Effects of donor unit and π‐bridge on photovoltaic properties of D–A copolymers based on benzo[1,2‐b:4,5‐c']‐dithiophene‐4,8‐dione acceptor unit

A series of donor‐π‐acceptor (D‐π‐A) conjugated copolymers ( PBDT‐AT, PDTS‐AT, PBDT‐TT , and PDTS‐TT ), based on benzo[1,2‐b:4,5‐c']dithiophene‐4,8‐dione (BDD) acceptor unit with benzodithiophene (BDT) or dithienosilole (DTS) as donor unit, alkylthiophene (AT) or thieno[3,2‐b]thiophene (TT) as conjugated π‐bridge, were designed and synthesized for application as donor materials in polymer solar cells (PSCs). Effects of the donor unit and π‐bridge on the optical and electrochemical properties, hole mobilities, and photovoltaic performance of the D‐π‐A copolymers were investigated. PSCs with the polymers as donor and PC₇₀BM as acceptor exhibit an initial power conversion efficiency (PCE) of 5.46% for PBDT‐AT , 2.62% for PDTS‐AT , 0.82% for PBDT‐TT , and 2.38% for PDTS‐TT . After methanol treatment, the PCE was increased up to 5.91%, 3.06%, 1.45%, and 2.45% for PBDT‐AT, PDTS‐AT, PBDT‐TT , and PDTS‐TT , respectively, with significantly increased FF. The effects of methanol treatment on the photovoltaic performance of the PSCs can be ascribed to the increased and balanced carrier transport and the formation of better nanoscaled interpenetrating network in the active layer. The results indicate that both donor unit and π‐bridge are crucial in designing a D‐π‐A copolymer for high‐performance photovoltaic materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1929–1940     

Fullerene derivative acceptors for high performance polymer solar cells

Polymer solar cells (PSCs) are composed of a blend film of a conjugated polymer donor and a soluble fullerene derivative acceptor sandwiched between a PEDOT?:?PSS coated ITO positive electrode and a low workfunction metal negative electrode. The conjugated polymer donor and the fullerene derivative acceptor are the key photovoltaic materials for high performance PSCs. For the acceptors, although [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(60)BM) and its corresponding C(70) derivative PC(70)BM are dominantly used as the acceptors in PSC at present, several series of new fullerene derivatives with higher-lying LUMO energy level and better solubility were reported in recent years for further improving the power conversion efficiency of the PSCs. In this perspective paper, we reviewed the recent research progress on the new fullerene derivative acceptors, including various PC(60)BM-like C(60) derivatives, PC(60)BM bisadduct, PC(70)BM bisadduct, indene-C(60) bisadduct and indene-C(70) bisadduct, trimetallic nitride endohedral fullerenes and other C(60) derivatives with multi side chains. The synthesis and physicochemical properties of PC(60)BM and PC(70)BM were also introduced considering the importance of the two fullerene acceptors.     

Comprehensive study of pyrido[3,4‐b]pyrazine‐based D–π–a copolymer for efficient polymer solar cells

Two D–π–A copolymers, based on the benzo[1,2‐b:4,5‐b′]‐dithiophene (BDT) as a donor unit and benzo‐quinoxaline (BQ) or pyrido‐quinoxaline (PQ) analog as an acceptor (PBDT‐TBQ and PBDT‐TPQ), were designed and synthesized as a p‐type material for bulk heterojunction (BHJ) photovoltaic cells. When compared with the PBDT‐TBQ polymer, PBDT‐TPQ exhibits stronger intramolecular charge transfer, showing a broad absorption coverage at the red region and narrower optical bandgap of 1.69 eV with a relatively low‐lying HOMO energy level at ?5.24 eV. The experimental data show that the exciton dissociation efficiency of PBDT‐TPQ:PC₇₁BM blend is better than that in the PBDT‐TBQ:PC₇₁BM blend, which can explain that the IPCE spectra of the PBDT‐TPQ‐based solar cell were higher than that of the PBDT‐TBQ‐based solar cell. The maximum efficiency of PBDT‐TPQ‐based device reaches 4.40% which is much higher than 2.45% of PBDT‐TBQ, indicating that PQ unit is a promising electron‐acceptor moiety for BHJ solar cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1822–1833     

Incorporation of Hexa‐peri‐hexabenzocoronene (HBC) into Carbazole–Benzo‐2,1,3‐thiadiazole Copolymers to Improve Hole Mobility and Photovoltaic Performance

Hexa‐peri‐hexabenzocoronene (HBC) is a discotic‐shaped conjugated molecule with strong π–π stacking property, high intrinsic charge mobility, and good self‐assembly properties. For a long time, however, organic photovoltaic (OPV) solar cells based on HBC demonstrated low power conversion efficiencies (PCEs). In this study, two conjugated terpolymers, poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5′‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PCDTBT)‐ 5 HBC and PCDTBT‐ 10 HBC, were synthesized by incorporating different amounts of HBC as the third component into poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5′‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PCDTBT) through Suzuki coupling polymerization. For comparison, the donor–acceptor (D –A) conjugated dipolymer PCDTBT was also synthesized to investigate the effect of HBC units on conjugated polymers. The HBC‐containing polymers exhibited higher thermal stabilities, broader absorption spectra, and lower highest‐occupied molecular orbital (HOMO) energy levels. In particular, the field‐effect mobilities were enhanced by more than one order of magnitude after the incorporation of HBC into the conjugated polymer backbone on account of increased interchain π–π stacking interactions. The bulk heterojunction (BHJ) polymer solar cells (PSCs) fabricated with the polymers as donor and PC₇₁BM as acceptor demonstrated gradual improvement of open‐circuit voltage (V_OC) and short‐circuit current (J_SC) with the increase in HBC content. As a result, the PCEs were improved from 3.21 % for PCDTBT to 3.78 % for PCDTBT‐ 5 HBC and then to 4.20 % for PCDTBT‐ 10 HBC.     

2,3‐bis(5‐Hexylthiophen‐2‐yl)‐6,7‐bis(octyloxy)‐5,8‐di(thiophen‐2‐yl) quinoxaline: A good construction block with adjustable role in the donor‐π‐acceptor system for bulk‐heterojunction solar cells

Three 2,3‐bis(5‐hexylthiophen‐2‐yl)‐6,7‐bis(octyloxy)‐5,8‐di(thiophen‐2‐yl)‐quinoxaline ( BTTQ )‐based conjugated polymers, namely, PF‐BTTQ ( P1 ), PP‐BTTQ ( P2 ), and PDCP‐BTTQ ( P3 ), were successfully synthesized for efficient polymer solar cells (PSCs) with electron‐rich units of fluorene and dialkoxybenzene and electron‐deficient unit dicyanobenzene, respectively. All the polymers exhibited good solubility in common organic solvents and good thermal stability. Their deep‐lying HOMO energy levels enabled them good stability in the air and the relatively low HOMO energy level assured a higher open circuit potential when used in PSCs. Bulk‐heterojunction solar cells were fabricated using these copolymers blended with a fullerene derivative as an acceptor. All of them exhibited promising performance, and the best device performance with power conversion efficiency up to 3.30% was achieved under one sun of AM 1.5 solar simulator illumination (100 mW/cm²). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

New quinoxaline derivatives as accepting units in donor–acceptor type low‐band gap polymers for organic photovoltaic cells

A series of new donor–acceptor‐type low‐band‐gap semiconducting polymers were synthesized as electron donors for organic photovoltaic cells. The polymers comprised quinoxaline derivatives as the acceptors and a benzodithiophene (BDT) derivative as the donors. 5,8‐Dibromoquinoxaline (Qx), 8,11‐dibromobenzo[a]phenazine (BPz), 10,13‐dibromodibenzo[a,c]phenazine (DBPz), and 8,11‐dibromo‐5‐(9H‐carbazol‐9‐yl)benzo[a]phenazine) (CBPz) were synthesized and polymerized with 2,6‐bis(trimethyltin)?4,8‐diethylhexyloxybenzo‐[1,2‐b;3,4‐b]dithiophene (BDT) through Stille cross‐coupling to produce four types of fully conjugated semiconducting polymers: PBDT‐Qx, PBDT‐BPz, PBDT‐DBPz, and PBDT‐CBPz , respectively. Intramolecular charge transfer between the electron donating and accepting units in the polymeric backbone induced a broad absorption from 300 to 800 nm. The optical band gap energies of the polymers were measured from their absorption onsets to be 1.54–1.80 eV depending on the polymer structure. Solution‐processed field‐effect transistors were fabricated to measure the hole mobilities of the polymers, and bulk hetero‐junction photovoltaic devices were fabricated using the synthesized polymers as electron donors and fullerene derivatives as electron acceptors. One of these devices showed a high power conversion efficiency of 3.87% with an open‐circuit voltage of 0.78 V, a short‐circuit current of 9.68 mA/cm², and a fill factor of 0.51 under air mass 1.5 global (AM 1.5 G) illumination conditions (100 mW/cm²). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4136–4149     

New low band‐gap semiconducting polymers consisting of 5‐(9H‐carbazol‐9‐yl)benzo[a]phenazine as a new acceptor unit for organic photovoltaic cells

A new carbazole‐based electron accepting unit, 5‐(2,7‐dibromo‐9H‐carbazol‐9‐yl)benzo[a]phenazine (CBP), was newly designed and synthesized as the acceptor part of donor‐acceptor type low band‐gap polymers for polymer solar cells. The CBP was copolymerized with electron donating monomers such as benzo[1,2‐b:4,5‐b′]dithiophene (BDT) or 4,8‐bis(2‐octyl‐2‐thienyl)‐benzo[1,2‐b:4,5‐b′]dithiophene (BDTT) through Stille cross‐coupling polymerization, and produced two alternating copolymers, PBDT‐CBP and PBDTT‐CBP. An alternating copolymer (PBDT‐CBZ) consisted of 2,7‐dibromo‐9‐(heptadecan‐9‐yl)‐9H‐carbazole (CBZ) and BDT units was also synthesized for comparison. PBDT‐CBZ showed the maximum absorption at 430 nm and did not show absorption at wavelengths longer than 513 nm. However, CBP containing polymers (PBDT‐CBP and PBDTT‐CBP) showed a broad absorption between 300 and 850 nm due to the intramolecular charge transfer interaction between the electron donating and accepting blocks in the polymeric backbone. Bulk heterojunction photovoltaic devices were fabricated using the synthesized polymers as electron donors and [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM) as electron acceptor. One of these devices showed a power conversion efficiency of 2.33%, with an open‐circuit voltage of 0.81 V, a short‐circuit current of 6.97 mA/cm², and a fill factor (FF) of 0.41 under air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW/cm²). © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2354–2365     

Bulk heterojunction polymer solar cells based on binary and ternary blend systems

Polymer solar cells (PSCs) were fabricated using a ternary blend film consisting two conjugated polymers and a soluble fullerene derivative as the donor and acceptor materials, respectively. And, to compare ternary blend system, the single‐component copolymers consisting of the repeating units of each of the copolymers, used in ternary blend solar cells, were designed and synthesized for use as the electron donor materials in binary blend solar cells. We systematically investigated the field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers. Under optimized conditions, the binary blend polymer systems showed power conversion efficiencies (PCEs) for the PSCs in the range 3.87–4.16% under AM 1.5 illumination (100 mW cm^?2). All polymers exhibited similar PCEs that did not depend on the ratio of repeating units. The binary blend solar cell containing a single‐component copolymer as the electron donor material performed better than the ternary blend solar cell in this work. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of three new 1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl) pyrrole‐based donor polymers and their bulk heterojunction solar cell applications

A series of three new 1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole‐based polymers such as poly[1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole] ( PTPT ), poly[1,4‐(2,5‐bis(octyloxy)phenylene)‐alt‐5,5'‐(1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole)] ( PPTPT ), and poly[2,5‐(3‐octylthiophene)‐alt‐5,5'‐(1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole)] ( PTTPT ) were synthesized and characterized. The new polymers were readily soluble in common organic solvents and the thermogravimetric analysis showed that the three polymers are thermally stable with the 5% degradation temperature >379 °C. The absorption maxima of the polymers were 478, 483, and 485 nm in thin film and the optical band gaps calculated from the onset wavelength of the optical absorption were 2.15, 2.20, and 2.13 eV, respectively. Each of the polymers was investigated as an electron donor blending with PC₇₀BM as an electron acceptor in bulk heterojunction (BHJ) solar cells. BHJ solar cells were fabricated in ITO/PEDOT:PSS/polymer:PC₇₀BM/TiO_x/Al configurations. The BHJ solar cell with PPTPT :PC₇₀BM (1:5 wt %) showed the power conversion efficiency (PCE) of 1.35% (J_sc = 7.41 mA/cm², V_oc = 0.56 V, FF = 33%), measured using AM 1.5G solar simulator at 100 mW/cm² light illumination. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of highly conjugated side‐group‐substituted benzo[1,2‐b:4,5‐b′]dithiophene‐based copolymer for use in organic solar cells

A new donor–acceptor (D–A) conjugated copolymer based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) was synthesized via a Stille cross‐coupling reaction. A highly conjugated thiophene‐based side group, tris(thienylenevinylene) (TTV), was incorporated into each BDT unit to generate the two‐dimensional D–A copolymer (PBDT‐TTV). An alkoxy‐substituted BDT‐based TPD copolymer (PBDT‐OR) was synthesized using the same polymerization method for comparison. PBDT‐TTV thin films produced two distinct absorption peaks. The shorter wavelength absorption (458 nm) was attributed to the BDT units containing the TTV group, and the longer wavelength band (567–616 nm) was attributed to intramolecular charge transfer between the BDT donor and the TPD acceptor. The highest occupied molecular orbital energy levels of PBDT‐OR and PBDT‐TTV were calculated to be −5.53 and −5.61 eV, respectively. PBDT‐TTV thin films harvested a broad solar spectrum covering the range 300–700 nm. A comparison with the PBDT‐OR films revealed stronger interchain π–π interactions in the PBDT‐TTV films and, thus, a higher hole mobility. A polymer solar cell device prepared using PBDT‐TTV as the active layer was found to exhibit a higher power conversion efficiency than a device prepared using PBDT‐OR under AM 1.5 G (100 mW/cm²) conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 653–660     

Synthesis and characterization of arylenevinylenearylene–naphthalene diimide copolymers as acceptor in all–polymer solar cells

Two n‐type conjugated D‐A copolymers, P(TVT‐NDI) and P(FVF‐NDI) with thienylene‐vinylene‐thienylene (TVT) or furanylene‐vinylene‐furanylene (FVF) as donor (D) units and naphthalene diimide (NDI) as the acceptor (A) units, were synthesized by the Stille coupling copolymerization. The two polymers possess good solubility, high thermal stability, and broad absorption bands with absorption edges at 866 nm for P(TVT‐NDI) and 886 nm for P(FVF‐NDI) . The LUMO energy levels of P(TVT‐NDI) and P(FVF‐NDI) are ?3.80 eV and ?3.76 eV respectively, so the two polymers are suitable for the application as acceptor in blending with most polymer donor in PSCs based on the energy level matching point of view. All polymer solar cells (all‐PSCs) were fabricated with P(TVT‐NDI) or P(FVF‐NDI) as acceptor and medium bandgap polymer J51 as donor for investigating the photovoltaic performance of the two n‐type conjugated polymer acceptors. And higher power conversion efficiency of 6.43% for P(TVT‐NDI) and 5.21% for P(FVF‐NDI) was obtained. The results indicate that arylenevinylenearylene–naphthalene diimide copolymer are promising polymer acceptor for all–PSCs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1757–1764     

Low‐bandgap quinoxaline‐based D–A‐type copolymers: Synthesis,characterization, and photovoltaic properties

Three classes of quinoxaline (Qx)‐based donor–acceptor (D–A)‐type copolymers, poly[thiophene‐2,5‐diyl‐alt‐2,3‐bis(4‐(octyloxy)phenyl‐quinoxaline‐5,8‐diyl] P(T‐Qx), poly{4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl‐alt‐2,3‐bis(4‐(octyloxy)phenyl‐quinoxaline‐5,8‐diy} P(BDT‐Qx), and poly{4,8‐bis(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(5′,8′‐di‐2‐thienyl‐2,3‐bis(4‐octyloxyl)phenyl)‐quinoxaline‐5,5‐diyl} P(BDT‐DTQx), were synthesized via a Stille coupling reaction. The Qx unit was functionalized at the 2‐ and 3‐positions with 4‐(octyloxy)phenyl to provide good solubility and to reduce the steric hindrance. The absorption spectra of the Qx‐containing copolymers could be tuned by incorporating three different electron‐donating moieties. Among these, P(T‐Qx) acted as an electron donor and yielded a high‐performance solar cell by assuming a rigid planar structure, confirmed by differential scanning calorimetry, UV–vis spectrophotometer, and density functional theory study. In contrast, the P(BDT‐Qx)‐based solar cell displayed a lower power conversion efficiency (PCE) with a large torsional angle (34.7°) between the BDT and Qx units. The BDT unit in the P(BDT‐DTQx) backbone acted as a linker and interfered with the formation of charge complexes or quinoidal electronic conformations in a polymer chain. The PCEs of the polymer solar cells based on these copolymers, in combination with [6,6]‐phenyl C70 butyric acid methyl ester (PC₇₁BM), were 3.3% [P(T‐Qx)], 1.9% [P(BDT‐Qx)], and 2.3% [P(BDT‐DTQx)], respectively, under AM 1.5G illumination (100 mW cm^?2). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of thieno[3,2‐b]thiophene‐isoindigo‐based copolymers as electron donor and hole transport materials for bulk‐heterojunction polymer solar cells

A novel class of thieno[3,2‐b]thiophene (TT) and isoindigo based copolymers were synthesized and evaluated as electron donor and hole transport materials in bulk‐heterojunction polymer solar cells (BHJ PSCs). These π‐conjugated donor‐acceptor polymers were derived from fused TT and isoindigo structures bridged by thiophene units. The band‐gaps and the highest occupied molecular orbital (HOMO) levels of the polymers were tuned using different conjugating lengths of thiophene units on the main chains, providing band‐gaps from 1.55 to 1.91 eV and HOMO levels from ?5.34 to ?5.71 eV, respectively. The corresponding lowest unoccupied molecular orbital (LUMO) levels were appropriately adjusted with the isoindigo units. Conventional BHJ PSCs (ITO/PEDOT:PSS/active layer/interlayer/Al) with an active layer composed of the polymer and PC₇₁BM were fabricated for evaluation. Power conversion efficiency from a low of 1.25% to a high of 4.69% were achieved with the best performing device provided by the D?π?A polymer with a relatively board absorption spectrum, high absorption coefficient, and more uniform blend morphology. These results demonstrate the potential of this class of thieno[3,2‐b]thiophene‐isoindigo‐based polymers as efficient electron donor and hole transport polymers for BHJ PSCs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Effects of alkyl side chain length of low bandgap naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole‐based copolymers on the optoelectronic properties of polymer solar cells

Two donor‐π‐acceptor (D‐π‐A) type naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole (NT)‐based conjugated copolymers (CPs), namely, PBDT‐TT‐DTNT‐HD and PBDT‐TT‐DTNT‐OD, containing different side chain length (2‐hexyldecyl, HD and 2‐octyldodecyl, OD) anchoring to thiophene π‐bridge between the two‐dimensional (2D) 5‐((2‐butyloctyl)thieno[3,2‐b]thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT‐TT) unit and NT moiety are developed and fully characterized. The resultant two copolymers exhibited broader absorption in wide range of 300–820 nm and obviously deepened E_HOMO of approximately −5.50 eV. The effects of side chain length on film‐forming ability, absorption, energy levels, aggregation, dielectric constant (ɛ_r), mobility, morphology, and photovoltaic properties are further systematically investigated. It was found that the side chain length had little impact on solution‐processability, absorption, energy levels, and aggregation in CB solution of resultant CPs. However, tinily increasing side chain length promoted to form the more ordered structure of neat polymer film even if the corresponding ɛ_r decreased. As a result, the side‐chain‐extended PBDT‐TT‐DTNT‐OD:PC₇₁BM‐based device achieved 32% increased FF than that of PBDT‐TT‐DTNT‐HD:PC₇₁BM and thus the PCE was significantly raised from 3.99% to 5.21%, which were benefited from 2 times higher SCLC hole mobility, more favorable phase separation, and improved exciton dissociation. These findings could provide an important and valuable insight by side chain modulation for achieving efficient PSCs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2059–2071     

Density functional study on the effect of substituent group for the monomer of donor‐acceptor copolymer

The effect of the substituent groups (alkyl or aryl) on the structure, electronic, optical properties, ionization potentials (IPs), electron affinities (EAs), and reorganization energy of the donor–acceptor monomers 5,8‐di‐2‐thienyl‐quinoxaline (T[Q]T), 4,9‐di‐2‐thienylpyrazine[2,3‐g]quinoxaline (T[PQ]T) were studied theoretically. The lowest‐lying absorption in assigned to π→π* transition, and the fluorescence can be described as originating from the ¹[ππ*] excited state. The lowest‐lying absorption and emission spectrum of T[Q]T and T[PQ]T with alkyl groups exhibit blue‐shifted, while T[Q]T and T[PQ]T with aryl groups exhibit the opposite result. The extra absorption bond at 400 nm of T[Q]T‐Bph is contributed by the π‐π* transitions between the biphenyl and acceptor fragment. Orbital compositions transfer coefficient (χ) of the donor in LUMOs is reduced with the aryl groups on the acceptor, which illuminates that the aryl contributes to intramolecular charge transfer, and the result is in accord with the analysis of reorganization energy. IPs is brought down by both of the alkyl and aryl groups, but EAs is raised only by aryl, therefore, aryl is conductive to forming excitons for D‐A‐D molecule. Consequently, T[Q]T and T[PQ]T with aryl groups are more reasonable monomers of donor–acceptor copolymers as a solar cell materials comparing with the alkyl‐introduced ones. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Fluorobenzotriazole-Based Medium-Bandgap Conjugated D–A Copolymers for Applications to Fullerene-Based and Nonfullerene Polymer Solar Cells

Two new medium-bandgap (MBG) donor–acceptor (D–A) conjugated polymers (PSTF and PDTS) with fluorobenzotriazole as an A unit and spiro[cyclopenta[1,2-b:5,4-b′]dithiophene-4,9′-fluorene] (STF) or dithienosilole (DTS) as the D unit are designed and synthesized as donor materials for polymer solar cell (PSC) applications. PSTF shows a broader absorption spectrum relative to PDTS reflecting an additional high-energy absorption band due to the conjugated thiophene side chains on STF moiety. Compared with PDTS, PSTF exhibits weaker π–π aggregation and lower lying HOMO level. Photovoltaic properties of the PSCs reveal that either PSTF or PDTS using PC₆₁BM as acceptor exhibits better performances than that of ITIC as acceptor, which results from the simultaneously increased V_oc, J_sc, and FF of PC₆₁BM-based PSCs. Moreover, when combined with PC₆₁BM and ITIC, the PSTF-based PSCs exhibit an efficiency of 3.66% and 2.42%, respectively, which is 45% and almost 1.5 times higher than that of the PDTS-based PSCs, respectively. This can be ascribed to the obviously improved V_oc and FF of PSTF-based PSCs benefitted from the deeper HOMO level and better active layer morphology. Our work demonstrates that using spiro-annulated building block as donor unit to construct MBG D-A copolymers is an alternative and effective approach for achieving efficient donor materials in PSCs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2330–2343     

Medium band gap conjugated polymers from thienoacene derivatives and pentacyclic aromatic lactam as promising alternatives of poly(3‐hexylthiophene) in photovoltaic application

Two alternating medium band gap conjugated polymers (PBDT‐TPTI and PDTBDT‐TPTI) derived from 4,8‐bis(4,5‐dioctylthien‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene (BDT‐T) or 5,10‐bis(4,5‐didecylthien‐2‐yl)dithieno[2,3‐d:2′,3′‐d′]benzo[1,2‐b:4,5‐b′]dithiophene (DTBDT‐T) with pentacyclic aromatic lactam of N,N‐didodecylthieno[2′,3′:5,6]pyrido[3,4‐g]thieno[3,2‐c]‐iso‐quinoline‐5,11‐dione (TPTI), are synthesized and characterized. The comparative investigation of the photostabilities of the copolymers revealed that the PDTBDT‐TPTI film exhibited the comparable photostability in relative to P3HT. Meanwhile, the inverted photovoltaic cells (i‐PVCs) from the blend films of PBDT‐TPTI and/or PDTBDT‐TPTI with PC₇₁BM, in which poly[(9,9‐bis(3′‐(N,N‐dimethylamino)propyl)‐2,7‐fluorene)‐alt‐2,7‐(9,9‐dioctylfluorene)] were used as cathode modifying interlayer, presented higher power conversion efficiencies (PCEs) of 5.98% and 6.05% with photocurrent response ranging from 300 nm to 650 nm in contrast with the PCEs of 4.48% for the optimal inverted PVCs from P3HT/PC₇₁BM under AM 1.5 G 100 mW/cm². The PCEs of the i‐PVCs from PBDT‐TPTI and PDTBDT‐TPTI were improved to 7.58% and 6.91% in contrast to that of 0.02% for the P3HT‐based i‐PVCs, and the photocurrent responses of the devices were extended to 300–792 nm, when the ITIC was used as electron acceptor materials. The results indicate that the PBDT‐TPTI and PDTBDT‐TPTI can be used as the promising alternatives of notable P3HT in the photovoltaic application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 85–95     

Polymer solar cells based on quinoxaline and dialkylthienyl substituted benzodithiophene with enhanced open circuit voltage

A poly[benzodithiophene‐alt‐di‐2‐thienyl‐quinoxaline] series (PBDTDPQ‐EH, PBDTDPQ‐OD, and PBDTDPQ‐HDT) was synthesized via Stille coupling. Deep highest occupied molecular orbital (HOMO) levels were achieved by the introduction of 2‐decyl‐4‐hexyl‐thiophen‐yl (HDT) side chains. The introduction of the various side chains increased the molecular weight of the polymers, and the polymers dissolved well in common organic solvents at room temperature. The HOMO energy level (?5.20 to ?5.49 eV) decreased because of the 2D conjugated structure. X‐ray diffraction analysis showed that PBDTDPQ‐OD had a slightly edge‐on structure. In the case of PBDTDPQ‐HDT, however, the structure was amorphous due to the thiophene side chain, and the extent of π stacking increased. After fabricating bulk‐heterojunction‐type polymer solar cells, the OPV characteristics were evaluated. The values of open‐circuit voltage (V_oc), short‐circuit current (J_sc), fill factor, and power conversion efficiency (PCE) were 0.88 V, 7.9 mA cm^?2, 45.4%, and 3.2%, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1028–1036     

Random fluorene copolymers with on‐chain quinoxaline acceptor units

Two series of novel random polyfluorene copolymers containing quinoxaline units were prepared by stressing the coupling according to Yamamoto. The first series contains 2,3‐bis‐(4′‐tert‐butyl‐biphenyl‐4‐yl)benzo[g]quinoxaline and the second series 2,3‐bis‐(4′‐tert‐butyl‐biphenyl‐4‐yl)quinoxaline as energy accepting unit. The copolymers were identified by gel permeation chromatography, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. Thermal properties were analyzed by thermal gravimetric analysis and differential scanning calorimetry revealing amorphous copolymers that are stable up to 430 °C. The morphology was investigated using atomic force microscopy. The optical properties in solutions and thin films were analyzed. Furthermore, the thin film electro‐optical properties were determined in monolayer polymer light‐emitting devices. Single layer devices were built with efficiencies ranging from 0.15 to 2.0 cd/A. For the random copolymers with 5 mol % benzo[g]quinoxazoline in the polyfluorene backbone some threefold efficiency enhancement from 1.1 to 3.0 cd/A was achieved by utilizing an ultra thin interlayer of poly(9,9‐di‐n‐octylfluorene‐2,7‐diyl)‐alt‐[1,4‐phenylene‐(4‐sec‐butylphenylimino)‐1,4‐phenylene] between PEDOT:PSS and the emissive random copolymer layer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4773–4785, 2007     

Ethynylene‐containing donor–acceptor alternating conjugated polymers: Synthesis and photovoltaic properties

Four ethynylene‐containing donor‐acceptor alternating conjugated polymers P1 – P4 with 2,5‐bis(dodecyloxy) substituted phenylene or carbazole as the donor unit and benzothiadiazole (BTZ) as the acceptor unit were synthesized and used as donor polymers in bulk heterojunction polymer solar cells. The optical, electrochemical, and photovoltaic properties of these four polymers with the ethylene unit located at different positions of the polymer chains were systematically investigated. Our results demonstrated that absorption spectra and the HOMO and LUMO energy levels of polymers could be tuned by varying the position of the ethynylene unit in the polymer chains. Photovoltaic devices based on polymer/PC₇₁BM blend films spin coated from chloroform and dichlorobenzene solutions were investigated. For all four polymers, open circuit voltages (V_oc) higher than 0.8 V were obtained. P4 , with ethynylene unit between BTZ and thiophene, shows the best performance among these four polymers, with a V_oc of 0.94 V, a J_sc of 4.2 mA/cm², an FF of 0.40, and a PCE of 1.6%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013