6. Thiophene-Based Conjugated Polymers
1.4 eV (Scheme 77). The absorption spectrum of P132 in chloroform shows a λ max at 650 nm and an onset at 720 nm
However, an onset significantly red-shifted to 860 nm and vibronic fine structure were observed when P132 was dissolved in o-dichlorobenzene (ODCB), which is indicative of strong intermolecular-interaction-induced semicrystalline aggregation. The film spin-cast from a chloroform solution of P132/PCBM showed amorphous polymer morphology due to the fast evaporation of the chloroform, which does not allow for the development of crystallinity. Therefore, the cell in which the active layer was processed from chloroform
only exhibited a very low EQE of 0.13 at 680 nm. It was found that by using a chloroform/ODCB mixture (4:1) to process the active layer, a large degree of semicrystallinity could be formed. On the basis of these optimal processing conditions, the best device using P132/PCBM (1:2, w/w) gave a PCE of 3.2%. By utilizing PC71BM as the acceptor, the photovoltaic performance was further improved and showed a high PCE of 4.0%, an FF of 0.58, a Vocof 0.61 V, and a Jscof 11.3 mA/cm2.
The synthesis of monomer 247 is shown in Scheme 78.
Reaction of 2-thiophenecarbonitrile (248) with 0.5 equiv of Scheme 68. Synthesis of P124-P126 by Stille Coupling Reactions
Scheme 69. Synthetic Route toward Monomer 222
Scheme 70. Synthetic Route toward Monomer 223
Scheme 71. Synthetic Route toward Monomer 224
di-n-butyl succinate ester in tert-amyl alcohol under basic conditions afforded an insoluble dimerization product (249) which was allowed to undergo N-alkylation with 162 to give compound 250. Bromination of 250 by NBS, followed by a Stille coupling and sequential bromination, produced the final monomer 247.
Janssen and co-workers310,311reported a series of side chain substituted conjugated polymers (P133, P134, and P135) that consist of alternating rich bithiophene and electron-deficient units including benzothiadiazole, thienopyrazine, and thiadiazoloquinoxaline, respectively. These polymers
were synthesized from the corresponding dibromo monomers 254-257 via a Yamamoto reductive reaction using Ni(COD)2as the dehalogenating reagent (Scheme 79). The advantage of Yamamoto coupling is that only a single component of monomer can self-polymerize to afford the alternating D-A polymer with moderate to high molecular weight. These polymers are very soluble in common organic solvents with the help of the branched (2-ethylhexyl)oxy side chains. The absorption edges of P133, P134, and P135 in solution are located at 720, 915, and 960 nm, respectively.
In the solid state, the band edges are further red-shifted to Scheme 72. Synthesis of P127 and P128 by Stille Coupling Reactions
Scheme 73. Synthetic Route toward Monomer 234
Scheme 74. Synthesis of P129 and P130 by Stille Coupling Reactions
800, 965, and 1034 nm corresponding to optical band gaps of 1.55, 1.28, and 1.20 eV for P133, P134, and P135, respectively. Again, the thienopyrazine unit is more capable of forming quinoid main chains than benzothiadiazole, leading to a much lower band gap. The slightly red-shifted absorption and lower optical band gap of P135 compared to P134 indicate improved conjugation caused by a more coplanar structure of the main chain in P135 due to the absence of bulky substituents, although P134 has stronger donating alkoxythiophene and P135 has a stronger acceptor due to the inductive effect of the alkoxy group in the meta-position of the phenyl ring. Therefore, in the present case, steric effects dominate over electronic effects. The
electron-donating (2-ethylhexyl)oxy side chains attached to the P134 backbone decrease the oxidation potential by 0.18 V compared to that of P135. The PSC device based on P134/
PCBM (1:4, w/w) gave a Voc of 0.39 V, a Jsc of 1.5 mA/
cm2, and a PCE of 0.29%. A similar device based on P135 showed much improved performance with a Vocof 0.56 V, a Jscof 3.1 mA/cm2, and a PCE of 1.1%. This is attributed to its lower HOMO and improved miscibility with PCBM compared to those of P134. On the other hand, a P133-based device reached a higher Vocof 0.77 V with a PCE of 0.9%.
The electron-accepting strength of benzothiadiazole can be further enhanced by fusing another pyrazine ring into the vacant sites of the phenyl ring to form thiadiazoloquinoxa-Scheme 75. Synthetic Route toward Monomer 241
Scheme 76. Synthesis of P131 by a Stille Coupling Reaction
Scheme 77. Synthesis of P132 by a Yamamoto Coupling Reaction
Scheme 78. Synthetic Route toward Monomer 247
line. By arranging thiadiazoloquinoxaline and bithiophene in an alternating fashion, the polymer P136 exhibits a strong absorption in the near-infrared region along with an ultras-mall band gap of 0.94 eV in solution.312The onsets of the oxidation and reduction waves of P136 are at -0.09 and -1.06 eV vs Fc/Fc+, respectively, and provide an electro-chemical band gap of 0.97 eV. However, the high electron affinity of thiadiazoloquinoxaline also significantly lowers the LUMO, resulting in negligible offset between P136 and PCBM and thus inefficient photoinduced electron transfer.
PC84BM with an electron affinity larger by 0.35 V than PCBM was therefore used to increase the LUMO offset between donor and acceptor.313The device based on P136/
PC84BM (1:4, w/w) showed a photoresponse up to about 1300 nm, which is one of furthest red shifts reported for a polymer BHJ solar cell. However, the overall device ef-ficiency still remains low.
Benzobis(thiadiazole), derived from benzothiadiazole fused with another thiadiazole ring, is an extremely electron-deficient unit due to its high tendency for the formation of quinoid structures and the hypervalent sulfur atom (Chart
20).314,315 A polymer (P137) containing quaterthiophene as the donor and benzobis(thiadiazole) as the acceptor was synthesized by Stille coupling (Scheme 80).316An analogous polymer (P138) using benzothiadiazole as the acceptor was also prepared for comparison. From the absorption spectra, P137 shows an extremely low band gap of 0.67 eV, which is 1 eV lower than 1.65 eV for P138 and even lower than that of polyisothianaphthene (1 eV). This result further demonstrates the exceptional electron-accepting power of the benzobis(thiadiazole) subunit. Solar cell devices with a large area (3 cm2) based on a P138/PCBM (1:2, w/w) blend gave a photovoltaic response with a PCE of 0.62%.317However, Scheme 79. Synthesis of P133-P136 by Yamamoto Coupling Reactions from 254-257
Chart 20. Resonance Structure of Benzobis(thiadiazole) (258)
the devices produced with P137 showed very low Vocand Jsc values, which is ascribed to the mismatch of LUMO energy levels between P137 and PCBM. This result again emphasizes the importance of controlling the band gap and corresponding energy levels of the polymer with respect to PCBM when the band gap starts to decrease.
2-Pyran-4-ylidenemalononitrile (PYM) is known to have strong electron-withdrawing abilities and has been intensively used as the electron acceptor part of red-emitting and nonlinear optical materials.318,319 A series of copolymers utilizing the PYM unit as the electron acceptor were reported by Dai and co-workers.320Different amounts of PYM units were copolymerized with thiophene units to yield the D-A-type copolymers P139 and P140 (Scheme 81). It was found that the properties of the polymer can be controlled by varying the PYM content ratio and the thiophene units.
Increasing the thiophenes from P139a through P139b to P139c results in red-shifted absorption spectra, gradually reduced band gaps (2.33, 2.21, and 1.99 eV), higher HOMO levels (-5.17, -5.10, and -5.01 eV), and relatively un-changed LUMO levels. As expected, the increasing trend in
Vocvalues was observed on going from P139c to P139b to P139a in accordance with the HOMO levels. The solar cells using a polymer/PCBM (1:1, w/w) blend achieved PCEs of 0.08%, 0.2%, and 0.6% for P139a, P139b, and P139c, respectively. Because the thiophene unit and PYM are connected through the meta-position of a phenyl ring, the effective conjugation of the main chain is disrupted. There-fore, increasing the content of thiophene units leads to enhanced charge transport and hence improved Jsc values and PCEs. When the phenyl group attached at the PYM moiety was replaced by a thiophene ring, P140 showed an enhanced absorption and a higher PCE of 0.9%.
6.14. Poly(thienylvinylene)s (PTVs)
Poly(thienylvinylene)s are another class of polythiophene-based conjugated polymers. These polymers display high nonlinear optical responses, moderate charge mobilities, and good electroluminescent properties. By inserting a vinylene unit between every thiophene unit to planarize the main chain and reduce aromaticity, PTVs exhibit more effective con-jugation and lower band gaps than polythiophenes. Much attention and effort has been paid to evaluate their potential for organic solar cell applications. Like the synthesis of PPV, there are two synthetic approaches used in the preparation of PTVs. One approach involves a straightforward polym-erization reaction in a single step using the appropriate monomers to generate the conjugated polymer. Two typical transition-metal-catalyzed reactions can be used to synthesize PTV directly. A Stille coupling of 2,5-dibromo-3-dodecylth-iophene (263) and 1,2-bis(tributylstannyl)ethylene (214) is expected to yield regiorandom PTV (Scheme 82). However, the resulting polymer with a regioregularity greater than 90%
was found.321This is because the oxidative addition of the palladium catalyst takes place selectively at the less sterically hindered 5-position of thiophene, leading to the formation of the intermediate compound 264, which continues to polymerize to afford regioregular P141.
Interestingly, the Heck reaction of the monomer 265 designed to prepare regioregular PTV turned out to form the regioirregular polymer P142 due to 15% R-arylation occur-ring duoccur-ring the reaction (Scheme 82). The regioregular P141 made by Stille coupling has a lower optical band gap, 1.6 eV, than regiorandom P142 made by the Heck coupling where the band gap is 1.8 eV. When P141 was blended with PCBM, an external quantum efficiency with a maximum response at 580 nm was detected. This is approximately 100 nm red-shifted compared to that of the device made from the MDMO-PPV/PCBM blend. The PSC device based on regioregular P141/PCBM (1:10, w/w) showed a moderate PCE of 0.24%.322
Scheme 80. Synthesis of Benzobis(thiadiazole)-Containing P137 and P138 by a Stille Coupling Reaction
Scheme 81. Synthesis of PYM-Containing P139 and P140 by Stille Coupling Reactions
The strategy of using branched side chains conjugated to the main chain of polythiophene has also been applied to poly(thienylenevinylene)s. 2,5-Dibromothiophene 266 with a bis(thienylenevinylene) side chain was copolymerized with 2,5-dibromo-3-hexylthiophene (104) and 1,2-bis(tributyl-stannyl)ethylene (214) by a Stille coupling to form the bis(thienylenevinylene)-branched poly(thienylenevinylene) P143 (Scheme 83).323With an m/n ratio of 0.35, this polymer shows a narrower band gap (1.57 eV) than poly((3-hexy-lthienylene)vinylene) (P3HTV) (1.62 eV) and a strong broad absorption band covering the whole visible region from 380 to 780 nm. The PCE of the PSC based on P143/PCBM (1:1, w/w) reached 0.32%, which is higher than 0.21% for P3HTV.
Another method is to prepare nonconjugated polymer precursors, which produce conjugated polymers in situ upon thermal or chemical treatment. This indirect approach is commonly applied to the synthesis of unsubstituted PTV to overcome the problematic processing resulting from the poor solubility of PTV. The sulfinyl route was developed by Vanderzande and co-workers to prepare the 3,4-dichloro- and 3,4-dibromo-PTV derivatives P144 (Scheme 84).324In the presence of sodium tert-butoxide as the base, the sulfinyl monomer 267 was polymerized via the thiophene analogues of the p-quinodimethane intermediate 268 to obtain the
polymer precursor 269, which can readily undergo thermal elimination of the sulfinyl group to produce the 3,4-dihalo-substituted P144 with a high molecular weight of >50000.
Its optical band gap was estimated to be ca. 1.55 eV. The active layer of a solar cell device was made by spin-casting the polymer precursor 269/PCBM (1:4, w/w) solution on top of the PEDOT substrate followed by thermally induced conversion at 70 °C to obtain the P144 and PCBM composite. After postproduction thermal annealing, the device based on poly((3,4-dichlorothienylene)vinylene) gave a PCE of 0.18%. Following a similar mechanism, dithio-carbamate thiophene derivative 270 has also been developed to serve as a facile precursor for the synthesis of poly((3,4-diphenyl-2,5-thienylene)vinylene) (P145), which has en-hanced thermal stability and a lower band gap of 1.7-1.8 eV (Scheme 85).325,326