Anthracene‐Containing Wide‐Band‐Gap Conjugated Polymers for High‐Open‐Circuit‐Voltage Polymer Solar Cells

The synthesis, characterization, and photophysical and photovoltaic properties of two anthracene‐containing wide‐band‐gap donor and acceptor (D–A) alternating conjugated polymers ( P1 and P2 ) are described. These two polymers absorb in the range of 300–600 nm with a band gap of about 2.12 eV. Polymer solar cells with P1 :PC₇₁BM as the active layer demonstrate a power conversion efficiency (PCE) of 2.23% with a high V_oc of 0.96 V, a J_sc of 4.4 mA cm⁻², and a comparable fill factor (FF) of 0.53 under simulated solar illumination of AM 1.5 G (100 mW cm⁻²). In addition, P2 :PC₇₁BM blend‐based solar cells exhibit a PCE of 1.42% with a comparable V_oc of 0.89 V, a J_sc of 3.0 mA cm⁻², and an FF of 0.53.

     

Dithieno[2,3‐d:2',3'‐d']benzo[1,2‐b:4,5‐b']dithiophene (DTBDAT)‐based copolymers for high‐performance organic solar cells

P(BDT‐TCNT) and P(DTBDAT‐TCNT) , which has an extended conjugation length, were designed and synthesized for applications in organic solar cell (OSCs). The solution absorption maxima of P(DTBDAT‐TCNT) with the extended conjugation were red‐shifted by 5–15 nm compared with those of P(BDT‐TCNT) . The optical band gaps and highest occupied molecular orbital (HOMO) energy levels of both P(BDT‐TCNT) and P(DTBDAT‐TCNT) were similar. The structure properties of thin films of these materials were characterized using grazing‐incidence wide‐angle X‐ray scattering and tapping‐mode atomic force microscopy, and charge carrier mobilities were characterized using the space‐charge limited current method. OSCs were formed using [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as the electron acceptor and 3% diphenylether as additive suppress aggregation. OSCs with P(BDT‐TCNT) as the electron donor exhibited a power conversion efficiency (PCE) of 4.10% with a short‐circuit current density of J_SC = 9.06 mA/cm², an open‐circuit voltage of V_OC = 0.77 V, and a fill factor of FF = 0.58. OSCs formed using P(DTBDAT‐TCNT) as the electron donor layer exhibited a PCE of 5.83% with J_SC = 12.2 mA/cm², V_OC = 0.77 V, and FF = 0.62. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3182–3192     

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 properties of mono‐ and di‐fluoro‐substituted 2,3‐didodecylquinoxaline‐based polymers for polymer solar cells

We synthesized two new alternating polymers, namely P(Tt‐FQx) and P(Tt‐DFQx) , incorporating electron rich tri‐thiophene and electron deficient 6‐fluoroquinoxaline or 6,7‐difluoroquinoxaline derivatives. Both polymers P(Tt‐FQx) and P(Tt‐DFQx) exhibited high thermal stabilities and the estimated 5% weight loss temperatures are 425 and 460 °C, respectively. Polymers P(Tt‐FQx) and P(Tt‐DFQx) displayed intense absorption band between 450 and 700 nm with an optical band gap (E_g) of 1.78 and 1.80 eV, respectively. The determined highest occupied/lowest unoccupied molecular orbital's (HOMO/LUMO) of P(Tt‐DFQx) (?5.48 eV/?3.68 eV) are slightly deeper than those of P(Tt‐FQx) ( ?5.32 eV/?3.54 eV). The polymer solar cells fabricated with a device structure of ITO/PEDOT:PSS/ P(Tt‐FQx) or P(Tt‐DFQx) :PC₇₀BM (1:1.5 wt %) + 3 vol % DIO/Al offered a maximum power conversion efficiency (PCE) of 3.65% with an open‐circuit voltage (V_oc) of 0.59 V, a short‐circuit current (J_sc) of 10.65 mA/cm² and fill factor (FF) of 59% for P(Tt‐FQx) ‐based device and a PCE of 4.36% with an V_oc of 0.69 V, a J_sc of 9.92 mA/cm², and FF of 63% for P(Tt‐DFQx) ‐based device. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 545–552     

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.     

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     

Tuning photovoltaic performance of 9,9‐dioctylfluorene‐alt‐5,7‐bis(thiophen‐2‐yl)‐2,3‐biphenylthieno[3,4‐b]pyrazine copolymeric derivatives by attaching additional donor units in pendant phenyl ring

A class of the 9,9‐dioctylfluorene‐alt‐5,7‐bis(thiophen‐2‐yl)‐2,3‐biphenylthieno [3,4‐b]pyrazine copolymeric derivatives (PFO‐3ThPz‐D) attaching additional donor (D) units in the pendant phenyl ring with a D‐A D structure was synthesized and investigated, where the additional D unit is a substituent group of fluorene, carbazole, and triphenylamine (Tpa). Their photovoltaic properties were significantly tuned by these pending donor units. Among these copolymers, the PFO‐3ThPz‐Tpa exhibited the best photovoltaic properties in the bulk heterojunction polymeric solar cells (BHJ‐PSC). The maximum power conversion efficiency (PCE) of 2.09% and the highest circuit current density (J_sc) of 7.91 mA/cm² were obtained in the cell using a blend of PFO‐3ThPz‐Tpa and PC₆₀BM (1:3, w/w) as active layer, which are 2.5 and 1.8 times higher than those corresponding levels in the other cell using the parent PFO‐3ThPz‐Ph copolymer instead of PFO‐3ThPz‐Tpa as donor, respectively. While PC₆₀BM was replaced by PC₇₀BM, the PFO‐3ThPz‐Tpa‐based BHJ‐PSC exhibited better photovoltaic properties with PCE of 3.08% and J_sc of 10.3 mA/cm². This work demonstrated that attaching donor units into the D‐A‐based copolymeric side‐chain is a simple and effective method to improve the photovoltaic properties for the resulting copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dithienosilole–phenylquinoxaline‐based copolymers with A‐D‐A‐D and A‐D structures for polymer solar cells

Two copolymers having D‐A‐D‐A ( P1 ) and D‐A ( P2 ) structures with quinoxaline acceptor unit and dithienosilole donor unit were synthesized and their optical and electrochemical (both experimental and theoretical) properties were investigated. The optical properties showed that these copolymers P1 and P2 exhibit optical bandgaps of 1.54 and 1.62 eV, respectively, with broader absorption profiles extending up to 800 nm and 770 nm, respectively. The electrochemical investigation of these two copolymers indicates that they exhibit suitable highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels for efficient exciton dissociation and high open circuit voltage in the resultant polymer solar cells (PSCs). These copolymers were used as donors along with the PC₇₁BM as acceptor for the fabrication of solution processed bulk heterojunction PSCs. The optimized P1 :PC₇₁BM and P2 :PC₇₁BM active layers treated with solvent vapor treatment showed overall power conversion efficiency (PCE) of 7.16% and 6.57%, respectively. The higher PCE of P1 ‐based device as compared to P2 might be attributed to higher crystallinity of P1 and good hole mobility resulting more balanced charge transport. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 376–386     

Polythiophenes bearing electron‐withdrawing groups in the side chain and their application to bulk heterojunction solar cells

Soluble polythiophenes bearing strong electron withdrawing groups, dicyanoethenyl [? CH?C(CN)₂] (PTDCN) and cyano‐methoxycarbonylethenyl [? CH?C(CO₂Me)CN] (PTCNME), in the side chains have been prepared. Optical band gaps calculated from onset absorption were 1.70 eV and 1.73 eV for PTDCN and PTCNME, respectively. Highest occupied molecular orbital energy levels measured with a surface analyzer (AC‐2) were ?5.53 eV and ?5.29 eV for PTDCN and PTCNME, respectively, which were much lower than that of poly(3‐hexylthiophene) (?4.81 eV). To investigate photovoltaic properties, bulk heterojunction polymer solar cells based on PTDCN and PTCNME were fabricated with a structure of ITO/PEDOT:PSS/active layer/LiF/Al, where the active layer was a blend film of polymer and [6,6]‐phenyl C₆₁ butyric acid hexyl ester (PC₆₁BH). Solar cell parameters were estimated from current density–voltage (J–V) characteristics under the illumination of AM1.5 at 100 mW/cm². The solar cell based on the blend film of PTCNME:PC₆₁BH (1:1) showed power conversion efficiency (PCE) of 0.72% together with the open current voltage (V_oc) of 0.61 V, the short current density (J_sc) of 3.90 mA/cm², and the fill factor of 30.3%. The PCE of a solar cell fabricated from PTDCN in a similar way was 0.56%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Alternating copolymers incorporating cyclopenta[2,1‐b:3,4‐b′]dithiophene unit and organic dyes for photovoltaic applications

We have synthesized six p‐type copolymers, CPDT ‐ co ‐ TPADCN , CPDT ‐ co ‐ TPADTA , CPDT ‐ co ‐ TPATCN , CPDT ‐ co ‐ DFADCN , CPDT ‐ co ‐ DFADTA , and CPDT ‐ co ‐ DFATCN , consisting of a cyclopenta[2,1‐b:3,4‐b′]dithiophene (CPDT) unit and an organic dye in an alternating arrangement. Triphenylamine (TPA) or difluorenylphenyl amine (DFA) units serve as the electron donors, whereas dicyanovinyl (DCN), 1,3‐diethyl‐2‐thiobarbituric acid, or tricyanovinyl (TCN) units act as the electron acceptors in the dyes. The target polymers were prepared via Stille coupling, followed by postfunctionalization to introduce the electron acceptors to the side chains. Because of the strongest withdrawing ability of TCN acceptor to induce efficient intramolecular charge transfer, CPDT ‐ co ‐ TPATCN and CPDT ‐ co ‐ DFATCN exhibit the broader absorption spectra covering from 400 to 900 nm and the narrower optical band gaps of 1.34 eV. However, the CPDT ‐ co ‐ TPATCN :PC₇₁BM and CPDT ‐ co ‐ DFATCN :PC₇₁BM based solar cells showed the power conversion efficiencies (PCEs) of 0.22 and 0.31%, respectively, due to the inefficient exciton dissociation. The DFA‐based polymers possess deeper‐lying HOMO energy levels than the TPA‐based polymer analogues, leading to the higher V_oc values and better efficiencies. The device based on CPDT ‐ co ‐ DFADTA :PC₇₁BM blend achieved the best PCE of 1.38% with a V_oc of 0.7 V, a J_sc of 4.57 mA/cm², and a fill factor of 0.43. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

New selenophene‐based low‐band gap conjugated polymers for organic photovoltaics

Low‐band gap selenophene‐based polymers were synthesized. Their optoelectronic and photovoltaic properties and space‐charge limited currents were compared with those of the related thiophene‐based polymers. The band gaps of the Se‐based derivatives were approximately 0.05–0.12 eV lower than those of their thiophene counterparts. Organic photovoltaic (OPV) devices based on the blends of these polymers and 1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐C₇₁ (PC₇₁BM) were fabricated, and the maximum power conversion efficiency of the OPV device based on PSPSBT and PC₇₁BM was 3.1%—with a short‐circuit current density (J_sc) of 9.3 mA cm^?2, an open‐circuit voltage (V_oc) of 0.79 V, and a fill factor of 0.42—under AM 1.5 G illumination (100 mW cm^?2). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4550–4557     

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 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     

Benzotriazole and benzodithiophene containing medium band gap polymer for bulk heterojunction polymer solar cell applications

An alternating donor‐acceptor copolymer based on a benzotriazole and benzodithiophene was synthesized and selenophene was incorporated as π‐bridge. The photovoltaic and optical properties of polymer were studied. The copolymer showed medium band gap and dual absorption peaks in UV‐Vis absorption spectra. Photovoltaic properties of P‐SBTBDT were performed by conventional device structure. The OSC device based on polymer: PC₇₁BM (1:1, w/w) exhibited the best PCE of 3.60% with a V_oc of 0.67 V, a J_sc of 8.95 mA/cm², and a FF of 60%. This finding was supported with morphological data and space charge limited current (SCLC) mobilities. The hole mobility of the copolymer was estimated through SCLC model. Although surface roughness of the active layer is really high, mobility of a polymer was found as 7.46 × 10^?3 cm²/Vs for optimized device that can be attributed to Se?Se interactions due to the larger, more‐polarizable Se atom. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 528–535     

Synthesis of phenanthro[1,10,9,8‐cdefg]carbazole‐based conjugated polymers for organic solar cell applications

Low bandgap polymers with dithienylquinoxaline moieties based on 6H‐phenanthro[1,10,9,8‐cdefg]carbazole were synthesized via the Suzuki coupling reaction. Alkoxy groups were substituted at two different positions on the phenyl groups of the quinoxaline units of these polymers: in the para‐position (PPQP) and in the meta‐position (PPQM). The two polymers showed similar physical properties: broad absorption in the range of 400–700 nm, optical bandgaps of ～1.8 eV, and the appropriate frontier orbital energy levels for efficient charge transfer/separation at polymer/PC₇₁BM interfaces. However, the PPQM solar cell achieved a higher PCE due to its higher J_sc. Our investigation of the morphologies of the polymer:PC₇₁BM blend films and theoretical calculations of the molecular conformations of the polymer chains showed that the polymer with the meta‐positioned alkoxy group has better miscibility with PC₇₁BM than the polymer with the para‐positioned alkoxy group because the dihedral angle of its phenyl group with respect to the quinoxaline unit is higher. This higher miscibility resulted in a polymer:PC₇₁BM blend film with a better morphology and thus in a higher PCE. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 796–803     

Synthesis and characterization of indenofluorene‐based copolymers containing 2,5‐bis(2‐thienyl)‐N‐arylpyrrole for bulk heterojunction solar cells and polymer light‐emitting diodes

Two novel alternating π‐conjugated copolymers, poly[2,8‐(6,6′,12,12′‐tetraoctyl‐6,12‐dihydroindeno‐[1,2b]fluorene‐ alt‐5(1‐(2,6‐diisopropylphenyl)‐2,5‐di(2‐thienyl)pyrrole) ( P1 ) and poly[2,8‐(6,6′,12,12′‐tetraoctyl‐6,12‐dihydroindeno‐[1,2b]fluorene‐ alt‐5(1‐(p‐octylphenyl)‐2,5‐di(2‐thienyl)pyrrole) ( P2 ), were synthesized via the Suzuki coupling method and their optoelectronic properties were investigated. The resulting polymers P1 and P2 were completely soluble in various common organic solvents and their weight‐average molecular weights (M_w) were 5.66 × 10⁴ (polydispersity: 1.97) and 2.13× 10⁴ (polydispersity: 1.54), respectively. Bulk heterojunction (BHJ) solar cells were fabricated in ITO/PEDOT:PSS/polymer:PC₇₀BM(1:5)/TiO_x/Al configurations. The BHJ solar cell with P1 :PC₇₀BM (1:5) has a power conversion efficiency (PCE) of 1.12% (J_sc= 3.39 mA/cm², V_oc= 0.67 V, FF = 49.31%), measured using AM 1.5 G solar simulator at 100 mW/cm² light illumination. We fabricated polymer light‐emitting diodes (PLEDs) in ITO/PEDOT:PSS/emitting polymer:polyethylene glycol (PEG)/Ba/Al configurations. The electroluminescence (EL) maxima of the fabricated PLEDs varied from 526 nm to 556 nm depending on the ratio of the polymer to PEG. The turn‐on voltages of the PLEDs were in the range of 3–8 V depending on the ratio of the polymer to PEG, and the maximum brightness and luminance efficiency were 2103 cd/m² and 0.37 cd/A at 12 V, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3169–3177, 2010     

Fused structures in the polymer backbone to investigate the photovoltaic and electrochromic properties of donor–acceptor‐type conjugated polymers

In this study, two new benzotriazole (BTz) and dithienothiophene (DTT) containing conjugated polymers were synthesized. After successful characterizations of the monomers by proton‐nuclear magnetic resonance (¹H NMR) and carbon‐NMR (¹³C NMR) techniques, poly(4‐(dithieno[3, 2‐b:2′,3′‐d]thiophen‐2‐yl)‐2‐(2‐octyldodecyl)‐2H‐benzo[d][1,2,3] triazole) P1 and poly(4‐(5‐(dithieno[3,2‐b:2′,3′‐d]thiophen‐2‐yl)thiophen‐2‐yl)‐2‐(2‐octyldodecyl)‐7‐(thiophen‐2‐yl)‐2H‐benzo[d][1,2,3]triazole) P2 were synthesized via a typical Stille coupling. Electrochemical and spectroelectrochemical studies showed that both polymers can be multipurpose materials and used in electrochromic and photovoltaic applications. Reported study indicated that incorporation of DTT into the structure leads to fast switching times compared with BTz‐based polymers and competent percentage transmittance in the near‐infrared region. Multichromism is important in the context of low‐cost flexible display device technology and both polymers are ambipolar and processable as well as multichromic. Throughout the preliminary photovoltaic studies, the best performances of photovoltaic devices were found as V_oc = 0.49 V, J_sc = 0.83 mA/cm², fill factor (FF) = 34.4%, and power conversion efficiency (PCE) = 0.14% for P1 , and as V_oc = 0.35 V, J_sc = 1.57 mA/cm², FF = 38.2%, and PCE = 0.21% for P2 . © 2013 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     

Novel Donor–Acceptor Polymer Containing 4,7‐Bis(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole for Polymer Solar Cells with Power Conversion Efficiency of 6.21%

In order to improve the solution processability of 4,7‐bis(thiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (DTBT)‐based polymers, novel donor–acceptor polymer PTOBDTDTBT containing DTBT and benzo[1,2‐b:4,5‐b′]dithiophene (BDT) with conjugated side chain is designed and synthesized with narrow band gap 1.67 eV and low lying HOMO energy level −5.4 eV. The blend film of PTOBDTDTBT and PC₇₁BM exhibits uniform and smooth film with root‐mean‐square (RMS) surface roughness 1.15 nm because of the excellent solubility of PTOBDTDTBT when six octyloxy side chains are introduced. The hole mobility of the blend film is measured to be 4.4 × 10⁻⁵ cm² V⁻¹s⁻¹ by the space‐charge‐limited current (SCLC) model. The optimized polymer solar cells (PSCs) based on PTOBDTDTBT /PC₇₁BM exhibits an improved PCE of 6.21% with V_oc = 0.80 V, J_sc = 11.94 mA cm⁻² and FF = 65.10%, one of the highest PCE in DTBT containing polymers.

     

Control of vertical distribution of thiophene‐based copolymers containing 4,7‐Dithien‐2‐yl‐benzo[C][1,2,5]thiadiazole and 3,6‐Dithien‐2‐yl‐pyrrolo[3,4‐C]pyrrole‐1,4(2H,5H)‐dione as Side Groups for Photovoltaics

Four new D—A type copolymers with 2D‐conjugated side‐chain identified PfToBT, PbToBT, PfTDPP and PbTDPP, containing two acceptors 4,7‐dithien‐2‐yl‐benzo[c][1,2,5]thiadiazole (DTBT), and diketopyrrolopyrrole (DPP) linked by thiophene donors, are obtained using Pd‐catalyzed Stille‐coupling reaction. These polymers show a broad visible‐near‐infrared absorption band (E_g = 1.79–1.66 eV) and possess a relatively low‐lying HOMO level at ?5.34 to ?5.12 eV. All the polymer:PC₇₀BM blend films showed edge‐on structure and have similar d_π‐spacing values. According to the structure of conjugated side‐chain, the vertical distributions of polymer chains and PC₇₀BM within the BHJ (bulk heterojunction) were different. When DPP used as an acceptor, conjugated side chains of the polymer coexisted with PC₇₀BM in same position. The BHJ film prepared from PfToBT, PbToBT had a discontinuous network between polymer and PC₇₀BM, whereas films from PfTDPP and PbTDPP formed continuous and evenly distributed network between them. This optimized vertical morphology promotes hole transport along respective pathways of polymers and fullerenes in the vertical direction, leading to high J_SC. PbTDPP shows PCE up to 2.9% (Jsc of 9.4 mA/cm², Voc of 0.68 V, and FF of 0.44). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2746–2759