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     

Novel low‐bandgap oligothiophene‐based donor‐acceptor alternating conjugated copolymers: Synthesis,properties, and photovoltaic applications

A series of novel soluble donor‐acceptor low‐bandgap‐conjugated polymers consisting of different oligothiophene (OTh) coupled to electron‐accepting moiety 2‐pyran‐4‐ylidenemalononitrile (PM)‐based unit were synthesized by Stille or Suzuki coupling polymerization. The combination of electron‐accepting PM building block with varied OTh_n (the number of thiophene unit increases from 3 to 5) results in enhanced π–π stacking in solid state and intramolecular charge transfer (ICT) transition, which lead to an extension of the absorption spectra of the copolymers. Cyclic voltammetry measurements and molecular orbital distribution calculations indicate that the highest occupied molecular orbitals (HOMO) energy levels could be fine‐tuned by changing the number of thiophene units of the copolymers, and the resulting copolymers possessed relatively low HOMO energy levels promising good air stability and high‐open circuit voltage (V_oc) for photovoltaic application. Bulk heterojunction photovoltaic devices were fabricated by using the copolymers as donors and (6,6)‐phenyl C₆₁‐butyric acid methyl ester as acceptor. It was found that the highest V_oc reached 0.94 V, and the short circuit currents (J_sc) were improved from 1.78 to 2.54 mA/cm², though the power conversion efficiencies of the devices were measured between 0.61 and 0.99% under simulated AM 1.5 solar irradiation of 100 mW/cm², which indicated that this series copolymers can be promising candidates for the photovoltaic applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2765–2776, 2010     

Thiophene π bridge effect on bulky side‐chained benzodithiophene‐based photovoltaic polymers

Recently, we have used terthiophene side chain to modify benzo[1,2‐b:4,5‐b′]dithiophene (BDT) to form novel building block for BDT polymers. In this paper, this building block is used to copolymerized with thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) and thieno[3,4‐b]thiophene (TT). This building block and TPD‐ or TT‐based polymers (P1 and P3) show high open circuit voltage (V_OC) (ca. 0.9–0.95 V) and low energy loss (E_g–eV_OC) in solar cells devices compared with similar polymers without bulky side chain. We further introduce thiophene π bridge into these polymers backbone to form two other polymers (P2 and P4). We find this thiophene π bridge does contribute to this bulky side chained benzodithiophene polymer photovoltaic performances, especially for power conversion efficiencies (PCEs). The polymer solar cells (PSCs) performances are moderate in this article due to the serious aggregation in the PSCs active layer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1615–1622     

A low bandgap polymer based on isoindigo and bis(dialkylthienyl)benzodithiophene for organic photovoltaic applications

A new conjugated polymer PBDTT‐ID based on N‐alkylated isoindigo (ID) and bis(2,3‐dialkylthienyl)‐substituted benzo[1,2‐b:4,5‐b′]dithiophene (BDTT) as repeating units was synthesized. It had an optical bandgap of 1.56 eV and a highest occupied molecular orbital (HOMO) energy level of ?5.71 eV. The optical, electrochemical, and photovoltaic properties of new polymer were compared with previous reported polymer PBDT‐ID , which was based on bis(alkoxy)‐substituted benzo[1,2‐b:4,5‐b′]dithiophene. The new polymer displayed lower HOMO energy level and better absorption properties than polymer PBDT‐ID . The solar cells fabricated with PBDTT‐ID /PC₆₁BM (1:2, w/w) blends as active layers exhibited photoresponse in the range of 300–800 nm. A power conversion efficiency of 4.02% and an open circuit voltage (V_oc) of 0.94 V were achieved in polymer solar cell device based on the new polymer. This was the highest V_oc realized among the isoindigo‐based polymers. The relatively high performances of new polymer in solar cell devices were interpreted in terms of material properties and morphologies of polymer/PCBM blends. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Random poly(3‐hexylthiophene‐co‐3‐cyanothiophene‐co‐3‐(2‐ethylhexyl)thiophene) copolymers with high open‐circuit voltage in polymer solar cells

For the purpose of developing poly(3‐hexylthiophene) (P3HT) based copolymers with deep‐lying highest occupied molecular orbital (HOMO) levels for polymer solar cells with high open‐circuit voltage (V_oc), we report a combined approach of random incorporation of 3‐cyanothiophene (CNT) and 3‐(2‐ethylhexyl)thiophene (EHT) units into the P3HT backbone. This strategy is designed to overcome CNT content limitations in recently reported P3HT‐CNT copolymers, where incorporation of more than 15% of CNT into the polymer backbone leads to impaired polymer solubility and raises the HOMO level. This new approach allows incorporation of a larger CNT content, reaching even lower‐lying HOMO levels. Importantly, a very low HOMO level of ?5.78 eV was obtained, representing one of the lowest HOMO values for exclusively thiophene‐based polymers. Lower HOMO levels result in higher V_oc and higher power conversion efficiencies (PCE) compared to the previously reported P3HT‐CNT copolymers containing only 3‐hexylthiophene and CNT units. As a result, solar cells based on P3HT‐CNT‐EHT(15:15) , which contains 70% of P3HT, 15% of CNT and 15% of EHT, yield a V_oc of 0.83 V in blends with PC₆₁BM while preserving high fill factor (FF) and high short‐circuit current density (J_sc), resulting in 3.6% PCE. Additionally, we explored the effect of polymer number‐average molecular weight (M_n) on the optoelectronic properties and solar cell performance for the example of P3HT‐CNT‐EHT(15:15). The organic photovoltaic (OPV) performance improves with polymer M_n increasing from 3.4 to 6.7 to 9.6 kDa and then it declines as M_n further increases to 9.9 and to 16.2 kDa. The molecular weight study highlights the importance of not only the solar cell optimization, but also the significance of individual polymer properties optimization, in order to fully explore the potential of any given polymer in OPVs. The broader ramification of this study lies in potential application of these high band gap copolymers with low‐lying HOMO level in the development of ternary blend photovoltaics as well as tandem OPV. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1526–1536     

Jacket‐like structure of donor–acceptor chromophores‐based conducting polymers for photovoltaic cell applications

Through the Stille coupling polymerization, a series of soluble acceptor/donor quinoxaline/thiophene alternating conducting polymers with a hole‐transporting moiety of carbazole as a side chain ( PCPQT ) has been designed, synthesized, and investigated. The UV–vis measurement of the charge‐transferred type PCPQT s of different molecular weights with low polydispersity exhibits a red shifting of their absorption maximum from 530 to 630 nm with increasing chain length (M_n: from 1100 to 19,200). The HOMO and LUMO energy levels of PCPQT can be determined from the cyclic voltammetry measurement to be ?5.36 and ?3.59 eV, respectively. Solar cells made from PCPQT/PCBM bulk heterojunction show a high open‐circuit voltage, V_oc of ～0.75 V, which is significantly higher than that of a solar cell made from conventional poly(3‐hexyl thiophene)/ PCBM as the active polymer PCPQT has lower HOMO level. Further improvements are anticipated through a rational design of the new low band‐gap and the structurally two‐dimensional donor–acceptor conducting polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1607–1616, 2010     

Preparation and characterization of solution processable phthalocyanine‐containing polymers via a combination of RAFT polymerization and post‐polymerization modification techniques

In this work, a benzenedinitrile functionalized monomer, 2‐methyl‐acrylic acid 6‐(3,4‐dicyano‐phenoxy)‐hexyl ester, was successfully polymerized via the reversible addition‐fragmentation chain transfer method. The polymerization behavior conveyed the characteristics of “living”/controlled radical polymerization: the first‐order kinetics, linear increase of number‐average molecular weight with monomer conversion, narrow molecular weight distribution, and successful chain‐extension experiment. The soluble Zn(II) phthalocyanine (Pc)‐containing (ZnPc) polymers were achieved by post‐polymerization modification of the obtained polymers. The Zn(II) phthalocyanine‐functionalized polymer was characterized by FTIR, UV–vis, fluorescence, atomic absorption spectroscopy, and thermogravimetric analysis. The potential application of above ZnPc‐functionalized polymer as electron donor material in bulk heterojunction organic solar cell was studied. The device with ITO/PEDOT:PSS/ZnPc‐Polymer/PC₆₁BM/LiF/Al structure provided a power conversion efficiency of 0.014%, fill factor of 0.24, open circuit voltage (V_oc) of 0.21 V, and short‐circuit current (J_sc) of 0.28 mA/cm². © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 691–698     

Synthesis of polymers containing 1,2,4‐oxadiazole as an electron‐acceptor moiety in their main chain and their solar cell applications

To explore the aptitude of 1,2,4‐oxadiazole‐based electron‐acceptor unit in polymer solar cell applications, we prepared four new polymers (P1–P4) containing 1,2,4‐oxadiazole moiety in their main chain and applied them to solar cell applications. Thermal, optical, and electrochemical properties of the polymers were studied using thermogravimetric, absorption, and cyclic voltammetry analysis, respectively. All four polymers showed high thermal stability (5% degradation temperature over 335 °C), and the optical band gaps were calculated to be 2.20, 1.72, 1.37, and 1.74 eV, respectively, from the onset wavelength of the film‐state absorption band. The energy levels of the polymers were found to be suitable for bulk heterojunction (BHJ) solar cell applications. The BHJ solar cells were prepared by using the synthesized polymers as a donor and PC₇₁BM as an electron acceptor with the configuration of ITO/PEDOT:PSS/polymer:PC₇₁BM (1:3 wt %)/LiF/Al. One of the polymers was found to show the maximum power conversion efficiency of 1.33% with a Jsc of 4.95 mA/cm², a V_oc of 0.68 V, and a FF of 40%, measured using AM 1.5 G solar simulator at 100 mW/cm₂ light illumination. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis,characterization, and application to polymer solar cells of polythiophene derivatives with ester‐ or ketone‐substituted phenyl side groups

Four polythiophene derivatives including regiorandom polymers P1 , P2 , and P3 and a regioregular polymer P4 , containing a phenyl side chain with electron‐withdrawing carbonyl groups such as an ester and a ketone at the 3‐position of the thiophene ring, were synthesized by Stille coupling reaction. Bulk‐heterojunction polymer solar cells (PSCs) based on these polymers as p‐type semiconductors and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) were fabricated, and their photovoltaic performances were evaluated for the first time. The PSC devices based on the regioregular polymer P4 :PCBM = 1:2 (w/w) exhibited a high‐open‐circuit voltage (V_oc) of 0.943 V because of the low‐lying highest occupied molecular orbit energy level of P4 . The short π–π stacking distance (0.355 nm) in the parallel direction to the substrate and “face‐on” rich orientation were observed by the grazing incidence wide‐angle X‐ray scattering experiment, which might reflect higher J_sc and FF values of the P4 :[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) PSC device than others. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 875–887     

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     

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     

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     

Conjugated polymers based on dicarboxylic imide‐substituted isothianaphthene and their applications in solar cells

Four new polymers containing a benzo[c]thiophene‐N‐dodecyl‐4,5‐dicarboxylic imide (DIITN) unit including the homopolymer and three donor–acceptor copolymers were designed, synthesized, and characterized. For these copolymers, DIITN unit with low bandgap was selected as an electron acceptor, whereas 5,5′‐(2,7‐bisthiophen‐2‐yl)‐9‐(2‐decyltetradecyl)‐9H‐carbazole), 5,5′‐(3,3′‐di‐n‐octylsilylene‐2,2′‐bithiophene), and 5,5′‐(2,7‐bisthiophen‐2‐yl‐9,9‐bisoctyl‐9H‐fluoren‐7‐yl) were chosen as the electron donor units to tune the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) levels of the copolymers for better light harvesting. These polymers exhibit extended absorption in the visible and near‐infrared range and are soluble in common organic solvents. The relative low lying HOMO of these polymers promises good air stability and high open‐circuit voltage (V_oc) for photovoltaic application. Bulk heterojunction solar cells were fabricated by blending the copolymers with [6,6]‐phenyl‐C61‐butyric acid methyl ester or [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM). The best power conversion efficiency of 1.6% was achieved under simulated sunlight AM 1.5G (100 mW/cm²) from solar cells containing 20 wt % of the fluorene copolymer poly[5,5′‐(2,7‐bisthiophen‐2‐yl‐9,9‐bisoctyl‐9H‐fluoren‐7‐yl)‐alt‐2,9‐(benzo[c]thiophene‐N‐dodecyl‐4,5‐dicarboxylic imide)] and 80 wt % of PC71BM with a high open‐circuit voltage (V_oc) of 0.84 V. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and photovoltaic properties of two‐dimensional D‐A copolymers with conjugated side chains

Four novel two‐dimensional (2D) donor–acceptor (D‐A) type copolymers with different conjugated side chains, P1 , P2 , P3 , and P4 (see Fig. 1 ), are designed and synthesized for the application as donor materials in polymer solar cells (PSCs). To the best of our knowledge, there were few reports to systematically study such 2D polymers with D‐A type main chains in this area. The optical energy band gaps are about 2.0 eV for P1 – P3 and 1.67 eV for P4 . PSC devices using P1 – P4 as donor and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester as acceptor in a weight ratio of 1:3 were fabricated and characterized to investigate the photovoltaic properties of the polymers. Under AM 1.5 G, 100 mA/cm² illumination, a high open‐circuit voltage (V_oc) of 0.9 V was recorded for P3 ‐based device due to its low HOMO level, and moderate fill factor was obtained with the best value of 58.6% for P4 ‐based device, which may mainly be the result of the high hole mobility of the polymers (up to 1.82 × 10^?3 cm²/V s). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Donor–acceptor copolymers based on phenanthrene as electron‐donating unit: Synthesis and photovoltaic performances

Using 9,10‐bis(dodecyloxy)phenanthrene as electron‐donating unit and 4,7‐dithienyl‐5,6‐bis(dodecyloxy)benzothiadiazole, 4,7‐dithienyl‐5,6‐bis(octyloxy)benzoxadiazole, 5,8‐dithienyl‐2,3‐bis(para‐octyloxyphenyl)quinoxaline, and 5,8‐dithienyl‐2,3‐bis(meta‐octyloxyphenyl)quinoxaline as electron‐accepting unit, four D–A copolymers PPA‐DTBT , PPA‐DTBX , PPA‐ p ‐DTQ , and PPA‐ m ‐DTQ , respectively, were successfully synthesized as new polymeric donors for photovoltaic cells. All the alternating copolymers can show two absorption bands, both in solutions and thin films. The optical bandgaps of the polymers are quite close, which are between 1.93 and 2.00 eV. The HOMO and LUMO levels of the polymers are also comparable of ?5.52 ± 0.03 eV and ?3.57 ± 0.03 eV, respectively. Thus, using the dialkoxyphenanthrene as the D unit could afford D–A copolymers with deep‐lying HOMO levels, which would be an important factor to achieve high open‐circuit voltages (V_oc) in bulk‐heterojunction solar cells. With the copolymers as the donor and PC₇₁BM as the acceptor, the resulting solar cells could display good V_oc between 0.86 and 0.88 V. Among the four copolymers, PPA‐DTBT containing the dialkoxybenzothiadiazole unit showed the best power conversion efficiency of 3.03% because of its relatively higher hole mobility and better phase separation. The results suggest that dialkoxyphenanthrene is a valuable electron‐donating unit in the constructions of D–A copolymers for efficient solar cells with high V_oc. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4966–4974     

Influence of fluorination on the microstructure and performance of diketopyrrolopyrrole‐based polymer solar cells

The solar cell performance and microstructure of DPP‐based polymers with different degrees of fluorination are reported. DPP‐based polymers with thiophene–phenyl–thiophene comonomer and thiophene flanking units are studied, with the degree of fluorination of the phenyl unit varied. With bifluorination of the phenyl ring, a higher open circuit voltage is achieved whilst maintaining or even improving the overall solar cell efficiency. While tetrafluorination leads to a further 0.1 V increase in V_OC, reaching a high photo voltage of 0.81 V, overall solar cell performance significantly drops. Microstructural studies using AFM, TEM, Grazing incidence wide‐angle X‐ray scattering (GIWAXS), and Resonant soft X‐ray scattering (R‐SoXS) reveal that bifluorination largely preserves the microstructure of the nonfluorinated system, whereas tetrafluorination results in coarse phase separation between the polymer donor and the fullerene acceptor. Our results demonstrate that the use of an extended comonomer is a promising strategy for optimizing the beneficial effects of fluorination for DPP‐based polymer solar cells, especially in improving the open circuit voltage. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 49–59     

Synthesis and characterization of isoindigo‐based polymers using CH‐arylation polycondensation reactions for organic photovoltaics

A series of three new low bandgap donor–acceptor–donor–acceptor^/ (D–A–D–A^/) polymers have been successfully synthesized based on the combination of isoindigo as the electron‐deficient acceptor and 3,4‐ethylenedioxythiophene as the electron‐rich donor, followed by CH‐arylation with different acceptors (4,7‐dibromo[c][1,2,5]‐(oxa, thia, and/or selena)diazole ( 4a‐c )). These polymers were used as donor materials for photovoltaic applications. All of the polymers are highly stable and show good solubility in chlorinated solvents. The highest power conversion efficiency of 1.6% was achieved in the bulk heterojunction photovoltaic device that consisted of poly ((E)?6‐(7‐(benzo‐[c][1,2,5]‐thiadiazol‐4‐yl)?2,3‐dihydrothieno‐[3,4‐b][1,4]dioxin‐5‐yl)?6′‐(2,3‐dihydrothieno‐[3,4‐b][1,4]‐dioxin‐5‐yl)?1,1′‐bis‐(2‐octyldodecyl)‐[3,3′‐biindolinylidene]‐2,2′‐dione) as the donor and PC₆₁BM as the acceptor, with a short‐circuit current density (J_sc) of 8.10 mA/cm², an open circuit voltage (V_oc) of 0.56 V and a fill factor of 35%, which indicates that these polymers are promising donors for polymer solar cell applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2926–2933     

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     

A novel planar D‐A alternating copolymer with D‐A integrated structures exhibiting H‐aggregate behaviors for polymer solar cells

With the D‐A integrated structure concept, a new donor–acceptor (D‐A) copolymer poly{(N‐dodecyl‐carbazole[3,4‐c:5,6‐c]bis[1,2,5]thiadiazole‐alt‐4,8‐di(2‐ethylhexy‐loxyl)benzo[1,2‐b:4,5‐b′]dithiophene)} has been designed and synthesized using a novel architecture N‐dodecyl‐carbazole[3,4‐c:5,6‐c]bis[1,2,5]thiadiazole, and di(2‐ethylhexy‐loxyl)benzo[1,2‐b:4,5‐b′]dithiophene) as the basic building blocks. The copolymer has a low‐lying highest occupied molecular orbital energy level of ?5.41 eV and a broaden absorption matching well with the main solar photon flux. Note that an H‐aggregation beneficial for charge transportation and collection is formed in the macromolecules film, which implies that the planar D‐A integrated structure favors the strong intermolecular interaction to render molecules aggregated via face‐to‐face self‐assembly. The aggregation becomes larger scale after thermal annealing. Additionally, obvious intramolecular charge transfer and energy transfer have occurred in created D‐A integration. Without any treatment, the resulting polymer achieved a efficiency of 2.0% and relatively high open‐circuit voltage (V_oc) value of 0.77 V when blended with [6,6]‐phenyl‐C61‐butyric acid methyl ester in a typical bulk heterojunction. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and photovoltaic properties of copolymers based on bithiophene and bithiazole

Three simple structured D‐A copolymers, PBTBTz‐1 , PBTBTz‐2 , and PBTBTz‐3 , containing bithiophene (BT) donor unit and bithiazole (BTz) acceptor unit with different alkyl chain length were synthesized by the Pd‐catalyzed Stille‐coupling method. The copolymers were characterized by thermogravimetric analysis, UV–vis absorption, electrochemical cyclic voltammetry, and photovoltaic measurements. The results indicate that the introduction of BTz unit to the polythiophene main chain effectively decreases highest occupied molecular orbital levels of the copolymers and increases the open circuit voltage (V_oc) of polymer solar cells (PSCs) based on the copolymers as donor, and the alkyl chain length influences the photovoltaic properties of the polymers significantly. The PSCs based on PBTBTz‐2 and PBTBTz‐3 show higher V_oc up to 0.77 and 0.81 V, respectively. The power conversion efficiency of the PSC based on PBTBTz‐2 :PC₇₀BM = 1:1(w/w) reached 2.58% with short circuit current of 8.70 mA/cm², under the illumination of AM1.5, 100 mW/cm². © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011