dihedral angels between thienyl groups and BT in PBDT- DTBT and PBDT-4DTBT are essentially localized on the DTsolBT. 2. Furthermore.2 17. Figure 4. at temperature 0 K and in vacuum. though a Calculations were carried out for one repeating unit of each poly- slightly biased toward the BDT unit compared with that mer. For levels of PBDT-DTBT and PBDT-4DTBT.1 10. Therefore.however slightly different. Calculated HOMO (left) and LUMO (right) orbitals of polymers.2 unit in PBDT-4DTBT. confirming the minimum steric PBDT-3DTBT 50. in gas phase.HOMO isosurfaces explain that only a slight between thienyl groups and central BT unit. Calculated Dihedral Angles of Polymersa delocalized along the conjugated backbone. No. as shown by a difference (0. as displayed by dihedral angle 1 dihedral angle 2 dihedral angle 3 the isosurface of the HOMO energy level of PBDT-DTBT polymer (deg) (deg) (deg) (Figure 4). Vol. participating aromatic units.2 19. However.2 14.816 Macromolecules.

For comparison. Therefore. By applying 3% 1. Figure 6.53 36.55 3. A mobilities. ground state. Adding additives appears to promote more characteristics of solar cells based on these four polymers ordering in the polymer domains. The severe steric hindrance would also weaken the the thinnest (65 nm) among all the polymer:PCBM films. (b) a much higher Jsc (5.01 PBDT-DTBT 1:1 65 0. 2. 43. compared with those of PBDT-DTBT.55 This noticeable red shift in the Because of its low solubility.2 V higher than that of PBDT- position of side chains. Not surprisingly. 3DTBT (0.72 .38 50. Vol.92 41. Characteristic J-V curves of the optimized devices of poly.94 24. an additive into the processing solvent (chloroform) to cated solar cell has a configuration of glass/ITO/PEDOT: modify the film morphology.92 mA/cm2). PV Performances of Polymers polymer polymer:PCBM thickness (nm) Voc (V) Jsc (mA/cm2) FF (%) η (%) PBDT-4DTBT (3% diiodooctane) 1:1 95 0. Furthermore. ing with PCBM without severe aggregation of polymers. noticeably aggregated when the solution cooled.Article Macromolecules.63 eV) of PBDT-DTBT. an overall conversion efficiency small efficiency of PBDT-DTsolBT is largely due to severely of 0.83 PBDT-3DTBT 1:1 85 0. Table 4. however. No. thin films with and without additive. which precipitated the polymer. solubilizing chains at 4-positions of these thienyl groups Photovoltaic Properties.17 PBDT-4DTBT 1:1 100 0. Bulk heterojunction photovoltaic (PBDT-4DTBT) has a minimum impact on the band gap devices were constructed to investigate the influence on and energy levels. The current-voltage FF (Table 4).21%) and PBDT-DTsolBT (0. likely due to the energy levels of PBDT-3DTBT and PBDT-DTsolBT are elevated HOMO energy level of PBDT-DTBT in the ag. leading to much increased band processable dispersion. disrupted conjugation between thienyl groups and the BT attaching these alkyl chains greatly improved the solubility unit (Table 3 and Figure 4).83%.69 eV) leads to PCBM at 1:1 weight ratio in chloroform at 5 mg/mL. anchoring of PBDT-DTsolBT. the IPCE data are shown Figure 5.89 0. low efficiencies were observed for both PBDT- despite the low band gap (1.01%). photovoltaic properties introduced by the subtle change in More importantly.8-diiodoocane as ployed to achieve similar film thicknesses.53 Thus.21 Films of PBDT-DTBT:PCBM are gaps. Representative red shift in the absorption maximum of blends processed performance parameters of solar cells are listed in Table 4. As discussed earlier. For fair comparison. the anchoring positions The BHJ devices of PBDT-DTBT and PBDT-4DTBT significantly impact the photovoltaic properties of related were further tested for their incident photon to current efficiency (IPCE).53. vices: (a) because this series of polymers have the identical Therefore.21 PBDT-DTsolBT 1:1 80 0.17% is achieved. the BHJ solar cell of PBDT-4DTBT:PCBM conjugated backbone with only variations on the size and displays a Voc of 0. mainly due to the noticeably increased Al(70 nm) (Experimental Section).72% is obtained for PBDT-DTBT.43 0.27 1.12 26. resulting in a the conjugated backbone. the newly acquired solubility/processa- positioning alkyl chains. Polymers the devices processed with additives. leading to an overall identical spin rate (1100 rpm) and time (1 min) were em. care was taken bility of PBDT-4DTBT renders a much improved intermix- during the processing to maintain similarly structured de. The low band gap (1.8 0.35 0. Shifting alkyl chains to the inner core of DTBT introduces the solution of PBDT-DTBT and PCBM was sonicated significant steric hindrance between the aromatic units on during cooling. the measured Jsc is only 3. Excessive aggregation would also likely lead delocalization would reduce the possibility of excitons to form polymers-only domains so large that excitons cannot moving to donor/acceptor interface and increase the gemi- reach a donor/acceptor interface before they decay to the nate recombination of the recently dissociated excitons.75 V (0. essentially localized at the BDT unit (Figure 4).55 V was observed. interaction between polymer chains. with additive (Figure 6). A typical fabri.75 5. PBDT-DTBT was dissolved absorption maximum might account for the improved Jsc of into chloroform at high temperature (∼60 C).54 a higher efficiency of PSS(40 nm)/polymer:PCBM blend (∼100 nm)/Ca(30 nm)/ 2. Comparison of absorption of PBDT-4DTBT:PCBM (1:1) mer-based BHJ solar cells under 1 Sun condition (100 mW/cm2). 2010 817 PBDT-3DTBT is between that of PBDT-4DTBT and that polymer-based BHJ PV cells.74 0. of resulting polymers.67 6.79 2. leading to low hole which is attributed to the low viscosity of the dispersion.37. the electron density of HOMO relatively low Voc of 0. The lack of gregated state. The very Together with a FF of 0. as indicated by a ∼50 nm blended with PCBM are shown in Figure 5. all polymers were blended with DTBT-based solar cell).53 mA/cm2 Therefore. efficiency of 1.

steric hindrance into the related D-A polymer (PBDT- 4DTBT).7%). PBDT-DTBT has a stated otherwise. with PBDT-4DTBT Experimental Section having slightly higher hole mobility. 1H nuclear magnetic further aggregation of PBDT-4DTBT while maintaining resonance (NMR) measurements were recorded either with a the connection between polymer only domains. Conclusions It has been demonstrated that introducing alkyl chains onto various positions of the dithienylbenzothiadiazole (DTBT) can significantly increase the molecular weight and solubility of related polymers. Since the film thickness of PBDT-4DTBT-based solar cells. 2. Therefore.56. However.29 On the other hand.e. If a PV performance of these two polymers. double that of the PBDT-DTBT/PCBM Strem. The IPCE curves follow individual film absorptions. which is desirable in improving necessary and purified by distillation. the measured mobilities are similar for both polymers (Table 5). The hole mobility difference is more noticeable in the polymer/PCBM blend. Thermogravi- molecular weight of PBDT-4DTBT. these indicate that charges have Finally. Gel permeation chromatography (GPC) interaction between different domains.60  10-6 cm2/(V s)). PBDT-DTBT and higher mobility together with better controlled morphology can PBDT-4DTBT. The obtained molecular positioned alkyl chains offer the excellent solubility and high weight is relative to the polystyrene standard. hole mobility values were estimated via be achieved by these new polymers. PBDT-4DTBT maintains almost identical band gap and energy levels compared with PBDT-DTBT together with the absorption of blended thin films (Figure 7). No. Mobility of Polymers under SCLC Conditions polymer only thickness (nm) mobility cm2/(V 3 s) polymer:PCBM thickness (nm) mobility cm2/(V 3 s) PBDT-4DTBT 55 4. possibly due to a higher hole For example. thereby improv.36  10-6 1:1 þ 3% diiodooctane 75 1. the properly with tetrahydrofuran (THF) as eluent. 43. Differential scanning calorimetry (DSC) measurements miscibility with PCBM in the processing solvent. with better control on the DTBT based film has slightly more absorption in the near-IR film morphology. were carried out with a model 2920 MDSC from TA Instru- tering of PCBM during solvent evaporation could help ments under a nitrogen atmosphere. temperature of degradation (Td) is correlated to a 5% weight more. in addition to a low band gap and a low HOMO device is only about 50% thicker than that of PBDT- energy level. 4DTBT can be employed in conjugation with other mobility in PBDT-4DTBT devices. Table 5. 2010 Zhou et al. significantly higher than that of PBDT-DTBT-based IPCE value of PBDT-4DTBT-based device is almost twice devices (0.60  10-5 1:1 75 9. the maximum 4DTBT. limit the microwave reactor. PBDT-4DTBT-based device.94  10-6 improving the hole mobility. As indicated earlier. However.818 Macromolecules. fused bithiophene-based polycyclic aromatics to construct D-A In order to further understand the dramatically different polymers with low band gap and low HOMO energy levels.58 Further. though the PBDT- to a more uniform mixture with PCBM. (unmodified DTBT). Our discovery reinforces the importance of high as much as that of PBDT-DTBT-based device (29% vs 16% molecular weight and good solubility of donor polymers for BHJ at 600 nm). Microwave-assisted mobility within a polymer-only domain. All these features of PBDT-4DTBT contri- region. However. Reagents and Instrumentation. These observations signify the importance of high molecular weight and good solubility of polymers in improving device efficiencies. we believe the strategy of “properly” modifying the much greater chance to reach the electrodes in the case of acceptor unit can be applied to other D-A polymers as well.20  10-6 PBDT-DTBT 55 2. More importantly. Vol.91  10-6 1:1 65 3.e. bute to a much enhanced efficiency (up to 2. an even higher efficiency can space-charge limit current (SCLC) by fabricating hole-only be expected. The ing the hole mobility in the polymer-only devices.57 For pure polymers..2%) of PBDT- with maxima at 430 and 600 nm. our study indicates that attaching alkyl chains on the 4-positions Figure 7. All reagents and chemicals The PBDT-4DTBT/PCBM blend demonstrates a much were purchased from commercial sources (Aldrich. heating rate of 10 C min-1 under a nitrogen atmosphere. The clus. which explains an even higher hole mobility (1. the good solubility of PBDT-4DTBT ensures a good loss. Fluka) and used without further purification unless blend (Table 5). the anchoring positions of these alkyl chains have a strong influence on the optical and electro- chemical properties of these structurally similar polymers with identical conjugated backbones. DTBT (100 nm vs 65 nm). IPCE and absorption of PBDT-DTBT and PBDT-4DTBT of these thienyl groups (i. long polymer chains) would PerkinElmer thermogravimetric analyzer (Pyris 1 TGA) at a connect locally ordered individual domains. Contrary to previous reports. these low polymerizations were conducted in a CEM Discover Benchmate molecular weight polymers.. higher mobility.. short chains. in order to further enhance the device efficiencies. the additional high These two films absorb light rather equally when the absorp- molecular weight and excellent solubility of PBDT-4DTBT lead tion is normalized by film thickness.e. further Bruker Avance 300 MHz AMX or a Bruker 400 MHz DRX . using additives appears to improve the film morphology with more ordering in the polymer domains. leading to an overall measurements were performed on a Waters 2695 separations module apparatus with a differential refractive index detector suppressed mobility. Acros. devices. The high molecular metric analysis (TGA) measurements were carried out with a weight of PBDT-4DTBT (i. In addition. i. Reagent grade solvents were dried when strong tendency to stack. 4DTBT) only introduces minimum (absorption is normalized by film thickness).

Internet at http://pubs. performed in gloveboxes under a nitrogen atmosphere. All the solutions (except in the case of PBDT-DTBT.4-ethylene-dioxythiophene):poly(styrenesulfonic internally calibrated by using the ferrocene/ferrocenium redox acid) (ITO/PEDOT:PSS) series resistance and contact resis- couple (Fc/Fcþ). μh is the hole mobility. Moet. E. 32. S. M. and DSC curves of all spun-coated onto precleaned glass slides from 10 mg/mL poly. A... 300 W) cali- d (doublet). X. L. poly(tetrafluoroethylene) (PTFE) filter and spun-cast at 1100 Cook. J. V is the voltage drop across the device. E. Nelson. 143506. From the plots of J0.. A... 1.. Heeger.. 2001. C. fluorescence spectra. Mater. polymers were cules.. of UV ozone over 30 min. for 10 min to give a thin film with a thickness of 40 nm. hole mobilities of copolymers can be energy levels of copolymers were calculated from the onset deduced from oxidation potentials (Eox onest) and onset reductive potentials (Ered onest). the 1995. which has a poor solubility) were filtered through a 0. R 2001. A filtered dispersion of PEDOT:PSS Funct. D.. F. D. Padinger. J. 841. P. Glass substrates coated with patterned indium-doped tin oxide (ITO) were References and Notes purchased from Thin Film Devices. blend of polymer and PCBM (1:1 w/w. M.. A. J... Lett. Chemical shifts were expressed in parts per million characterization was carried out under AM1. Wuhlbacher. R. H. Koppe. rpm for 60 s onto PEDOT:PSS layer.. and a Pt wire counter electrode was PSS layer onto ITO substrate. Moons.acs. J.. E. T. The electrochemical onsets were determined at built-in voltage Vbi which was taken as a compensation voltage the position where the current starts to differ from the base. J. Gong.. Adv. 071108. E. where ε0 is the permittivity of free space. a Ag/AgNO3 (0. K. Choulis. A. Brabec. Kroon. Gao. . EQE were detected under monochromatic carried out using a Bioanalytical Systems (BAS) Epsilon poten..59. Yang.. Phys. J. The 150 nm sputtered (1) Yu. C. D. Tencor Instruments). J. illumination (Oriel Cornerstone 260 1/4 m monochromator tiostat equipped with a standard three-electrode configuration.. with an active area of 12 mm2 per device. for 6 h. D. C.. H. polymers. There are eight devices ments were carried out with a Bruker 400 MHz DRX spectro. For the measurements of thin films. S. Lett.. O.... I. The thicknesses of films were polymers. LUMO ¼ -ðEonset ox þ 4:8Þ ðeVÞ ð2Þ Acknowledgment. Polymer films were drop-cast onto the were fabricated. McCulloch. Coupling constants J are re. 15. The applied voltage V was corrected from the measurements. and the calibration Typically. M. V.Article Macromolecules. Tencor In. struments). Vol. S.. 9 V2 mically determined band gaps were deduced from the difference J ¼ εr ε0 μh 3 between onset potentials from oxidation and reduction of 8 L copolymers as depicted in eq 3. Y.. C. Shimadzu UV-2401PC spectrophotometer. E. dried under a stream of nitrogen and subjected to the treatment (3) Ma. The de. J.1 M) mobility measurements. Yang. C. G. 5. Sci.. silicon diode.5 vs V plots of mobility measurement of all mer solutions in chloroform. 2006. Mater. A. J. brated by a NREL certified standard silicon cell. 1789. F. Tuladhar.. respectively. which is found to be around 35 Ω from a reference of -4. Prior to use. Hummelen. 2. The experimental dark current densities J of glassy carbon working electrode from a 2. 2007. Nat.05 V and the voltage drop Vrs across the indium tin line. atmosphere for 12 h.. Bj€ orstr€ om.. The thicknesses of films were recorded by a (9) Andersson. Waldauf. Inc. Havinga. O.. a DuPont Science and Engineering Grant. L. The electroche. ITO substrates at 4000 rpm for 60 s and then baked at 140 C (5) Kim. M.. Lett. M. Shrotriya. Magnusson. according to eqs 1 and 2. 1H spectra.. 2005. Bradley. UV-vis absorption spectra were obtained by a N000140911016). F.8 eV. 2007. C. M. Yao. potential (I-V) curves were recorded with a Keithley 2400 Electrochemistry. N. mers) was dissolved in chloroform with heating at 60 C (6) Scharber. Andersson. 2006. Mater. 2005. Heeger. Vekemans. Denk.5 mg/mL chloro. 13C nuclear magnetic resonance (NMR) measure.. Wudl. 10 mg/mL for poly. The measurements were done in anhydrous acetoni.. C. G. Science ITO pattern had a resistivity of 15 Ω/0. J. Brabec. G. C.. vices were finished for measurement after thermal deposition of (10) Slooff. 18. Heeger. Current versus ported in hertz (Hz). S. Fluorescence spec- tra were recorded on a Shimadzu RF-5301PC spectrofluoro. and splitting patterns are designated as s (singlet). a 30 nm film of calcium and a 70 nm aluminum film as the Sweelssen. Mater. Phys. M.. T. The potential of Ag/AgNO3 reference electrode was oxide/poly(3. F. Appl. Adv. Mater. substrates were ultrasonicated for 20 min in acetone followed (2) Shaheen. which has a known reduction potential tance. Moriarty. A.01 M in anhydrous acet. M. The substrates were then (8) Zhang. M. For trile with tetrabutyl ammonium hexafluorophosphate (0. Mater. Phys.45 μm (7) van Mullekom. Lee. 90. Cyclic voltammetry measurements were digital source meter. Huang. J. 1617. with the intensity of 100 mW/cm2 (Oriel 91160.. profilometer (Alpha-Step 200. A Durrant. a DuPont Young Professor Award. Polymer Solar Cell Fabrication and Testing. Ingan€as. a three-electrode cell equipped with a glass carbon of the incident light was performed with a monocrystalline working electrode. Ha.. This work was supported by the Univer- sity of North Carolina at Chapel Hill. No. the hole-only devices in a configuration as the supporting electrolyte under an argon atmosphere at a of ITO/PEDOT:PSS (40 nm)/copolymer-PCBM/Pd (50 nm) scan rate of 100 mV/s. Veenstra. and characterizations were employed.60 The highest occupied molecular orbital device without the polymer layer. Y. All fabrication steps after adding the PEDOT: onitrile) reference electrode. S. R. V. S. Nat. M. 667.. W. C. C.. per substrate. 2006. (4) Li. Giles. Koetse. 4.. J 0. Sariciftci. A. in water (Baytron PH500) was then spun-cast onto clean K. Hummelen. M... M. Ingan€as. Y. L. D.. J. L. and Office of Naval Research (Grant Spectroscopy. 2010 819 spectrometer. 43. Adv. Eng.. polymer:PCBM blends were measured when applied with vol- form solution and dried under house nitrogen stream prior to tage from 0 to 6 V. dried at room temperature in the glovebox under a nitrogen Yartsev. 197. Jespersen. J. Sundstr€ om. Device meter.-S. and m (multiplet). Svensson. Vbi=Voc þ 0. Funct. This material is available free of charge via the recorded by a profilometer (Alpha-Step 200. Appl. Y. 16. the National Science Foundation STC Program at UNC Chapel Hill (CHE- EC Egap ¼ ðEonset ox -Eonset red Þ ð3Þ 9876674). K. and L is the film thickness of active layer. 270. 78.. S.. Emery. by deionized water and then 2-propanol. 789.. W. 91.. The substrates were Fromherz. Zhang.5G irradiation (ppm).. cathode at a pressure of ∼1  10-6 mbar.5 vs V (HOMO) and lowest unoccupied molecular orbital (LUMO) (Supporting Information). C. M.. Ree.. εr is the dielectric constant of the polymer which is assumed to be around 3 for the HOMO ¼ -ðEonset ox þ 4:8Þ ðeVÞ ð1Þ conjugated polymers. Appl.. 864. equipped with Oriel 70613NS QTH lamp). J. Supporting Information Available: Synthesis of all mole- photometer. K.. J..

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