Thienopyrazine or dithiadiazatrindene containing low band gap conjugated polymers for polymer solar cells

Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28-2.07 eV and the highest occupied molecular orbital （HOMO） energy levels are in the range of-4.99 eV to -5.28 eV. Bulk heterojunction polymer solar cells （PSCs） of the polymers were fabricated with phenyl-C61-butyric acid methyl ester （PC61BM） as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.     

A near-infrared porphyrin-based electron acceptor for non-fullerene organic solar cells

A star-shaped electron acceptor with porphyrin as core and rhodanine-benzothiadiazole as end groups linked with ethynyl units was developed for non-fullerene solar cells, in which a PCE of 1.9% with broad photo response was achieved when combining with a diketopyrrolopyrrole-polymer as electron donor.     

The recent progress of wide bandgap donor polymers towards non-fullerene organic solar cells

The recent progress of wide bandgap (WBG) donor polymers for non-fullerene polymer solar cells (NF-PSCs) were reviewed in detail, which was classified by D-type and D-A type molecular backbones to discuss the related structure-property correlations and put forward an outlook for future innovations.     

聚合物太阳能电池给体材料研究进展

随着能源和环境问题日益严重,人们日益关注于太阳能的开发和应用。同时,无机太阳能电池因其自身原因而受到限制,聚合物太阳能电池受到更多的关注。在聚合物基的太阳能电池中,给体材料制约着电池效率的提高,其中材料的带隙和能级是影响其性能的主要因素。而通过研究和选取具有合适带隙和能级的给体材料可以有效地调节电池器件的效率。本文介绍了太阳能电池给体材料的设计原则与主要影响因素,并叙述了近年来该领域内的研究进展和以及发展前景。     

Donor-acceptor (D-A) terpolymers based on alkyl-DPP and t-BocDPP moieties for polymer solar cells

A series of low band gap terpolymers based on 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b¢] dithiophene (BDTT) and diketopyrrolopyrrole (DPP) with varied solubilizing groups (i.e., tert-butoxycarbonyl, t-Boc and 2-octyldodecyl) are developed as electron donors for bulk heterojunction (BHJ) polymer solar cells (PSCs). The results reveal that the one with 50% t-Boc concentration (P3) performs better than the other terpolymers used in this study in conventional PSC devices with a power conversion efficiency of 2.92%.     

Synthesis and properties of novel low band-gap polymers bearing squaraine units

<正>Novel main-chain-conjugated poly(carbazol-alt-squaraine) and poly(dipyridyl-alt-squaraine) were successfully synthesized through direct polycondensation of 9-(2-ethylhexyl)carbazole-bridged or dipyridyl-bridged bispyrrole and squaric acid.The structures and properties of the polymers were characterized using ~1H NMR,FT-IR,UV-vis and cyclic voltammetry.Both polymers exhibit excellent solubility in common organic solvents and good thermal stability.Their UV-vis absorption spectra indicated the polymers have broad and strong spectral responses from 200 nm to 900 nm,which reveals a low optical band gap around 1.38 eV, suggesting that they may be promising candidates for organic solar cells.     

Donor–acceptor semiconducting polymers for organic solar cells

This review describes the synthesis and photovoltaic performance of donor–acceptor (D–A) semiconducting polymers that have been reported during the last decade. 9,9‐Dialkyl‐2,7‐ fluorene, 2,7‐carbazole, cyclopenta[2,1‐b:3,4‐b′]dithiophene, dithieno[3,2‐b:2′,3′‐d]silole, dithieno[3,2‐b:2′,3′‐d]pyrrole, benzo[1,2‐b:4,5‐b′]dithiophene, benzo[1,2 b:4,5 b′]difuran building blocks, and their D–A copolymers are described in this review. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Twisted olefinic building blocks for low bandgap polymers in solar cells and ambipolar field‐effect transistors

A series of polymers based on 8,8′‐biindeno[2,1‐b]thiophenylidene for use in photovoltaic devices and field‐effect transistors are reported. These structurally twisted olefins are effective building blocks for preparation of low bandgap polymers with optical bandgaps of 1.2–1.5 eV. Device performance, such as V_oc and J_sc, in solar cell devices could be successfully modulated by incorporation of a variety of comonomers. Ambipolar properties in field‐effect transistors using Au electrodes were also studied, with PtBTPDPP exhibiting balanced charge transport properties with hole and electron mobilities of 0.09 and 0.12 cm²·V^?1·s^?1, respectively. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 889–899     

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％.     

Diketopyrrolopyrrole-based conjugated polymers as additives to optimize morphology for polymer solar cells

Novel random copolymers for optimizing the morphology of the active layer for high performance organic photovoltaic devices have been demonstrated. Three ternary random copolymers PTBDTDPPSi CN(3/7), PTBDTDPPSi CN(5/5), PTBDTDPPSi CN(7/3) were prepared by polymerization of electron-donating thienyl-substituted benzodithiophene(TBDT) with 2,5-bis[8-(1,1,3,3,5,5,5-heptamethyltrisiloxane-3-yl)octly]-pyrrolo[3,4-c]pyrrole-1,4-dione(DPPSi) and 2,5-dio[5-(5-cyano-5,5-dimethyl-pentyl)]-3,6-dithiophen-2-yl-pyrrolo[3,4-c]pyrrole-1,4-dione(DPPCN) of different ratios. The DPPCN block can well-tune the light absorption and molecular packing, while the DPPSi block is in favor of enhancing the charge mobility. And the formation of organic Si―O―Si networks is beneficial to stabilize the morphology of the active layer. These new copolymers have narrow bandgaps and broaden visible light absorption from 500 nm to 1000 nm. Careful balance of the contents of the trimethoxysilyl group and the cyano group can well-tune the surface energy and morphology of the copolymers. Incorporation of these novel copolymers as additives into the blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C60-butyric acid methyl ester(PC_(61)BM) is found to effectively broaden the light absorption, improve the compatibility and morphology of the active layer. As a result, some devices with certain ratios of these copolymers as additives achieve the enhanced efficiency compared with the device based on pristine P3HT:PC_(61)BM.     

Effect of spacer insertion in a commonly used dithienosilole/benzothiadiazole-based low band gap copolymer for polymer solar cells

Dithienosilole-benzothiadiazole based low bandgap copolymers remain promising material for organic photovoltaics. A new copolymer, poly[(4,4′-dioctyldithieno[3,2-b:2′,3′-d]silole-2,6-diyl)-alt-{4,7-bis[2-(3-hexyl)thienyl]-2,1,3-benzothiadiazole-5,5′-diyl}] (PDTSDTBT) was designed by introducing a thiophene spacer bearing a hexyl chain at β-position in the main backbone and compared to its analog poly[(4,4′-dioctyldithieno[3,2-b:2′,3′-d]silole-2,6-diyl)-alt-(2,1,3-benzothiadiazole-4,7-diyl)] (PDTSBT). In PDTSDTBT, linear alkyl chains on silicon were chosen due to facile and cheap access and the inserted 3-hexylthiophene units were chosen to increase solubility and molar mass, a weak point with PDTSBT. The two parameters are important to optimize photovoltaic performances. To compare characteristics, PDTSDTBT of molar masses greater than, and equal to a sample of PDTSBT, were prepared. Pd-catalyzed Stille cross-coupling reactions in a micro-wave reactor to promote an efficient copolymerisations. A strong absorption ranging from 370 nm to 800 nm and a good thermal stability were observed. PDTSDTBT showed better solubility and higher degree of crystallinity. Facile synthesis of high molar masses meant that higher efficiencies, around 40% greater, could be obtained with PDTSDTBT. The polymer was demonstrated to be susceptible to improvement through the use of device-additives. For example, under initial optimisations using PDTSDTBT:PC₆₀BM blend at a ratio of 1:1 delivered a power conversion efficiency of 2.13% with J_SC = 7.73 (mA/cm²), under AM 1.5 (100 mW/cm²) illumination.     

Synthesis and characterization of new low bandgap polyfluorene copolymers for bulk heterojunction solar cells

Two new low bandgap alternating polyfluorene copolymers based on dioctylfluorene and donor‐acceptor‐donor monomers have been synthesized via a Suzuki polymerization reaction. The resulting copolymers have low optical bandgaps at 1.99–1.98 eV. The bulk heterojunction polymer solar cells were fabricated with the conjugated polymers as the electron donor and 6.6‐phenyl C₆₁‐butyric acid methyl ester as the electron acceptor. The power conversion efficiencies of the solar cells based on copolymers 1 and 2 are 0.37 and 0.42%, respectively, under the illumination of AM 1.5, 100 mW/cm². The results indicate that the two copolymers are promising conjugated polymers for polymer solar cells. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5336–5343, 2009     

High-performance fullerene-free polymer solar cells with solution-processed conjugated polymers as anode interfacial layer

A series of conjugated polymers based on PFS derivatives with π-conjugated 5-(9H-fluoren-2-yl)-2,2′-bithiophene(fluorene-alt-bithiophene) backbones, namely PFS-3C, PFS-4C and PFS-6C, were synthesized for their use as the anode interfacial layers(AILs) in the efficient fullerene-free polymer solar cells(PSCs). Alkyl sulfonate pendants with different lengths of alkyl side chains were introduced in the three polymers in order to investigate the effect of the alkyl chain length on the anode modification. The obtained three polymers exhibited similar absorption bands and energy levels, indicating that changing the length of the alkyl side chains did not affect the optoelectronic properties of the conjugated polymers. Based on the PBDB-T:ITIC active layer, we fabricated the fullerene-free PSCs using the three polymers as the AILs. The superior performance of the fullerene-free PSC device was achieved when PFS-4C was used as the AIL, showing a power conversion efficiency(PCE) of 10.54%. The high performance of the PFS-4C-modified device could be ascribed to the high transmittance, suitable work-function(WF) and smooth surface of PFS-4C. To the best of our knowledge, the PCE obtained in the PFS-4C-modified device is among the highest PCE values in the fullerene-free PSCs at present. These results demonstrate that the PFS derivatives are promising candidates in serving as the AIL materials for high-performance fullerene-free PSCs.     

Rylene diimide and dithienocyanovinylene copolymers for polymer solar cells

Two polymers containing(E)-2,3-bis(thiophen-2-yl)acrylonitrile(CNTVT) as a donor unit, perylene diimide(PDI) or naphthalene diimide(NDI) as an acceptor unit, are synthesized by the Stille coupling copolymerization, and used as the electron acceptors in the solution-processed organic solar cells(OSCs). Both polymers exhibit broad absorption in the region of 300–850 nm. The LUMO energy levels of the resulted polymers are ca. –3.93 eV and the HOMO energy levels are –5.97 and –5.83 eV. In the binary blend OSCs with PTB7-Th as a donor, PDI polymer yields the power conversion efficiency(PCE) of up to 1.74%, while NDI polymer yields PCE of up to 3.80%.     

A solution-processable electron acceptor based on diketopyrrolopyrrole and naphthalenediimide motifs for organic solar cells

A novel, solution-processable small molecular electron acceptor (HP1) based on diketopyrrolopyrrole and naphthalenediimide fragments was designed and synthesized via a Stille coupling reaction, characterized by spectroscopic means, and exhibited excellent solubility and thermal stability. HP1 exerted strong and very broad absorption tailing into the near infra-red region, with appropriate energy levels matching with the archetypal electron donor, poly(3-hexylthiophene) (P3HT), and afforded 1.02% power conversion efficiency with a high open-circuit voltage (1.05 V) when tested in solution-processable bulk-heterojunction devices.     

A non-fullerene acceptor enables efficient P3HT-based organic solar cells with small voltage loss and thickness insensitivity

The large D core of DFPCBR results in efficient P3HT-based OSCs with a high V_OC and thickness insensitivity.     

Diketopyrrolopyrrole‐based conjugated polymers and small molecules for organic ambipolar transistors and solar cells

The present highlight discusses major work in the synthesis of low bandgap diketopyrrolopyrrole ( DPP )‐based polymers with donor–acceptor–donor ( D–A–D ) approach and their application in organic electronics. It examines the past and recent significant advances which have led to development of low bandgap DPP ‐based materials with phenyl and thiophene as donors. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4241–4260     

Tuning the energy gap of conjugated polymer zwitterions for efficient interlayers and solar cells

Narrow band gap conjugated polymer zwitterions (CPZs) were synthesized by Suzuki polymerization and characterized to understand their electronic properties and utility as cathode modification layers in solar cells. The polymers were prepared from diketopyrrolopyrrole (DPP) and iso-indigo monomers containing sulfobetaine (SB) pendant groups, benefiting from an ion-rich aqueous phase in the polymerizations. UV–vis absorption spectroscopy revealed the optical energy gap value for the CPZs, ranging from 1.7 to 1.2 eV. Ultraviolet photoelectron spectroscopy of the CPZs as thin layers on Ag metal showed that the pendent zwitterions impart an interfacial dipole (Δ) to the metal and a work function reduction of ∼0.9 eV. OPVs fabricated using a conventional bulk heterojunction (BHJ) device architecture of ITO/PEDOT:PSS/(PTB7:PC₇₁BM)/CPZ/Ag led to dramatic improvements in power conversion efficiency (PCE) values relative to devices having bare Ag cathodes (PCE < 2% for bare Ag vs. 6.7–7.7% for CPZ/Ag). The benzothiadiazole (BT)/DPP polymer denoted as PT₂BTDPPSB gave an optimal PCE of 7.7% in a conventional BHJ OPV device architecture fabricated on a Ag cathode. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 327–336     

All-polymer solar cells utilizing low band gap polymers as donor and acceptor

All-polymer solar cells based on blends of the low band gap polymers 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]} (PTB7) and poly{[N,N-9-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,59-(2,29-bithiophene)} (P(NDI2OD-T2)) are demonstrated. The use of the donor polymer PTB7 instead of poly(3-hexylthiophene) results in a higher open-circuit voltage and an overall spectral response better matched to the solar spectrum. A power conversion efficiency of 1.1% is reported with a peak external quantum efficiency of 18% at a wavelength of 680 nm. The microstructure of PTB7:P(NDI2OD-T2) blends is also investigated using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS), near-edge X-ray fine-structure (NEXAFS) spectroscopy, atomic force microscopy (AFM), and scanning transmission X-ray microscopy (STXM). GIWAXS measurements show that PTB7:P(NDI2OD-T2) blends contain P(NDI2OD-T2) crystallites with a (100) thickness of 9.5 nm dispersed in an amorphous PTB7 matrix. STXM measurements indicate a lack of mesoscale phase separation, with AFM and NEXAFS measurements revealing a P(NDI2OD-T2)-rich top surface with fibrillar morphology. These results indicate that the pairing of low band gap polymers as both donor and acceptor polymers in all-polymer solar cells may be an effective strategy for realizing high-efficiency all-polymer solar cells. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013