Synthesis of all‐conjugated poly(3‐hexylthiophene)‐block‐ poly(3‐(4′‐(3″,7″‐dimethyloctyloxy)‐3′‐pyridinyl)thiophene) and its blend for photovoltaic applications

New all‐conjugated block copolythiophene, poly(3‐hexylthiophene)‐block‐poly(3‐(4′‐(3″,7″‐dimethyloctyloxy)‐3′‐pyridinyl)thiophene) (P3HT‐b‐P3PyT) was successfully prepared by Grignard metathesis polymerization. The supramolecular interaction between [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) and P3PyT was proposed to control the aggregated size of PCBM and long‐term thermal stability of the photovoltaic cell, as evidenced by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and optical microscopy. The effect of different solvents on the electronic and optoelectronic properties was studied, including chloroform (CL), dichlorobenzene (DCB), and mixed solvent of CL/DCB. The optimized bulk heterojunction solar cell devices using the P3HT‐b‐P3PyT/PCBM blend showed a power conversion efficiency of 2.12%, comparable to that of P3HT/PCBM device despite the fact that former had a lower crystallinity or absorption coefficient. Furthermore, P3HT‐b‐P3PyT could be also used as a surfactant to enhance the long‐term thermal stability of P3HT/PCBM‐based solar cells by limiting the aggregated size of PCBM. This study represents a new supramolecular approach to design all‐conjugated block copolymers for high‐performance photovoltaic devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Enhanced properties of photovoltaic devices tailored with novel supramolecular structures based on reduced graphene oxide nanosheets grafted/functionalized with thiophenic materials

For verifying the influence of donor–acceptor supramolecules on photovoltaic properties, different hybrids were designed and used in organic solar cells. In this respect, reduced graphene oxide (rGO) was functionalization with 2‐thiophene acetic acid (rGO‐f‐TAA) and grafted with poly(3‐dodecylthiophene) (rGO‐g‐PDDT) and poly(3‐thiophene ethanol) (rGO‐g‐PTEt) to manipulate orientation of poly(3‐hexylthiophene) (P3HT) assemblies. Face‐on, edge‐on, and flat‐on orientations were detected for assembled P3HTs on rGO and its functionalized and grafted derivatives, respectively. Alteration of P3HT orientation from face‐on to flat‐on enhanced current density (J _sc), fill factor (FF), and power conversion efficiency (PCE) and thus J _sc = 7.11 mA cm^?2, FF = 47%, and PCE = 2.14% were acquired. By adding phenyl‐C71‐butyric acid methyl ester (PC71BM) to active layers composed of pre‐designed P3HT/rGO, P3HT/rGO‐f‐TAA, P3HT/rGO‐g‐PDDT, and P3HT/rGO‐g‐PTEt hybrids, photovoltaic characteristics further improved, demonstrating that supramolecules appropriately mediated in P3HT:PC71BM solar cells. Phase separation was more intensified in best‐performing photovoltaic systems. Larger P3HT crystals assembled onto grafted rGOs (95–143 nm) may have acted as convenient templates for the larger and more intensified phase separation in P3HT:PCBM films. The best performances were reached for P3HT:P3HT/rGO‐g‐PDDT:PCBM (J _sc = 9.45 mA cm^?2, FF = 54%, and PCE = 3.16%) and P3HT:P3HT/rGO‐g‐PTEt:PCBM (J _sc = 9.32 mA cm^?2, FF = 53%, and PCE = 3.11%) photovoltaic systems. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1877–1889     

Effects of amorphous poly(3‐hexylthiophene) on active‐layer structure and solar cells performance

A key challenge to the development of polymer‐based organic solar cells is the issue of long‐term stability, which is mainly caused by the unstable time‐dependent morphology of active layers. In this study, poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl C60‐butyric acid methyl ester (PCBM) blend is used as a model system to demonstrate that the long‐term stability of power conversion efficiency can be significantly improved by the addition of a small amount of amorphous regiorandom P3HT into semicrystalline regioregular one. The optical properties measured by UV–vis absorption and photoluminescence reveal that regiorandom P3HT can intimately mix with PCBM and prevent the segregation of PCBM. In addition, X‐ray scattering techniques were adopted to evidence the retardation of phase separation between P3HT and PCBM when regiorandom P3HT is added, which is further confirmed by optical microscopy that shows a reduction of large PCBM crystals after annealing at high temperature in the presence of regiorandom P3HT. The improvement of the long‐term stability is attributed to the capability of amorphous P3HT to be thermodynamically miscible with PCBM, which allows the active layer to form a more stable structure that evolves slower and hence decelerates the device decay. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 975–985     

Synthesis and Photovoltaic Properties of Ester Group Functionalized Polythiophene Derivatives

To increase the open circuit voltage (V_OC) of polymer solar cells (PSCs) based on polythiophene, two new ester group functionalized polythiophene derivatives, PCTDT and PCTBDT, were designed and synthesized via alternating copolymerization of thiophene‐3‐carboxylate (CT) with the 2,2′‐bithiophene (DT) and benzodithiophene (BDT) units, respectively. The resulting copolymers exhibited broad and strong absorptions in the visible region, which was similar to that of the commonly used poly(3‐hexylthiophene) (P3HT). Through cyclic voltammetry measurements, it was found that both copolymers showed lower HOMO energy levels (−5.27 eV for PCTDT and −5.36 eV for PCTBDT) than that of P3HT (−5.03 eV), indicating that the HOMO energy level could be efficiently reduced by introducing the ester group into the polymer side chain. Photovoltaic properties of the copolymers blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) as electron acceptor were investigated. The obtained two devices possessed both relatively large short circuit current (I_SC) and higher V_OC than that of P3HT:PCBM blend. For PCTBDT:PCBM blend, a power conversion efficiency (PCE) up to 2.32%, an I_SC of 6.94 mA · cm⁻², and a V_OC of 0.80 V were observed while PCTDT:PCBM system demonstrated a PCE of 1.75% with a V_OC of 0.68 V.

     

Photoluminescence Study on Charge Transfer Behavior of Poly(3‐hexylthiophene) and PCBM Blends

Charge transfer behavior of Poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl eser (PCBM) in solutions and in films were examined by photoluminescence (PL) spectroscopy. PL study in solutions indicated that separation distance between P3HT and PCBM affected charge transfer efficiency more seriously than the interface area issue between P3HT and PCBM. P3HT/PCBM film showed very effective photo‐induced charge transfer before post‐thermal annealing on the bi‐layer P3HT/PCBM film. Charge transfer efficiency was gradually diminished by the annealing‐induced phase separation between P3HT and PCBM as revealed by increasing PL emission intensity of P3HT.     

用CdSe/ZnS量子点提高体异质结有机太阳电池的效率

通过掺杂吸收光谱在可见光波段的量子点可提高聚合物对可见光的吸收,因此掺杂CdSe/ZnS核-壳结构量子点(CQDs)能提高聚(3-己基噻吩):[6,6]-苯基-C61-丁酸甲酯(P3HT:PCBM)体异质结太阳电池的能量转换效率.本文研究了CdSe/ZnS量子点在P3HT:PCBM中的不同掺杂比例及其表面配体对太阳电池光伏性能的影响,优化器件ITO(氧化铟锡)/PEDOT:PSS(聚(3,4-乙撑二氧噻吩:聚苯乙烯磺酸)/P3HT:PCBM:(CdSe/ZnS)/Al的能量转换效率达到了3.99%,与相同条件下没有掺杂量子点的参考器件ITO/PEDOT:PSS/P3HT:PCBM/Al相比,其能量转换效率提高了45.1%.     

Effect of multiple adduct fullerenes on charge generation and transport in photovoltaic blends with poly(3‐hexylthiophene‐2,5‐diyl)

The effect of replacing [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) by its multiadduct analogs (bis‐PCBM and tris‐PCBM) in bulk heterojunction organic solar cells with poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) is studied in terms of blend film microstructure, photophysics, electron transport properties, and device performance. Although the power conversion efficiency of the blend with bis‐PCBM is similar to the blend with PCBM, the performance of the devices with tris‐PCBM is considerably lower as a result of small photocurrent. Despite the lower electron affinity of the fullerene multiadducts, μs‐ms transient absorption measurements show that the charge generation efficiency is similar for all three fullerenes. The annealed blend films with multiadducts show a lower degree of fullerene aggregation and lower P3HT crystallinity than the annealed blend films with PCBM. We conclude that the reduction in performance is due largely to poorer electron transport in the blend films from higher adducts, due to the poorer fullerene network formation as well as the slower electron transport within the fullerene phase, confirmed here by field effect transistor measurements. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Impact of side‐chain length on the phase structures of P3ATs and P3AT:PCBM films as revealed by SSNMR and FTIR

It is known that poly(3‐alkylthiophene) (P3AT) side‐chain length notably influences the photovoltaic performances of relating devices. However, comprehensively study on its impact on the structures of P3ATs and their blends with [6, 6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) is insufficient. By using solid‐state NMR and FTIR techniques, four P3ATs and their PCBM blends are investigated in this work, focusing on the phase structures as modulated by side‐chain length. Recently, we revealed multiple crystalline main‐chain packings of packing a and b together with a mesophase in poly(3‐butylthiophene) (P3BT) films (DOI: 10.1021/acs.macromol.6b01828). Here, the semicrystalline structures are investigated on poly(3‐hexylthiophene) (P3HT), poly(3‐octylthiophene) (P3OT), and poly(3‐dodecylthiophene) (P3DDT) with traditional form I modification, where packing a and the amorphous phase are probed. Furthermore, crystallized side chain within packing a is detected in both P3OT and P3DDT films, which shows a FTIR absorption at 806 cm⁻¹. Structural studies are also conducted on P3AT:PCBM blends. Compared with the pure P3ATs, the polymer crystallinities of the blends show reduction of about 40% for P3OT and P3DDT, whereas only about 10% for P3HT. Moreover, in P3BT:PCBM and P3HT:PCBM, the crystalline polymers and PCBM are phase separated, while in P3OT:PCBM and P3DDT:PCBM, blend components are mostly miscible. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 751–761     

Phthalimide and Naphthalimide end‐Capped Diketopyrrolopyrrole for Organic Photovoltaic Applications

Two small molecules named PI‐DPP and NI‐DPP with a DPP core as the central strong acceptor unit and phthalimide/naphthalimide as the terminal weak acceptor were designed and synthesized. The effects of terminal phthalimide/naphthalimide units on the thermal behavior, optical and electrochemical properties, as well as the photovoltaic performance of these two materials were systematically studied. Cyclic voltammetry revealed that the lowest unoccupied molecular orbitals (LUMO) (~ ‐3.6 eV) of both molecules were intermediate to common electron donor (P3HT) and acceptor (PCBM). This indicated that PI‐DPP and NI‐DPP may uniquely serve as electron donor when blended with PCBM, and as electron acceptor when blended with P3HT, where sufficient driving forces between DPPs and PCBM, as well as between P3HT and DPPs should be created for exciton dissociation. Using as electron donor materials, PI‐DPP and NI‐DPP devices exhibited low power conversion efficiencies (PCEs) of 0.90% and 0.76% by blending with PCBM, respectively. And a preliminary evaluation of the potential of the NI‐DPP as electron acceptor material was carried out using P3HT as a donor material, and P3HT: NI‐DPP device showed a PCE of 0.6%, with an open circuit voltage (V _OC) of 0.7 V, a short circuit current density (J _SC) of 1.91 mA•cm^‐2, and a fill factor (FF) of 45%.     

A novel donor–donor polymeric dyad of Poly(3‐hexylthiophene‐block‐oligo(anthracene‐9,10‐diyl): Synthesis,solid‐state packing,and electronic properties

A new polymeric dyad of oligo‐anthracene‐block‐poly(3‐hexylthiophene) (Oligo‐ANT‐b‐P3HT) has been synthesized as a donor–donor dyad building block for organic photovoltaics. The polymer dyad and oligomer of anthracene‐9,10‐diyl (Oligo‐ANT) are prepared by Grignard Metathesis. The higher order of crystallinity and molecular chains ordering at solid phase reveal the intrinsic optical and electrical properties of polymeric dyad resulting in relatively higher light harvesting ability compared to the oligo(anthracene‐9,10‐diyl). The UV‐visible spectrum of (Oligo‐ANT‐b‐P3HT) in solution shows broad absorption with two sets of absorption from both anthracene and thiophene core units, covering a wide range of the visible spectrum. The test devices of the blends of polymeric dyad with fullerene C₆₁ (PCBM) show improved photovoltaic performance with a power conversion efficiency of 3.26% upon subjecting to pre‐fabrication thermal treatments. With optimized morphology of the interpenetrating network and the shorter fluorescence lifetime of the annealed dyad/PCBM blends, the effective charge transfer from the donor dyad to PCBM has evidenced. Thus, these studies will allow further synthetic advances to make potential high crystalline polymeric dyads with significantly improved light harvesting capability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3032–3045     

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     

Potential of bifluorenylidene derivatives as nonfullerene small-molecule acceptor for heterojunction organic photovoltaics: a density functional theory study

To maximize the efficiency of heterojunction organic photovoltaics (HJOPVs), it is imperative to increase not only the open-circuit voltage (V _OC) but also the short-circuit current (I _SC). Therefore, it is desirable to find an organic acceptor material that possesses a higher lowest unoccupied molecular orbital (LUMO) level for higher V _OC and can absorb photons in the solar spectrum efficiently for larger I _SC. In this paper, in comparison with the typical donor poly(3-hexylthiophene) (P3HT) and acceptor [6,6]-phenyl-C₆₁-butyric acid ester ([60]PCBM), the geometries, electronic structures, absorption spectra, and transport properties of a series of organic compounds containing 9,9′-bifluorenylidene (9,9′BF) were systematically investigated using density functional and the semiclassical Marcus charge transfer theory calculation to evaluate their potential severing as acceptor. Our results indicate that the absorption spectra of 99′BF derivatives have better overlap with the solar spectrum than those of [60]PCBM, and higher LUMOs result in a significant enhancement of V _OC when they are used in HJOPVs with P3HT as donor materials. On the other hand, these compounds own higher electron carrier mobilities comparing with [60]PCBM. The study also demonstrates that the H-shaped compounds based on the 99′BF backbone possess good photophysical and charge transport properties, can be promising organic semiconductor for heterojunction photovoltaics.     

Effect of Device Fabrication Conditions on Photovoltaic Performance of Polymer Solar Cells Based on Poly(3‐hexylthiophene) and Indene‐C70 Bisadduct

Effect of the device fabrication conditions on photovoltaic performance of the polymer solar cells based on poly(3‐hexylthiophene) (P3HT) as donor and indene‐C₇₀ bisadduct (IC₇₀BA) as acceptor was studied systematically. The device fabrication conditions we studied include pre‐thermal annealing temperature, active layer thickness, and the P3HT:IC₇₀BA weight ratios. For devices with a 188‐nm‐thick active layer of P3HT:IC₇₀BA (1:1, w:w) blend film and pre‐thermal annealing at 150°C for 10 min, maximum power conversion efficiency (PCE) reached 5.82% with V_oc of 0.81 V, I_sc of 11.37 mA/cm², and FF of 64.0% under the illumination of AM1.5G, 100 mW/cm².     

Coating on a Cold Substrate Largely Enhances Power Conversion Efficiency of the Bulk Heterojunction Solar Cell

Spin‐coating a mixture solution of P3HT and PCBM on a cold substrate largely enhanced the power conversion efficiency (PCE) of the bulk heterojunction (BHJ) solar cells. This concept was based on the abrupt decrease in the solubility of P3HT as solution temperature decreased. The selective precipitation of P3HT on the PEDOT:PSS‐coated cold substrate facilitated a desirable rich composition of P3HT at the interface with the PEDOT:PSS layer. The high crystallinity of P3HT suppressed the movement of PCBM during thermal annealing, preventing aggregation of PCBM. The morphological excellence of the pristine film gave a comparable PCE to that made by the conventional fabrication process. After thermal annealing, the device made via coating on a cold substrate showed above 30% increase in PCE from the BHJ solar cells made by the conventional method.

     

Vinyl‐Type Polynorbornenes with Pendant PCBM: A Novel Acceptor for Organic Solar Cells

Vinyl addition homo‐ and copolymerization of norbornene monomer ( M1 ) functionalized with a PCBM moiety using a Pd(II) catalyst in combination with a 1‐octene chain transfer agent efficiently produces polynorbornenes with side‐chain PCBM groups. Characterization by NMR spectroscopy and elemental analysis reveals that the copolymers constitute a well‐defined polymer structure with controlled incorporation of M1 . Although the homopolymer is insoluble in organic solvents, the copolymers containing 62 mol% ( P2 ) and 50 mol% ( P3 ) of the PCBM moiety are soluble in chlorinated solvents such as o‐dichlorobenzene. The bulk‐heterojunction organic photovoltaic devices fabricated based on the P3HT: P3 blends show that P3 can adequately function as an electron acceptor, leading to a cell with a power conversion efficiency of 1.5%, which is outstanding among the polymeric rivals.     

Photoactive Polythiophene:Titania Hybrids with Excellent Miscibility for Use in Polymer Photovoltaic Cells

A series of poly{(3‐hexylthiophene)‐co‐[3‐(6‐hydroxyhexyl)thiophene]}:titania (P3HT‐OH:TiO₂) hybrids were synthesized via the in situ polycondensation of titanium (IV) n‐butoxide in the presence of P3HT‐OH. Introducing a hydroxyl moiety onto the side‐chain of poly(3‐hexylthiophene) (P3HT) significantly promotes the polymer‐titania interaction, resulting in the formation of homogeneous hybrid colloids. The UV‐vis spectra of P3HT‐OH:TiO₂ films demonstrate that TiO₂ markedly affects the stacking structure and the chain conformation of P3HT‐OH. The maximum absorption wavelength of these hybrid materials can be tailor‐made by merely varying the weight percentage of TiO₂. Moreover, P3HT‐OH:TiO₂ can be further utilized as an efficient compatibilizer in preparing photoactive P3HT:P3HT‐OH:TiO₂ films with excellent miscibility. The photovoltaic cell based on such a hybrid exhibited a 2.4‐fold higher value of power‐conversion efficiency compared to the cell based on P3HT:TiO₂.

     

Design and synthesis of dithieno[3,2‐b:2′3′‐d]pyrrole‐based conjugated polymers for photovoltaic applications: consensus between low bandgap and low HOMO energy level

A strategy of the fine‐tuning of the degree of intrachain charge transfer and aromaticity of polymer backbone was adopted to design and synthesize new polymers applicable in photovoltaics. Three conjugated polymers P1 , P2 , and P3 were synthesized by alternating the electron‐donating dithieno[3,2‐b:2′3′‐d]pyrrole (D) and three different electron‐accepting (A) segments ( P1 : N‐(2‐ethylhexyl)phthalimide; P2 : 1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole; and P3 : thiophene‐3‐hexyl formate) in the polymer main chain. Among the three polymers, P2 possessed the broadest absorption band ranging from 300 to 760 nm, the lowest bandgap (1.63 eV), and enough low HOMO energy level (?5.27 eV) because of the strong intrachain charge transfer from D to A units and the appropriate extent of quinoid state in the main chain of P2 , which was convinced by the theoretical simulation of molecular geometry and front orbits. Photovoltaic study of solar cells based on the blends of P1 – P3 and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) demonstrated that P2 :PCBM exhibited the best performance: a power conversion efficiency of 1.22% with a high open‐circuit voltage (V_OC) of 0.70 V and a large short‐circuit current (I_SC) of 5.02 mA/cm² were achieved. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Donor–acceptor alternating π‐conjugated polymers containing Di(thiophen‐2‐yl)pyrene and 2,5‐Bis(2‐octyldodecyl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione for organic thin‐film transistors

New diketopyrrolopyrrole (DPP)‐containing conjugated polymers such as poly(2,5‐bis(2‐octyldodecyl)‐3‐(5‐(pyren‐1‐yl)thiophen‐2‐yl)‐6‐(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione) (P(DTDPP‐alt‐(1,6)PY)) and poly(2,5‐bis(2‐octyldodecyl)‐3‐(5‐(pyren‐2‐yl)thiophen‐2‐yl)‐6‐(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione) (P(DTDPP‐alt‐(2,7)PY)) were successfully synthesized via Suzuki coupling reactions under Pd(0)‐catalyzed conditions. P(DTDPP‐alt‐(2,7)PY), incorporating 2,5‐bis(2‐octyldodecyl)‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione (DTDPP) at the 2,7‐position of a pyrene ring showed a lower band‐gap energy (E. = 1.65 eV) than the 1,6‐substituted analog, P(DTDPP‐alt‐(1,6)PY) (E = 1.71 eV). The energies of the molecular frontier orbitals of the substituted polymers were successfully tuned by changing the anchoring position of DTDPP from the 1,6‐ to the 2,7‐position of the pyrene ring. An organic thin‐film transistor fabricated using the newly synthesized P(DTDPP‐alt‐(2,7)PY), as a semiconductor material exhibited a maximum mobility of up to 0.23 cm² V^?1 s^?1 (I_on/off ～ 10⁶), which was much larger than that obtained using P(DTDPP‐alt‐(1,6)PY). This distinction is attributed to morphological differences in the solid state arising from differences between the geometrical configurations of DTDPP and the pyrene ring. In addition, the organic phototransistor devices made of P(DTDPP‐alt‐(2,7)PY) showed interesting photoinduced enhancement of drain current when irradiating the excitation light whose intensity is very small. Based on the photoinduced effect on I_DS, photocontrolled memory could be realized under the variation of gate voltages. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

4,9‐Dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione functionalized copolymers for organic photovoltaic devices

The synthesis of conjugated polymers 1 – 5 functionalized with 4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione in the backbone is reported and their use in the construction of organic solar cells is demonstrated. Increasing the molar ratio of 2,7‐dibromo‐3,8‐dihexyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione, relative to 4,4′‐dihexyl‐5,5′‐dibromo‐2,2′‐bithiophene, in the copolymer synthesis significantly lowers the solubility of these polymers. The incorporation of highly conjugated 3,8‐dihexyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐4,9‐dione unit into the polymer backbone has been confirmed by UV–vis absorption. The observation of decreasing quantum yield for the emission in the order of 1 , 2 , 3 is consistent with copolymers with different comonomer content. The power conversion efficiencies of solar cells using blends of these polymers with PCBM ([6,6]‐phenyl C₆₁‐butyric acid methyl ester) were determined to be 0.11% for polymer 1 , 0.33% for 2 , and 0.26% for 3 , respectively. Under identical white light illumination, the power conversion efficiency of the device based on polymer 2 /PCBM as the active layer was three times higher compared to that of device based on polymer 1 /PCBM. Owing to the limited solubility and poor film‐forming ability of polymer 3 , the power conversion efficiency of solar cell based on 3 /PCBM blend is lower than that of 2 /PCBM blend, but is still larger than that of 1 /PCBM blend. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2680–2688, 2008     

Morphology and Performance of Poly(2-methoxy-5-(20-ethyl-hexyloxy)-p-phenylenevinylene) (MEH-PPV)∶(6,6)-Phenyl-C61-butyric Acid Methyl Ester (PCBM) Based Polymer Solar Cells

Polymer solar cells were fabricated based on composite films of poly(2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐1,4‐phenylenevinylene) (MEH‐PPV):fullerene derivative (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) with weight blend ratio of 1:3, 1:4 and 1:5, spin‐coated from chloroform (CF), chlorobenzene (CB), and o‐dichlorobenzene (ODCB) solutions, respectively. Photoinduced current and power conversion efficiency (PCE) of the devices show a dependence on the solvents. The solar cells have the highest PCE at 1:5 blend ratio. Transmission electron microscopy (TEM) morphology reveals that there are some voids in MEH‐PPV:PCBM films. The void number decreases with the solvent from CF to CB and ODCB. We found the voids are located at the bottom of the films through electron tomography technique by TEM and film bottom‐side morphology study by atomic force microscopy. The charge carrier transport efficiency and collection efficiency should decrease greatly due to the voids, and the more voids the film has, the more degree the efficiencies decrease. PCE of the solar cell prepared from CF is lower than that of the solar cells prepared from CB and ODCB. The void phenomenon of MEH‐PPV:PCBM based solar cell and method to investigate the void position provide an experimental evidence and research mentality to fabricate polymer solar cell with high performance.