Synthesis of bistriphenylamine‐ and benzodithiophene‐based random conjugated polymers for organic photovoltaic applications

In this study, donor–acceptor random polymers containing benzotriazole acceptor and bistriphenylamine and benzodithiophene donors, P1 and P2 , were successfully synthesized by Stille coupling polymerization. The effect of bistriphenylamine moiety and thiophene π‐conjugated linker on electrochemical, spectroelectrochemical, and optical behaviors of the polymers were investigated. Optoelectronic properties and photovoltaic performance of the polymers were examined under the illumination of AM 1.5G, 100 mW cm^?2. The polymers were characterized by cyclic voltammetry, UV‐Vis‐NIR absorption spectroscopy, gel permeation chromatography. HOMO/LUMO energy levels of P1 and P2 were calculated as ?5.47 eV/–3.41 eV and ?5.43 eV/–3.27 eV, respectively. Bulk heterojunction type solar cells were constructed using blends of the polymers (donor) and [6,6]‐phenyl C₇₁ butyric acid methyl ester (PC₇₁BM) (acceptor). Photovoltaic studies showed that the highest power conversion efficiency of these photovoltaic devices were recorded as 3.50% with open circuit voltage; 0.79 V, short circuit current; 9.45 mA cm^?2, fill factor; 0.53 for P1 :PC₇₁BM (1:2, w/w) in 3% o‐dichlorobenzene (o‐DCB) solution and 3.15% with open circuit voltage; 0.75 V, short circuit current; 8.59 mA cm^?2, fill factor; 0.49 for P2 :PC₇₁BM (1:2, w/w) in 2% chlorobenzene (CB) solution. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3705–3715     

The new low‐band gap polymers comprising C‐, Si‐, or N‐bridged dithiophene and alkoxy‐modified 2,1,3‐benzooxadiazole units for bulk heterojunction solar cells

In this study, we used Stille coupling polymerization to synthesize a series of new low‐band gap‐conjugated polymers— PCyTBO , PCySiTBO , and PCyNTBO —comprising mainly electron‐rich C‐, Si‐, and N‐bridged dithiophene units in conjugation with electron‐deficient alkoxy‐modified 2,1,3‐benzooxadiazole moieties. The highest occupied molecular orbital energy levels of these polymers become higher as the electron‐donating ability of C‐, Si‐, or N‐bridged dithiophene units increases. These polymers also displayed excellent thermal stability and broad spectral absorptions, with PCySiTBO revealing some crystallinity. As a result, the photovoltaic device incorporating the PCySiTBO /PC₇₁BM (1:1) blend system and 1,8‐diiodooctane (2 vol %) as an additive exhibited excellent performance, under AM 1.5 G irradiation (100 mW cm^?2), with a value of V_oc of 0.64 V, a short‐circuit current density of 13.8 mA cm^?2, a fill factor of 0.57, and a promising power conversion efficiency of 5.0%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Thiazolothiazole‐containing polythiophenes with low HOMO level and high hole mobility for polymer solar cells

Two regiochemically defined polythiophenes containing thiazolothiazole acceptor unit were synthesized by palladium(0)‐catalyzed Stille coupling reaction. The thermal, electrochemical, optical, charge transport, and photovoltaic properties of these copolymers were examined. Compared to P1 with head‐to‐head coupling of two middle thiophenes, P2 with head‐to‐tail coupling of two middle thiophenes exhibits 40 nm red shift of absorption spectrum in film and 0.3 eV higher HOMO level. Both polymers exhibit field‐effect hole mobility as high as 0.02 cm² V^?1 s^?1. Polymer solar cells (PSCs) were fabricated based on the blend of the polymers and methanofullerene[6,6]‐phenyl C71‐butyric acid methyl ester (PC₇₁BM). The PSC based on P1 :PC₇₁BM (1:2, w/w) exhibits a power conversion efficiency of 2.7% under AM 1.5, 100 mW cm^?2, two times of that based on P2 :PC₇₁BM. The higher efficiency is attributed to lower HOMO (?5.6 eV) and smaller phase separation scale in P1 :PC₇₁BM blend. Tiny change in thiophene connection of P1 and P2 lead to great difference in HOMO, phase separation scale, and efficiency of their photovoltaic devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

2,1,3‐benzothiadiazole‐5,6‐dicarboxylicimide based semicrystalline polymers for photovoltaic cells

Two semicrystalline low band gap polymers based on highly electron‐deficient 2,1,3‐benzothiadiazole‐5,6‐dicarboxylicimide (BTI) were synthesized by considering the chain planarity via intrachain noncovalent coulombic interactions. The thiophene‐BTI and thienothiophene‐BTI based PPDTBTI and PPDTTBTI have a low band gap (～1.5 eV) via strong intramolecular charge transfer interaction, showing a broad light absorption covering 300～850 nm. Semicrystalline film morphology was observed for both polymers in the grazing incidence wide angle X‐ray scattering measurements. Interestingly, PPDTBTI showed a pronounced edge on packing structure but PPDTTBTI showed predominantly a face on orientation in both pristine and blend films. Different packing patterns influenced significantly the charge carrier transport, recombination and resulting photovoltaic characteristics. The best power conversion efficiency was measured to be 5.47% for PPDTBTI and 6.78% for PPDTTBTI, by blending with the fullerene derivative, PC₇₁BM. Compared to the PPDTBTI blend, PPDTTBTI: PC₇₁BM suffered from the lower open‐circuit voltage but showed the substantially higher hole mobility and short‐circuit current density with smaller charge recombination, showing very good agreements with molecular structures and morphological characteristics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3826–3834     

Silole‐containing polymers for high‐efficiency polymer solar cells

Silole‐containing conjugated polymers ( P1 and P2 ) carrying methyl and octyl substituents, respectively, on the silicon atom were synthesized by Suzuki polycondensation. They show strong absorption in the region of 300–700 nm with a band gap of about 1.9 eV. The two silole‐containing conjugated polymers were used to fabricate polymer solar cells by blending with PC₆₁BM and PC₇₁BM as the active layer. The best performance of photovoltaic devices based on P1 /PC₇₁BM active layer exhibited power conversion efficiency (PCE) of 2.72%, whereas that of the photovoltaic cells fabricated with P2 /PC₇₁BM exhibited PCE of 5.08%. 1,8‐Diiodooctane was used as an additive to adjust the morphology of the active layer during the device optimization. PCE of devices based on P2 /PC₇₁BM was further improved to 6.05% when a TiO_x layer was used as a hole‐blocking layer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and applications of cyano‐vinylene‐based polymers containing cyclopentadithiophene and dithienosilole units for photovoltaic cells

Two β‐cyano‐thiophenevinylene‐based polymers containing cyclopentadithiophene ( CPDT‐CN ) and dithienosilole ( DTS‐CN ) units were synthesized via Stille coupling reaction with Pd(PPh₃)₄ as a catalyst. The effects of the bridged atoms (C and Si) and cyano‐vinylene groups on their thermal, optical, electrochemical, charge transporting, and photovoltaic properties were investigated. Both polymers possessed the highest occupied molecular orbital (HOMO) levels of about ?5.30 eV and the lowest unoccupied molecular orbital (LUMO) levels of about ?3.60 eV, and covered broad absorption ranges with narrow optical band gaps (ca. 1.6 eV). The bulk heterojunction polymer solar cell (PSC) devices containing an active layer of electron‐donor polymers ( CPDT‐CN and DTS‐CN ) blended with an electron‐acceptor, that is, [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM), in different weight ratios were explored under 100 mW/cm² of AM 1.5 white‐light illumination. The PSC device based on DTS‐CN: PC₇₁BM (1:2 w/w) exhibited a best power conversion efficiency (PCE) value of 2.25% with V_oc = 0.74 V, J_sc = 8.39 mA/cm², and FF = 0.36. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Side‐chain effects on phenothiazine‐based donor–acceptor copolymer properties in organic photovoltaic devices

A series of new phenothiazine‐based donor–acceptor copolymers, P1 and P2, were synthesized via a Suzuki coupling reaction. The weight‐averaged molecular weights (M_w) of P1 and P2 were found to be 16,700 and 16,100, with polydispersity indices of 1.74 and 1.39, respectively. The UV–visible absorption spectra of the polymer thin films contained three strong absorption bands in the ranges 318–320 nm, 430–436 nm, and 527–568 nm. The absorption peaks at 320 and 430 nm originated mainly from the phenothiazine‐based monomer units, and the longer wavelength absorption band at 527–568 nm was attributed to the increased effective conjugation length of the polymer backbones. Solution‐processed field‐effect transistors fabricated with these polymers exhibited p‐type organic thin film transistor characteristics. The field‐effect mobilities of P1 and P2 were measured to be 1.0 × 10^?4 and 7.5 × 10^?5 cm² V^?1 s^?1, respectively, with on/off ratios in the order of 10⁴ for all polymers. A photovoltaic device in which a P2/PC₇₁BM (1/3) blend film was used as the active layer exhibited an open‐circuit voltage (V_OC) of 0.70 V, a short‐circuit current (J_SC) of 6.79 mA cm⁽², a fill factor of 0.39, and a power conversion efficiency of 1.86% under AM 1.5 G (100 mW cm^?2) illumination. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and applications of low‐bandgap conjugated polymers containing phenothiazine donor and various benzodiazole acceptors for polymer solar cells

A series of soluble donor‐acceptor conjugated polymers comprising of phenothiazine donor and various benzodiazole acceptors (i.e., benzothiadiazole, benzoselenodiazole, and benzoxadiazole) sandwiched between hexyl‐thiophene linkers were designed, synthesized, and used for the fabrication of polymer solar cells (PSC). The effects of the benzodiazole acceptors on the thermal, optical, electrochemical, and photovoltaic properties of these low‐bandgap (LBG) polymers were investigated. These LBG polymers possessed large molecular weight (M_n) in the range of 3.85?5.13 × 10⁴ with high thermal decomposition temperatures, which demonstrated broad absorption in the region of 300?750 nm with optical bandgaps of 1.80?1.93 eV. Both the HOMO energy level (?5.38 to ?5.47 eV) and LUMO energy level (?3.47 to ?3.60 eV) of the LBG polymers were within the desirable range of ideal energy level. Under 100 mW/cm² of AM 1.5 white‐light illumination, bulk heterojunction PSC devices containing an active layer of electron donor polymers mixed with electron acceptor [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) in different weight ratios were investigated. The best performance of the PSC device was obtained by using polymer PP6DHTBT as an electron donor and PC₇₁BM as an acceptor in the weight ratio of 1:4, and a power conversion efficiency value of 1.20%, an open‐circuit voltage (V_oc) value of 0.75 V, a short‐circuit current (J_sc) value of 4.60 mA/cm², and a fill factor (FF) value of 35.0% were achieved. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Benzodithiophene‐thiophene‐based photovoltaic polymers with different side‐chains

A series of benzodithiophene‐thiophene‐based alternating copolymers were synthesized with different side‐chains, and their photovoltaic characteristics were examined. The choice of solubilizing side‐chains influences significantly the chain conformation, frontier orbital energy levels, intermolecular organization, and the resulting optical, morphological, and photovoltaic properties. The incorporation of an e‐withdrawing carbonyl group in the side‐chain decreased the highest occupied molecular orbital (HOMO, ca. ?5.4 eV) level and improved the chain planarity through intrachain hydrogen bonding. The shortest π–π stacking distance (3.72 Å) was also measured for the alkylcarbonyl‐substituted BDTCOT:PC₇₁BM blended film by two dimensional grazing incidence X‐ray scattering. With compared to other polymers, the BDTCOT:PC₇₁BM device showed a substantially improved open‐circuit voltage and short‐circuit current density, leading to a 4.66% power conversion efficiency. The side‐chains need to be designed to be multifunctional to induce a deep HOMO level and chain planarity (for interchain ordering) as well as good solution processability. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 854–862     

Synthesis and characterization of naphtho[2,1‐b:3,4‐b′]dithiophene‐based polymers with extended π‐conjugation systems for use in bulk heterojunction polymer solar cells

Two novel polymeric semiconductor materials based on naphtho[2,1‐b:3,4‐b']dithiophene (NDT), PNDT‐TTT and PNDT‐TET , were designed and synthesized. These synthesized polymers were tested in bulk heterojunction solar cells as blends with the acceptor [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM). PNDT‐TTT contained tri‐thiophene units, and PNDT‐TET contained bi‐thiophene units coupled by ethylenic linkages. Comparison to the properties of PNDT‐T , which contained single thiophene units, these polymers exhibit red‐shifted absorption spectra as a result of the enhanced conjugation lengths. These effects resulted in high short circuit currents (J_SC) in the organic solar cells. The PNDT‐TET ‐ and PNDT‐TTT ‐based devices exhibited considerably better photovoltaic performances, with power conversion efficiencies of 3.5 and 3.3%, respectively, compared to the PNDT‐T ‐based device (1.3%). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4742–4751     

Reduced‐bandgap triphenylamine‐alt‐benzo[1,2‐b:4,5‐b′]dithiophene copolymers pending benzothiadiazole or diketopyrrolopyrrole units for efficient polymer solar cells

Two new side‐chain donor–acceptor (D‐A)‐based triphenylamine‐alt‐benzo[1,2‐b:4,5‐b′]dithiophene (TPA‐alt‐BDT) copolymers ( P1 and P2 ) with pendant benzothiadiazole (BT)/diketopyrrolopyrrole (DPP) in TPA unit were synthesized by Stille coupling polymerization. Their thermal, photophysical, electrochemical, blend film morphology and photovoltaic properties were investigated. Efficient bulk heterojunction polymer solar cells (PSCs) were obtained by solution process using both copolymers as donor materials and PC₇₁BM as acceptor. The maximum power conversion efficiency (PCE) of 3.17% with a highest open‐circuit voltage (V_oc) of 0.86V was observed in the P1 ‐based PSCs, while the maximum short‐circuit current (J_sc) of 10.77 mA cm^?2 was exhibited in the P2 ‐based PSCs under the illumination of AM 1.5, 100 mW cm^?2. The alternating binary donor units and pending acceptor groups played a significant role in tuning photovoltaic properties for this class of the side‐chain D–A‐based copolymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4103–4110     

Synthesis and characterization of novel low‐bandgap triphenylamine‐based conjugated polymers with main‐chain donors and pendent acceptors for organic photovoltaics

A series of novel low‐bandgap triphenylamine‐based conjugated polymers ( PCAZCN , PPTZCN , and PDTPCN ) consisting of different electron‐rich donor main chains (N‐alkyl‐2,7‐carbazole, phenothiazine, and cyclopentadithinopyrol, respectively) as well as cyano‐ and dicyano‐vinyl electron‐acceptor pendants were synthesized and developed for polymer solar cell applications. The polymers covered broad absorption spectra of 400–800 nm with narrow optical bandgaps ranging 1.66–1.72 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels of the polymers measured by cyclic voltammetry were found in the range of ?5.12 to ?5.32 V and ?3.45 to ?3.55 eV, respectively. Under 100 mW/cm² of AM 1.5 white‐light illumination, bulk heterojunction photovoltaic devices composing of an active layer of electron‐donor polymers ( PCAZCN , PPTZCN , and PDTPCN ) blended with electron‐acceptor [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) in different weight ratios were investigated. The photovoltaic device containing donor PCAZCN and acceptor PC₇₁BM in 1:2 weight ratio showed the highest power conversion efficiency of 1.28%, with V_oc = 0.81 V, J_sc = 4.93 mA/cm², and fill factor = 32.1%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of low‐bandgap copolymers based on dihexyl‐2h‐benzimidazole and cyclopentadithiophene

A series of new semiconducting polymers based on 4,4‐dihexyl‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene, 2,2‐dihexyl‐2H‐benzimidazole, and thiophene units was synthesized. The polymers show good solubility at room temperature in organic solvents owing to long alkyl chain in new acceptor, 2,2‐dihexyl‐2H‐benzimidazole. The advantage of dihexyl‐2H‐benzimidazole compared to the benzothiadiazole is to improve the solubility of the polymer. It was found that these polymers can finely be tuned for photovoltaic application by adjusting the contents ratio of the dihexyl‐2H‐benzimidazole unit. The spectra of the solid films show absorption bands with maximum peaks in the range of 421–577 nm and the absorption onsets at 588–683 nm, corresponding to band gaps of 2.11–1.82 eV. The devices with PCPDTDTHBI‐1 :PC₇₁BM showed an open‐circuit voltage (V_OC) of 0.46 V, a short‐circuit current density (J_SC) of 3.83 mA/cm², and a fill factor of 0.36, giving a power conversion efficiency of 0.64%. Decrease of the dihexyl‐2H‐benzimidazole contents in the polymers induced red‐shift of the UV absorptions, and increased V_OC and J_SC values, to improve the efficiency of organic photovoltaics. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

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     

Synthesis and applications of 2,7‐carbazole‐based conjugated main‐chain copolymers containing electron deficient bithiazole units for organic solar cells

A series of low‐band‐gap (LBG) donor–accepor conjugated main‐chain copolymers ( P1 – P4 ) containing planar 2,7‐carbazole as electron donors and bithiazole units (4,4′‐dihexyl‐2,2′‐bithiazole and 4,4′‐dihexyl‐5,5′‐di(thiophen‐2‐yl)‐2,2′‐bithiazole) as electron acceptors were synthesized and studied for the applications in bulk heterojunction (BHJ) solar cells. The effects of electron deficient bithiazole units on the thermal, optical, electrochemical, and photovoltaic (PV) properties of these LBG copolymers were investigated. Absorption spectra revealed that polymers P1 – P4 exhibited broad absorption bands in UV and visible regions from 300 to 600 nm with optical band gaps in the range of 1.93–1.99 eV, which overlapped with the major region of the solar emission spectrum. Moreover, carbazole‐based polymers P1 – P4 showed low values of the highest occupied molecular orbital (HOMO) levels, which provided good air stability and high open circuit voltages (V_oc) in the PV applications. The BHJ PV devices were fabricated using polymers P1 – P4 as electron donors and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) or (6,6)‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as electron acceptors in different weight ratios. The PV device bearing an active layer of polymer blend P4:PC₇₁BM (1:1.5 w/w) showed the best power conversion efficiency value of 1.01% with a short circuit current density (J_sc) of 4.83 mA/cm², a fill factor (FF) of 35%, and V_oc = 0.60 V under 100 mW/cm² of AM 1.5 white‐light illumination. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Poly((2‐alkylbenzo[1,2,3]triazole‐4,7‐diyl)vinylene)s for organic solar cells

Poly((2‐Alkylbenzo[1,2,3]triazole‐4,7‐diyl)vinylene)s (pBTzVs) synthesized by Stille coupling show different absorption spectra, solid‐state morphology, and photovoltaic performance, depending on straight‐chain versus branched‐chain (pBTzV12 and pBTzV20) pendant substitution. Periodic boundary condition density functional computations show limited alkyl pendant effects on isolated chain electronic properties; however, pendants could influence polymer backbone conjugative planarity and polymer solid film packing. The polymers are electronically ambipolar, with best performance by pBTzV12 with hole and electron transport mobilities of 4.86 × 10^?6 and 1.96 × 10^?6 cm² V^?1 s^?1, respectively. pBTzV12 gives a smooth film morphology, whereas pBTzV20 gives a very different fibrillar morphology. For ITO/PEDOT:PSS/(1:1 w/w polymer:PC₇₁BM)/LiF/Al devices, pBTzV12 gives power conversion efficiency (PCE) up to 2.87%, and pBTzV20 gives up to PCE = 1.40%; both have open‐circuit voltages of V_OC = 0.6–0.7 V. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1539–1545     

Development of naphthalene and quinoxaline‐based donor–acceptor conjugated copolymers for delivering high open‐circuit voltage in photovoltaic devices

Two new quinoxaline‐based polymers, poly[1,5‐didecyloxynaphthalene‐alt‐5,5′‐(5,8‐dithiophen‐2‐yl)‐2,3‐bis(4‐octyloxyphenyl)quinoxaline (PNQx‐p) and poly[1,5‐didecyloxynaphthalene‐alt‐5,5′‐(5,8‐dithiophen‐2‐yl)‐2,3‐bis(3‐octyloxyphenyl)quinoxaline (PNQx‐m), were synthesized by Suzuki coupling reaction and characterized. Thermogravimetric analysis revealed that these polymers are thermally stable with degradation temperature up to 320 °C. As evident from the electrochemical and optical studies, the copolymers have comparable optical band gap (～2 eV) and nearly similar deep highest occupied molecular orbital (HOMO) energy levels of ?5.59 (PNQx‐p) and ?5.61 eV (PNQx‐p). The resulting copolymers possessed relatively low HOMO energy levels promising good air stability and high open circuit voltage (V_oc) for photovoltaic applications. The optimized photovoltaic device with a structure of ITO/PEDOT:PSS/PNQx‐m:PC₇₁BM (1:2, w/w)/LiF/Al shows a power conversion efficiency up to 2.29% with a short circuit current density of 5.61 mA/cm², an V_oc of 0.93 V and a fill factor of 43.73% under an illumination of AM 1.5, 100 mW/cm². The efficiency of the PNQx‐m polymer improved from 2.29 to 2.95% using 1,8‐diiodoocane as an additive (0.25%). © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

New π‐Conjugated polymers containing 4H,4′H‐[1,1′‐Bithieno [3,4‐C]Pyrrole]‐4,4′,6,6′(5H,5′H)‐Tetraone (biTPD) units and their application to thin‐Film transistors and photovoltaic cells

We successfully synthesized new D‐A copolymers that employ 1,10‐bithienopyrrolodione (biTPD), thiophene, and selenophene‐based donor monomeric units. Two polymers, PBTPDEBT and PBTPDEBS , exhibited high degrees of crystallinity and unique polymer chain arrangements on the substrate, which is attributed to their enhanced coplanarity and intermolecular interactions between the polymer chains. Among the thin‐film transistor devices made of PBTPDEBT and PBTPDEBS , the annealed PBTPDEBS device displayed relatively high hole mobility, which was twice that of the PBTPDEBT ‐based device. In addition, an organic photovoltaic device based on a PBTPDEBS :PC₇₁BM blend displayed the maximum power conversion efficiency of 3.85%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1228–1235     

Synthesis and photovoltaic properties of 2,6‐bis(2‐thienyl) benzobisazole and 4,8‐bis(thienyl)‐benzo[1,2‐B:4,5‐B′]dithiophene copolymers

In an effort to design efficient low‐cost polymers for use in organic photovoltaic cells the easily prepared donor–acceptor–donor triad of a either cis‐benzobisoxazole, trans‐benzobisoxazole or trans‐benzobisthiazole flanked by two thiophene rings was combined with the electron‐rich 4,8‐bis(5‐(2‐ethylhexyl)‐thien‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene. The electrochemical, optical, morphological, charge transport, and photovoltaic properties of the resulting terpolymers were investigated. Although the polymers differed in the arrangement and/or nature of the chalcogens, they all had similar highest occupied molecular orbital energy levels (?5.2 to ?5.3 eV) and optical band gaps (2.1–2.2 eV). However, the lowest unoccupied molecular orbital energy levels ranged from ?3.1 to ?3.5 eV. When the polymers were used as electron donors in bulk heterojunction photovoltaic devices with PC₇₁BM ([6,6]‐phenyl C₇₁‐butyric acid methyl ester) as the acceptor, the trans‐benzobisoxazole polymer had the best performance with a power conversion efficiency of 2.8%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 316–324     

Donor–acceptor photovoltaic polymers based on 1,4‐dithienyl‐2,5‐dialkoxybenzene with intramolecular noncovalent interactions

Donor–acceptor (D–A) conjugated polymers bearing non‐covalent configurationally locked backbones have a high potential to be good photovoltaic materials. Since 1,4‐dithienyl‐2,5‐dialkoxybenzene ( TBT ) is a typical moiety possessing intramolecular S…O interactions and thus a restricted planar configuration, it was used in this work as an electron‐donating unit to combine with the following electron‐accepting units: 3‐fluorothieno[3,4‐b]thiophene ( TFT ), thieno‐[3,4‐c]pyrrole‐4,6‐dione ( TPD ), and diketopyrrolopyrrole ( DPP ) for the construction of such D–A conjugated polymers. Therefore, the so‐designed three polymers, PTBTTFT , PTBTTPD , and PTBTDPP , were synthesized and investigated on their basic optoelectronic properties in detail. Moreover, using [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as acceptor material, polymer solar cells (PSCs) were fabricated for studying photovoltaic performances of these polymers. It was found that the optimized PTBTTPD cell gave the best performance with a power conversion efficiency (PCE) of 4.49%, while that of PTBTTFT displayed the poorest one (PCE = 1.96%). The good photovoltaic behaviors of PTBTTPD come from its lowest‐lying energy level of the highest occupied molecular orbital (HOMO) among the three polymers, and good hole mobility and favorable morphology for its PC₇₁BM‐blended film. Although PTBTDPP displayed the widest absorption spectrum, the largest hole mobility, and regular chain packing structure when blended with PC₇₁BM, its unmatched HOMO energy level and disfavored blend film morphology finally limited its solar cell performance to a moderate level (PCE: 3.91%). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 689–698