New Conjugated Molecules with Two and Three Dithienyldiketopyrrolopyrrole (DPP) Moieties Substituted at meta Positions of Benzene toward p‐ and n‐Type Organic Photovoltaic Materials

Two conjugated molecules, TADPP3 and TADPP2‐TT , are reported, in which three and two dithienyldiketopyrrolopyrrole (DPP) moieties, respectively, are substituted at the meta positions of benzene. Based on cyclic voltammetry and absorption data, TADPP3 and TADPP2‐TT possess similar HOMO and LUMO energies of about ?5.2 and ?3.4 eV, respectively. Thin films of TADPP3 and TADPP2‐TT exhibit p‐type semiconducting behavior with hole mobilities of 2.36×10^?3 and 3.76×10^?4 cm² V^?1 s^?1 after thermal annealing. Molecules TADPP3 and TADPP2‐TT were utilized as p‐type photovoltaic materials to fabricate organic solar cells after blending with phenyl C₇₁ butyric acid methyl ester ( PC₇₁BM ) and phenyl C₆₁ butyric acid methyl ester ( PC₆₁BM ). The relatively low J_SC and fill factor values can be attributed to poor film morphologies based on AFM and XRD studies. A solar cell with a thin film of TADPP3 with PC₇₁BM in a weight ratio of 1:2 exhibits a high open‐circuit voltage (V_OC) of 0.99 V and a power conversion efficiency (PCE) of 2.47 %. Interestingly, TADPP3 can also be employed as an n‐type photovoltaic material. The blended thin film of TADPP3 with P3HT in a weight ratio of 1:2 gave a high V_OC of 1.11 V and a PCE of 1.08 % after thermal annealing.     

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     

Bay‐annulated indigo based near‐infrared sensitive polymer for organic solar cells

A new conjugated polymer (PBAIIDTT) based on bay‐annulated indigo and indacenodithieno[3,2‐b]thiophene was designed, synthesized, and characterized. PBAIIDTT shows strong absorption in 400–500 and 600–800 nm, and its HOMO and LUMO energy levels are −5.45 eV and −3.65 eV, respectively. In organic field‐effect transistors, the polymer exhibits a relatively high hole mobility of 0.39 cm² V⁻¹ s⁻¹. PBAIIDTT was added to poly(3‐hexylthiophene) (P3HT) and phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) based organic solar cells. Ternary blend solar cells with 10% PBAIIDTT show an increased short circuit current density due to the broadened photocurrent generated in the near‐infrared region, and a power conversion efficiency of 3.78%, which is higher than that of the P3HT:PC₆₁BM binary control devices (3.33%). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 213–220     

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     

Free Carrier Generation in Organic Photovoltaic Bulk Heterojunctions of Conjugated Polymers with Molecular Acceptors: Planar versus Spherical Acceptors

A comparative study of the photophysical performance of the prototypical fullerene derivative PC₆₁BM with a planar small‐molecule acceptor in an organic photovoltaic device is presented. The small‐molecule planar acceptor is 2‐[{7‐(9,9‐di‐n‐propyl‐9H‐fluoren‐2‐yl)benzo[c][1,2,5]thiadiazol‐4‐yl}methylene]malononitrile, termed K12. We discuss photoinduced free charge‐carrier generation and transport in blends of PC₆₁BM or K12 with poly(3‐n‐hexylthiophene) (P3HT), surveying literature results for P3HT:PC₆₁BM and presenting new results on P3HT:K12. For both systems we also review previous work on film structure and correlate the structural and photophysical results. In both cases, a disordered mixed phase is formed between P3HT and the acceptor, although the photophysical properties of this mixed phase differ markedly for PC₆₁BM and K12. In the case of PC₆₁BM the mixed phase acts as a free carrier generation region that can efficiently shuttle carriers to the pure polymer and fullerene domains. As a result, the vast majority of excitons quenched in P3HT:PC₆₁BM blends yield free carriers detected by the contactless time‐resolved microwave conductivity (TRMC) method. In contrast, approximately 85 % of the excitons quenched in P3HT:K12 do not result in free carriers over the nanosecond timescale of the TRMC experiment. We attribute this to poor electron‐transport properties in the mixed P3HT:K12 phase. We propose that the observed differences can be traced to the respective shapes of PC₆₁BM and K12: the three‐dimensional nature of the fullerene cage facilitates coupling between PC₆₁BM molecules irrespective of their relative orientation, whereas for K12 strong electronic coupling is only expected for molecules oriented with their π systems parallel to each other. Comparison between the eutectic compositions of the P3HT:PC₆₁BM and P3HT:K12 shows that the former contains enough fullerene to form a percolation pathway for electrons, whereas the latter contains a sub‐percolating volume fraction of the planar acceptor. Furthermore, the planar K12 co‐assembles with P3HT into a disordered, glassy phase that partly accounts for the poor electron‐transport properties, and may also enhance recombination due to the strong intermolecular interactions between the donor and the acceptor. The implication for the performance of organic photovoltaic devices with the two acceptors is also discussed.     

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     

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

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

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     

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     

Enhanced efficiency of ternary organic solar cells by doping a polymer material in P3HT:PC61BM

Doping a low‐bandgap polymer material (PDTBDT‐DTNT) as a complementary electron donor in poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyricacid methyl ester (PC₆₁BM) blend is experimented to improve the power conversion efficiency (PCE) of organic solar cells (OSCs). The PCE of OSCs was increased from 3.19% to 3.75% by doping 10 wt% PDTBDT‐DTNT, which was 17.55% higher than that of the OSCs based on binary blend of P3HT:PC₆₁BM (host cells). The short‐circuit current density (J_sc) was increased to 10.11 mA·cm⁻² compared with the host cells. Although the PCE improvement could partly be attributed to more photon harvest for complementary absorption of 2 donors by doping appropriate PDTBDT‐DTNT, the promotion of charge separation and transport as well as the suppression of charge recombination due to a matrix of cascade energy levels is also important. And the better morphology of the active layer films is beneficial to the optimized performance of ternary devices.     

Regioregular poly(3‐alkanoylthiophene): Synthesis and electrochemical,photophysical, charge transport,and photovoltaic properties

Head‐to‐tail regioregular poly(3‐heptanoylthiophene) (PHOT) was synthesized by Ni‐catalyzed polycondensation of the 2,2‐dimethyl‐1,3‐propanediol‐protected Grignard monomer followed by deprotection. Cyclic voltammetric (CV) study demonstrates that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of PHOT are 0.5 eV lower in energy than those of the head‐to‐tail poly(3‐hexylthiophene) (HT‐P3HT). Their optical band gaps are essentially the same. Incomplete photoluminescence (PL) quenching was observed in thin films of the 1:1 blend of PHOT and HT‐P3HT. PHOT displayed a glass transition at ～269 °C and decomposed at ～300 °C according to differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Wide‐angle X‐ray diffraction (WAXD) study showed that PHOT exists in a not highly ordered state in solid films especially in the π‐stacking direction. Only p‐channel activity was observed in field‐effect transistors (FETs) for PHOT. The hole mobility was on the order of 10^?4 cm² V^?1 s^?1. Photovoltaic devices with an active layer of 1:1 blend of PHOT and PC₇₁BM had a power conversion efficiency (PCE) of ～0.5%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

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.     

Impact of 1,8-diiodooctane on the morphology of organic photovoltaic (OPV) devices – A Small Angle Neutron Scattering (SANS) study

The impact of the additive 1,8-diiodooctane on the morphology of bulk-heterojunction solar cells based on the systems P3HT:PC₇₁BM, PTB7:PC₇₁BM and PTB7-Th:PC₇₁BM is studied using a combination of Small Angle Neutron Scattering (SANS) and Atomic Force Microscopy (AFM). The results clearly show that while in the P3HT:PC₇₁BM system, the additive DIO promotes a slight coarsening of the phase domains (type I additive), in the systems PTB7:PC₇₁BM and PTB7-Th:PC₇₁BM, DIO promotes a large decrease in the size of the phase domains (type II additive). SANS is demonstrated as being particularly useful at detecting the minor morphological changes observed in the P3HT:PC₇₁BM system, which can be hardly seen in AFM. This work illustrates how SANS complements AFM and both techniques when used together provide a deeper insight into the nanoscale structure in thin organic photovoltaic (OPV) device films.     

A Pentacyclic Nitrogen‐Bridged Thienyl–Phenylene–Thienyl Arene for Donor–Acceptor Copolymers: Synthesis,Characterization, and Applications in Field‐Effect Transistors and Polymer Solar Cells

A pentacyclic benzodipyrrolothiophene ( BDPT ) unit, in which two outer thiophene rings are covalently fastened with the central phenylene ring by nitrogen bridges, was synthesized. The two pyrrole units embedded in BDPT were constructed by using one‐pot palladium‐catalyzed amination. The coplanar stannylated Sn‐BDPT building block was copolymerized with electron‐deficient thieno[3,4‐c]pyrrole‐4,6‐dione ( TPD ), benzothiadiazole ( BT ), and dithienyl‐diketopyrrolopyrrole ( DPP ) acceptors by Stille polymerization. The bridging nitrogen atoms make the BDPT motif highly electron‐abundant and structurally coplanar, which allows for tailoring the optical and electronic properties of the resultant polymers. Strong photoinduced charge‐transfer with significant band‐broadening in the solid state and relatively higher oxidation potential are characteristic of the BDPT‐based polymers. Poly(benzodipyrrolothiophene‐alt‐benzothiadiazole) ( PBDPTBT ) achieved the highest field‐effect hole mobility of up to 0.02 cm² V^?1 s^?1. The photovoltaic device using the PBDPTBT /PC₇₁BM blend (1:3, w/w) exhibited a V_oc of 0.6 V, a J_sc of 10.34 mA cm^?2, and a FF of 50 %, leading to a decent PCE of 3.08 %. Encouragingly, the device incorporating poly(benzodipyrrolothiophene‐alt‐thienopyrrolodione) ( PBDPTTPD )/PC₇₁BM (1:3, w/w) composite delivered a highest PCE of 3.72 %. The enhanced performance arises from the lower‐lying HOMO value of PBDPTTPD to yield a higher V_oc of 0.72 V.     

Theoretical Prediction on Photovoltaic Properties of 4Cl‐BPPQ/PC61BM System via Density Functional Theory Calculations

Designing and synthesizing high‐performable electron donor materials are very important for fabricating organic solar cell devices with high power conversion efficiency (PCE). In this work, quantum chemical and molecular dynamics calculations coupled with the Marcus‐Hush charge transfer model were used to investigate the photovoltaic properties of 4Cl‐BPPQ/PC₆₁BM. Results reveal that 4Cl‐BPPQ/PC₆₁BM system theoretically possesses a large open‐circuit voltage (1.29 V), high fill factor (0.90), and over 9% PCE. Moreover, calculations also reveal that the 4Cl‐BPPQ/PC₆₁BM system has a middle‐sized exciton binding energy (0.492 eV), but relatively small charge‐dissociation and charge‐recombination reorganization energies (0.345 eV and 0.355 eV). Based on the 4Cl‐BPPQ/PC₆₁BM complex, the charge‐dissociation rate constant, k_dis, is estimated to be as large as 6.575×10¹² s^?1, while the charge‐recombination one, k_rec, is very small (<1.0 s^?1) under the same condition due to the very small driving force (ΔG_rec=?1.900 eV). In addition, by means of an amorphous cell containing one hundred 4Cl‐BPPQ molecules, the hole carrier mobility of 4Cl‐BPPQ solid is estimated as high as 3.191×10^?3 cm²·V^?1·s^?1. In brief, our calculation shows that 4Cl‐BPPQ/PC₆₁BM system is a very promising organic solar cell system, and is worth of making further device research by experiments.     

Copolymers of fluorene and thiophene with conjugated side chain for polymer solar cells: Effect of pendant acceptors

Two copolymers of fluorene and thiophene with conjugated side‐chain pending acceptor end group of cyanoacetate ( P2 ) and malononitrile ( P3 ) were synthesized. Both polymers exhibit good thermal stability and low highest occupied molecular orbital level (?5.5 eV). In comparison with P2 , P3 exhibits stronger UV–vis absorption and higher hole mobility. Polymer solar cells based on P3 :PC₇₁BM exhibits a power conversion efficiency of 1.33% under AM 1.5, 100 mW/cm², which is three times of that based on P2 :PC₇₁BM. The higher efficiency is attributed to better absorption, higher hole mobility, and the reduced phase separation scale in P3 :PC₇₁BM blend. The aggregate domain size in P3 :PC₇₁BM blend is 50 nm, much smaller than that in P2 :PC₇₁BM blend (200 nm). Tiny difference in the end groups on side chains of P2 and P3 leads to great difference in phase separation scale, charge transport, and efficiency of their photovoltaic devices. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

Synthesis and photovoltaic properties of conjugated D–A copolymers based on thienyl substituted pyrene and diketopyrrolopyrrole for polymer solar cells

A new donor‐acceptor conjugated copolymer (PDTPyDPP), comprising 2,7‐di‐2‐thienyl‐4,5,9,10‐tetrakis(hexyloxy)pyrene as a donor and diketopyrrolopyrrole (DPP) as an acceptor, was synthesized. PDTPyDPP showed good solubility in common organic solvents, broad visible absorption from 300 to 900 nm, and a moderate hole mobility up to 6.3 × 10^?3 cm² V^?1 s^?1. The power conversion efficiency of the photovoltaic device based on the PDTPyDPP/PC₇₁BM photoactive layer reached 4.43% with 0.66 V of open‐circuit voltage (V_oc), 10.52 mA cm^?2 of short‐circuit current (J_sc) and 64.11% of fill factor. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3198–3204     

Poly(3‐hexylthiophene)‐b‐poly(3‐cyclohexylthiophene): Synthesis,microphase separation,thin film transistors,and photovoltaic applications

We report the synthesis, characterization, microphase separation, field‐effect charge transport, and photovoltaic properties of regioregular poly(3‐hexylthiophene)‐b‐poly(3‐cyclohexylthiophene) (P3HT‐b‐P3cHT). Two compositions of P3HT‐b‐P3cHT (HcH63 and HcH77) were synthesized with weight‐average molecular weights of 155,500 and 210,800 and polydispersity indices of 1.45 and 1.57, respectively. Solvent‐casted HcH77 was found to self‐assemble into nanowires with a width of 12.5 ± 0.9 nm and aspect ratios of 50–120, as observed by TEM imaging. HcH77 and HcH63 annealed 280 °C were observed by small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) to be microphase‐separated with characteristic length scales of 17.0–21.7 nm. The microphase‐separated domains were shown to be crystalline with interlayer backbone (100) d‐spacings of 1.69 and 1.40 nm, which correspond to the P3HT and P3cHT blocks, respectively. Field‐effect transistors fabricated from P3HT‐b‐P3cHT thin films showed a mobility of holes (0.0019 cm²/Vs) which is independent of thermal annealing. Bulk heterojunction solar cells based on HcH77/fullerene (PC₇₁BM) blend thin films had a maximum power conversion efficiency of 2.45% under 100 mW/cm² AM1.5 solar illumination in air. These results demonstrate that all‐conjugated block copolymers are suitable semiconductors for applications in field‐effect transistors and bulk heterojunction solar cells. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 614–626, 2010     

Polymer Photovoltaic Cells Based on Polymethacrylate Bearing Semiconducting Side Chains

Polymethacrylate with semiconducting side chains ( P1 ), synthesized by free radical polymerization, was used as a donor material for polymer solar cells. P1 is of high molecular weight (M _n = 82 kg mol⁻¹), good thermal stability, narrow band gap (1.87 eV), and low‐lying HOMO energy level (−5.24 eV). P1 possesses not only the good film‐forming ability of polymers but also the high purity of small organic molecules. Power conversion efficiencies (PCEs) of 0.63% and 1.22% have been obtained for solar cells with M1 :PC₇₁BM and P1 :PC₇₁BM as the active layers, respectively. With PC₆₁BM as the acceptor, PCEs of M1 and P1 based devices decrease to 0.61% and 0.76%, respectively. To the best of our knowledge, this is the first report that free radical polymerization can be used to prepare polymer donors for photovoltaic applications.