Physical mechanisms responsible for the water-induced degradation of PC61BM P3HT photovoltaic thin films

We show that [6,6]-phenyl-C61-butyric acid methyl ester (PC₆₁BM) at the surface of thin film blends of poly(3-hexylthiophene) (P3HT):PC₆₁BM can be patterned by water. Using a series of heating and cooling steps, water droplets condense onto the blend film surface. This is possible due to the liquid-like, water swollen layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Breath pattern water deformation and subsequent drying on the film surface results in isolated PC₆₁BM structures, showing that migration of PC₆₁BM takes place. This was confirmed by selective wavelength illumination to spatially map the photoluminescence from the P3HT and PC₆₁BM. Within a device, redistribution of the surface PC₆₁BM into aggregates would be catastrophic, as it would markedly alter device performance. We also postulate that repeated volume change of the poly(3,4-ethylenedioxythiophene) polystyrene sulfonate layer by water swelling may be, in part, responsible for the delamination failure mechanism in thin film solar cells devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 141–146     

聚(3-己基噻吩)作为光谱增感层在有机太阳电池光谱响应增强中的应用

报道了利用聚(3-己基噻吩)(P3HT)作为前置缓冲层来弥补(4,8-双-(2-乙基己氧基)-苯并[1,2-b:4,5-b']二噻吩)-(4-氟代噻并[3,4-b]噻吩(PBDT-TT-F):[6,6]-苯基-C₆₁-丁酸甲酯(PC₆₁BM)共混体相异质结(BHJ)电池对450-600 nm处光谱响应不足的新的器件结构设计思路. 光谱带隙为1.8 eV的PBDT-TT-F 在550-700 nm处有很强的光谱吸收, 在有机太阳电池器件上有很好的应用潜能. 但其在350-550 nm处的吸收不强, 影响了器件对太阳光谱的利用效率. 与此相比, P3HT薄膜的光谱吸收主要在450-600 nm范围内, 同PBDT-TT-F 形成良好的互补关系. 新设计的器件外量子效率(EQE)研究结果表明, 利用P3HT 作为前置缓冲层可以与PBDT-TT-F:PC₆₁BM薄膜中的PC₆₁BM形成平面异质结, 从而拓展了器件在450-600 nm处的光谱响应范围,实现光谱增感作用. 优化P3HT的厚度为20 nm左右, 器件对外输出的短路光电流密度从11.42 mA·cm^-2提高到12.15 mA·cm^-2, 达到了6.3%的提升.     

Transport and recombination dynamics studies of polymer/fullerene based solar cells

We have studied the electron/hole transport and recombination dynamics in blends of poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene], (MDMO-PPV) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) at room temperature, as a function of laser excitation density and PCBM concentration. The experimental results of these studies indicate the important role played by hole-trap states in MDMO-PPV. Electron and hole transport are not balanced within the blend. PCBM is a less disordered material than MDMO-PPV and electron transport dominates the response of the solar cell device.     

Synthesis and characterization of cyclic P3HT as a donor polymer for organic solar cells

In this study, cyclic poly(3‐hexylthiophene‐2,5‐diyl) (c‐P3HT) with a controlled M_n was synthesized by the intramolecular cyclization of α‐bromo‐ω‐ethynyl‐functionalized P3HT via the Sonogashira coupling reaction. The effect of the cyclic structure, which does not have terminal groups of polymers, on the photoelectric conversion characteristics was investigated in comparison to linear P3HT (l‐P3HT). c‐P3HT was successfully synthesized with M_n ≈ 17,000, dispersity ≈ 1.2, and regioregularity ≈ 99%. The hole mobility was determined to be 5.1 × 10^?4 cm² V^?1 s^?1 by time‐of‐flight (TOF) experiment. This was comparable to that of l‐P3HT of 5.6 × 10^?4 cm² V^?1 s^?1. Organic solar cell systems were fabricated with each polymer by blending them with [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM). The l‐P3HT:PC₇₁BM system showed a dispersive TOF photocurrent profile for electron transport, whereas a nondispersive profile was observed for c‐P3HT:PC₇₁BM. In addition, an amount of collected electrons in c‐P3HT:PC₇₁BM was greater than that in l‐P3HT:PC₇₁BM for TOF experiments. The photoelectric conversion characteristics were improved by using c‐P3HT rather than l‐P3HT (power conversion efficiency [PCE] = 4.05% vs 3.23%), reflecting the nondispersive transport and the improvement of electron collection. PCEs will be much improved by applying this cyclic concept to highly‐efficient OSC polymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 266–271     

Significance of miscibility in multidonor bulk heterojunction solar cells

Ternary organic blends have potential in realizing efficient bulk heterojunction (BHJ) organic solar cells by harvesting a larger portion of the solar spectrum than binary blends. Several challenging requirements, based on the electronic structure of the components of the ternary blend and their nanoscale morphology, need to be met in order to achieve high power conversion efficiency in ternary BHJs. The properties of a model ternary system comprising two donor polymers, poly(3-hexylthiophene) (P3HT) and a furan-containing, diketopyrrolopyrrole-thiophene low-bandgap polymer (PDPP2FT), with a fullerene acceptor, PC₆₁BM, were examined. The relative miscibility of PC₆₁BM with P3HT and PDPP2FT was examined using diffusion with dynamic secondary ion mass spectrometry (dynamic SIMS) measurements. Grazing incidence small and wide angle X-ray scattering analysis (GISAXS and GIWAXS) were used to study the morphology of the ternary blends. These measurements, along with optoelectronic characterization of ternary blend solar cells, indicate that the miscibility of the fullerene acceptor and donor polymers is a critical factor in the performance in a ternary cell. A guideline that the miscibility of the fullerene in the two polymers should be matched is proposed and further substantiated by examination of known well-performing ternary blends. The ternary blending of semiconducting components can improve the power conversion efficiency of bulk heterojunction organic photovoltaics. The blending of P3HT and PDPP2FT with PC₆₁BM leads to good absorptive coverage of the incident solar spectrum and cascading transport energy levels. The performance of this ternary blend reveals the impact of the miscibility of PC₆₁BM in each polymer as a function of composition, highlighting an important factor for optimization of ternary BHJs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 237–246     

Platinum(II)-bis(aryleneethynylene) complexes for solution-processible molecular bulk heterojunction solar cells

Four new solution-processible small-molecular platinum(II)-bis(aryleneethynylene) complexes consisting of benzothiadiazole as the electron acceptor and triphenylamine and/or thiophene as the electron donor were conveniently synthesized and characterized by physicochemical and computational methods, and utilized as the electron-donor materials in the fabrication of solution-processed bulk heterojunction (BHJ) solar cells. The effect of different electron-donor groups in these small molecules on the optoelectronic and photovoltaic properties was also examined. The optical and time-dependent density functional theory studies showed that the incorporation of stronger electron-donor groups significantly enhanced the solar-absorption abilities of the complexes. These molecular complexes can serve as good electron donors for fabricating BHJ devices by blending them with the [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(70)BM) as the electron acceptor. The best power conversion efficiency of 2.37% was achieved with the open-circuit voltage of 0.83 V, short-circuit current density of 7.10 mA cm(-2) and fill factor of 0.40 under illumination of an AM 1.5 solar-cell simulator. The spin-coated thin films showed p-channel field-effect charge transport with hole mobilities of up to 2.4×10(-4) cm(2) V(-1) s(-1) for these molecules. The present work illuminates the potential of well-defined organometallic complexes in developing light-harvesting small molecules for efficient power generation in organic photovoltaics implementation.     

Triplet exciton generation in bulk-heterojunction solar cells based on endohedral fullerenes

Organic bulk-heterojunctions (BHJ) and solar cells containing the trimetallic nitride endohedral fullerene 1-[3-(2-ethyl)hexoxy carbonyl]propyl-1-phenyl-Lu(3)N@C(80) (Lu(3)N@C(80)-PCBEH) show an open circuit voltage (V(OC)) 0.3 V higher than similar devices with [6,6]-phenyl-C[61]-butyric acid methyl ester (PC(61)BM). To fully exploit the potential of this acceptor molecule with respect to the power conversion efficiency (PCE) of solar cells, the short circuit current (J(SC)) should be improved to become competitive with the state of the art solar cells. Here, we address factors influencing the J(SC) in blends containing the high voltage absorber Lu(3)N@C(80)-PCBEH in view of both photogeneration but also transport and extraction of charge carriers. We apply optical, charge carrier extraction, morphology, and spin-sensitive techniques. In blends containing Lu(3)N@C(80)-PCBEH, we found 2 times weaker photoluminescence quenching, remainders of interchain excitons, and, most remarkably, triplet excitons formed on the polymer chain, which were absent in the reference P3HT:PC(61)BM blends. We show that electron back transfer to the triplet state along with the lower exciton dissociation yield due to intramolecular charge transfer in Lu(3)N@C(80)-PCBEH are responsible for the reduced photocurrent.     

Phase diagram of P3HT:PC70BM thin films based on variable-temperature spectroscopic ellipsometry

In this article, we present the research on the influence of the composition of thin films of a blend of poly (3-hexylthiophene −2,5-diyl) - P3HT with fullerene derivatives [6,6]-phenyl-C71-butyric acid methyl ester – PC70BM and [6,6]-phenyl-C61-butyric acid methyl ester – PC60BM on their thermal transitions. The influence of molar mass (Mw) of P3HT (Mw = 65.2; 54.2 and 34.1 kDa) and PCBM (PC60BM – Mw = 911 g/mol and PC70BM – Mw = 1031 g/mol) is examined in details. The article presents significantly expanded research compared to our previous work on thermal transitions in thin films of blend P3HT (Mw = 65.2 kDa) with PC60BM. For this reason, we also compare current results with previous ones. Here, we present for the first time a phase diagram of thin films of the P3HT(Mw = 65.2 kDa):PC70BM blend using variable-temperature ellipsometry. Our research reveals the presence of characteristic temperatures of pure phases in thin films of P3HT: PCBM blends. It turns out that the cold crystallization temperature of the P3HT phase in P3HT(Mw = 65.2 kDa):PC70BM blend films is lower than corresponding temperature in P3HT(Mw = 65.2 kDa):PC60BM blend films. At the same time, the cold crystallization temperature of the PC70BM phase behaves inversely. We demonstrate also that variable-temperature spectroscopic ellipsometry is a very sensitive technique for studying thermal transitions in these thin films. In addition, we show that the entire phase diagram can be determined based on the raw ellipsometric data analysis, e.g. using a delta angle at wavelength λ = 280 nm.     

Large open-circuit voltage polymer solar cells by poly(3-hexylthiophene) with multi-adducts fullerenes

Polymer solar cells (PSCs) made by poly(3-hexylthiophene) (P3HT) with multi-adducts fullerenes, [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), PC61BM-bisadduct (bisPC61BM) and PC61BM-trisadduct (trisPC61BM), were reported. Electrochemistry studies indicated that PC61BM, bisPC61BM and trisPC61BM had step-up distributional lowest unoccupied molecular orbital (LUMO) energy. PSCs made by P3HT with above PC61BMs show a trend of enlarged open-circuit voltages, which is in good agreement with the energy difference between the LUMO of PC61BMs and the HOMO of P3HT. On the contrary, reduced short-circuit currents (Jsc) were observed. The investigation of photo responsibility, dynamics analysis based on photo-induced absorption of composite films, P3HT:PC61BMs and n-channel thin film field-effect transistors of PC61BMs suggested that the short polaron lifetimes and low carrier mobilities were response for reduced Jsc. All these results demonstrated that it was important to develop an electron acceptor which has both high carrier mobility, and good compatibility with the electron donor conjugated polymer for approaching high performance PSCs.     

Structural tuning of low band gap intermolecular push/pull side-chain polymers for organic photovoltaic applications

A series of novel low band gap donor-acceptor (D-A) type organic co-polymers (BT-F-TPA,BT-CZ-TPA and BT-SI-TPA) consisting of electron-deficient acceptor blocks both in main chains (M1) and at the pendant (M2) were polymerized with different electron rich donor (M3-M5) blocks,i.e.,9,9-dihexyl-9H-fluorene,N-alkyl-2,7-carbazole,and 2,6-dithinosilole,respectively,via Suzuki method.These polymers exhibited relatively low band gaps (1.65-1.88 eV) and broad absorption ranges (680-740 nm).Bulk heterojunction (BHJ) solar cells incorporating these polymers as electron donors,blended with [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 were fabricated and tested under 100 mW/cm2 of AM 1.5 with white-light illumination.The photovoltaic device containing donor BT-SI-TPA and acceptor PC71BM in 1:2 weight ratio showed the best power conversion efficiency (PCE) value of 1.88％,with open circuit voltage (Voc) =0.75 V,short circuit current density (Jsc) =7.60 mA/cm2,and fill factor (FF) =33.0％.     

Hydrogen Bonding as a Supramolecular Tool for Robust OFET Devices

In the present study, we demonstrated the effect of hydrogen bonding in the semiconducting behaviour of a small molecule used in organic field-effect transistors (OFETs). For this study, the highly soluble dumbbell-shaped molecule, Boc-TATDPP based on a Boc-protected thiophene-diketopyrrolopyrrole (DPP) and triazatruxene (TAT) moieties was used. The two Boc groups of the molecule were removed by annealing at 200 °C, which created a strong hydrogen-bonded network of NH-TATDPP supported by additional π–π stacking. These were characterised by thermogravimetric analysis (TGA), UV/Vis and IR spectroscopy, XRD and high-resolution (HR)-TEM measurements. FETs were fabricated with the semiconducting channel made of Boc-TATDPP and NH-TATDPP separately. It is worth mentioning that the Boc-TATDPP film can be cast from solution and then annealed to get the other systems with NH-TATDPP. More importantly, NH-TATDPP showed significantly higher hole mobilities compared to Boc-TATDPP. Interestingly, the high hole mobility in the case of NH-TATDPP was unaffected upon blending with [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM). Thus, this robust hydrogen-bonded supramolecular network is likely to be useful in designing efficient and stable organic optoelectronic devices.     

Charge trapping and storage by composite P3HT/PC60BM nanoparticles investigated by fluorescence-voltage/single particle spectroscopy

Fluorescence-voltage/single particle spectroscopy (F-V/SPS) was employed to study exciton-hole polaron interactions and interfacial charge transfer processes for pure poly(3-hexylthiophene) (P3HT) nanoparticles (NPs) and composite P3HT/PC(60)BM NPs in functioning hole-injection devices. F-V/SPS data collected on a particle-by-particle basis reveal an apparent bistability in the fluorescence-voltage modulation curves for composite NPs of P3HT and [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(60)BM) that is absent for pure P3HT NPs. A pronounced deep trapping of free electrons photogenerated from the composite P3HT/PC(60)BM NPs at the NP/dielectric interface and hole trapping by fullerene anions in composite P3HT/PC(60)BM NPs under photoexcitation lies at the basis of this finding. The deep electron trapping effect reported here for composite conjugated polymer/fullerene NPs presents an opportunity for future application of these NPs in nanoscale memory and imaging devices.     

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.     

The phase behavior of a polymer‐fullerene bulk heterojunction system that contains bimolecular crystals

Polymer:fullerene blends have been widely studied as an inexpensive alternative to traditional silicon solar cells. Some polymer:fullerene blends, such as blends of poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (pBTTT) with phenyl‐c71‐butyric acid methyl ester (PC₇₁BM), form bimolecular crystals due to fullerene intercalation between the polymer side chains. Here we present the determination of the eutectic pBTTT:PC₇₁BM phase diagram using differential scanning calorimetry (DSC) and two‐dimensional grazing incidence X‐ray scattering (2D GIXS) with in‐situ thermal annealing. The phase diagram explains why the most efficient pBTTT:PC₇₁BM solar cells have 75–80 wt % PC₇₁BM since these blends lie in the center of the only room‐temperature phase region containing both electron‐conducting (PC₇₁BM) and hole‐conducting (bimolecular crystal) phases. We show that intercalation can be suppressed in 50:50 pBTTT:PC₇₁BM blends by using rapid thermal annealing to heat the blends above the eutectic temperature, which forces PC₇₁BM out of the bimolecular crystal, followed by quick cooling to kinetically trap the pure PC₇₁BM phase. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Novel conjugated copolymers based on dithiafulvalene moiety for bulk heterojunction solar cells

New conjugated copolymers, P1‐P3 , based on dithiafulvalene‐fused entity and different conjugated segments have been synthesized. Incorporation of electron‐deficient conjugated segments into the conjugated copolymers results in red shifting the absorption band and lowering the hole mobility. Bulk heterojunction solar cells using on these polymers as the donor and [6,6]‐phenyl‐C61 ‐butyric acid methyl ester (PC₆₁BM) as the acceptor were fabricated by solution process. The cells based on the blend of P1‐P3 /PC₆₁BM (1:1, w/w) have power conversion efficiencies (PCEs) ranging from 0.53 to 0.93%. Among these, the cell of P1 /PC₆₁BM exhibited the highest open‐circuit voltage at 0.85 V, and the cell of P3/PC₆₁BM exhibited the best PCE at 0.93% with the short‐circuit current (J_SC) of 4.88 mA/cm². © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of thieno[3,2‐b]thiophene‐isoindigo‐based copolymers as electron donor and hole transport materials for bulk‐heterojunction polymer solar cells

A novel class of thieno[3,2‐b]thiophene (TT) and isoindigo based copolymers were synthesized and evaluated as electron donor and hole transport materials in bulk‐heterojunction polymer solar cells (BHJ PSCs). These π‐conjugated donor‐acceptor polymers were derived from fused TT and isoindigo structures bridged by thiophene units. The band‐gaps and the highest occupied molecular orbital (HOMO) levels of the polymers were tuned using different conjugating lengths of thiophene units on the main chains, providing band‐gaps from 1.55 to 1.91 eV and HOMO levels from ?5.34 to ?5.71 eV, respectively. The corresponding lowest unoccupied molecular orbital (LUMO) levels were appropriately adjusted with the isoindigo units. Conventional BHJ PSCs (ITO/PEDOT:PSS/active layer/interlayer/Al) with an active layer composed of the polymer and PC₇₁BM were fabricated for evaluation. Power conversion efficiency from a low of 1.25% to a high of 4.69% were achieved with the best performing device provided by the D?π?A polymer with a relatively board absorption spectrum, high absorption coefficient, and more uniform blend morphology. These results demonstrate the potential of this class of thieno[3,2‐b]thiophene‐isoindigo‐based polymers as efficient electron donor and hole transport polymers for BHJ PSCs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

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     

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     

An acrylated fullerene derivative for efficient and thermally stable polymer solar cells

The continuous microstructure evolution occurring in active layers of polymer-fullerene solar cells is one of the main causes for their device instability. With aim to tackle it, this work developed a new polymerizable fullerene acceptor, [6,6]-phenyl-C₆₁-butyl acrylate (PC₆₁BA). It was found that PC₆₁BA has similar light-absorption properties and HOMO and LUMO energy levels as [6,6]-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), and can be converted into insoluble oligomers upon heating at 150 °C. Polymer-fullerene solar cells using poly(3-hexylthiophene) (P3HT) as donor and PC₆₁BA as acceptor exhibited an optimized efficiency of 3.54%, the performance comparable to P3HT/PC₆₁BM cells (optimized efficiency: 3.70%). But, the former possess much better thermal stability than the latter owing to aggregation suppression by the polymerized PC₆₁BA. These results indicate that PC₆₁BA, unlike most previous reported, is a unique polymerizable fullerene derivative that can be used alone as acceptor to achieve both efficient and thermally stable polymer solar cells.     

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