Novel polymer acceptors achieving 10.18% efficiency for all-polymer solar cells

Polymer acceptors based on extended fused ring p skeleton has been proven to be promising candidates for all-polymer solar cells(all-PSCs), due to their remarkable improved light absorption than the traditional imide-based polymer acceptors. To expand structural diversity of the polymer acceptors, herein,two polymer acceptors PSF-IDIC and PSi-IDIC with extended fused ring p skeleton are developed by copolymerization of 2,20-((2 Z,20 Z)-((4,4,9,9-tetrahexadecyl-4,9-dihydro-s-indaceno [1,2-b:5,6-b']dithio phene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1 H-indene-2,1-diylidene))dimalononitrile(IDIC-C16) block with sulfur(S) and fluorine(F) functionalized benzodithiophene(BDT) unit and silicon(Si) atom functionalized BDT unit, respectively. Both polymer acceptors exhibit strong light absorption.The PSF-IDIC exhibits similar energy levels and slightly higher absorption coefficient relative to the PSi-IDIC. After blended with the donor polymer PM6, the functional atoms on the polymer acceptors show quite different effect on the device performance. Both of the acceptors deliver a notably high open circuit voltage(V_OC) of the devices, but PSi-IDIC achieves higher V OCthan PSF-IDIC. All-PSC based on PM6:PSi-IDIC attains a power conversion efficiency(PCE) of 8.29%, while PM6:PSF-IDIC-based device achieves a much higher PCE of 10.18%, which is one of the highest values for the all-PSCs reported so far. The superior device performance of PM6:PSF-IDIC is attributed to its higher exciton dissociation and charge transport, decreased charge recombination, and optimized morphology than PM6:PSi-IDIC counterpart. These results suggest that optimizing the functional atoms of the side chain provide an effective strategy to develop high performance polymer acceptors for all-PSCs.     

8.0% Efficient all-polymer solar cells based on novel starburst polymer acceptors

The polymer N2200, with its π-conjugated backbone composed of alternating naphthalene diimide(NDI) and bithiophene(DT)units, has been widely used as an acceptor for all-polymer solar cells(all-PSCs) owing to its high electron mobility and suitable ionization potential and electron affinity. Here, we developed two naphthalene diimide derivatives by modifying the molecular geometry of N2200 through the incorporation of a truxene unit as the core and NDI-DTas the branches. These starburst polymers exhibited absorption spectra and molecular orbital energy levels that were comparable to N2200. These copolymers were paired with the wide-bandgap polymer donor PTz BI-O to fabricate all-polymer solar cells(all-PSCs), which displayed impressive power conversion efficiencies up to 8.00%. The improved photovoltaic performances of all-PSCs based on these newly developed starburst acceptors can be ascribed to the combination of increased charge carrier mobilities, reduced bimolecular recombination, and formation of more favorable film morphology. These findings demonstrate that the construction of starburst polymer acceptors is a feasible strategy for the fabrication of high-performance all-PSCs.     

Reducing energy loss via tuning energy levels of polymer acceptors for efficient all-polymer solar cells

Science China Chemistry - The open-circuit voltage (Voc) of all-polymer solar cells (all-PSCs) is typically lower than 0.9 V even for the most efficient ones. Large energy loss is the main reason...     

Synthesis and application of poly(fluorene-alt-naphthalene diimide) as an n-type polymer for all-polymer solar cells

A new alternating copolymer of fluorene and naphthalene diimide, PF-NDI, was synthesized and characterized. The highest power conversion efficiency of all-polymer solar cells based on P3HT:PF-NDI reached 1.63% with a relatively high fill factor of 0.66 by using 1,8-diiodooctane as a solvent additive to optimize the mixing morphology.     

Printable and stable all-polymer solar cells based on non-conjugated polymer acceptors with excellent mechanical robustness

All-polymer solar cells(all-PSCs)trigger enormous commercial applications,and great progress has been made in recent years.However,from small-area devices to large-area modules,the poor adaption of the materials for printing methods and the large efficiency loss are still great challenges.Herein,three novel non-conjugated polymer acceptors(PTH-Y,PTClm-Yand PTClo-Y)are developed for all-PSCs.It can be found that non-conjugated polymer acceptors can effectively minimize the technique and efficiency gaps between small-area spin-coating and large-area blade-printing method,which can facilitate the preparation of large-area flexible device.By directly inheriting the spin-coating condition,the blade-coating processed device based on PTCloY achieves an impressive power conversion efficiency(PCE)of 12.42%,comparable to the spin-coating processed one(12.74%).Such a non-conjugated polymer system also can well tolerate large-scale preparation and flexible substrate.Notable PCE of 11.94%for large-area rigid device and 11.56%for large-area flexible device are obtained,which is the highest value for large-area flexible all-PSCs fabricated by blade-coating.In addition,the non-conjugated PTClo-Y-based devices show excellent thermal stability and mechanical robustness.These results demonstrate that the non-conjugated polymer acceptors are potential candidates for the fabrication of highly-efficient,large-area and robust flexible all-PSCs by printing methods.     

Eco-friendly solution processing of all-polymer solar cells: Recent advances and future perspective

All-polymer solar cells (all-PSCs) exhibit great potentials in commercial applications. All-PSCs have observed steady performance gains with power conversion efficiency now reaching over 17% in the open literature. However, the current processing of all-PSCs relies predominantly on toxic, chlorinated solvents in moisture-free environments, representing a significant barrier for their commercialization due to the added costs to handle and dispose of such solvents. There is thus an urgent need for safe, environmentally benign, and sustainable ink-based processing methods to produce all-PSC devices reliably and reproducibly in ambient air. In this perspective, fundamental insights on the interplay between all-polymer blend morphologies and eco-friendly solvents are provided. Also, we discuss the recent successes of the green processing methods to manipulate the photoactive morphologies for high-efficiency all-PSCs. In the end, we provide an outlook on future challenges and opportunities of eco-friendly solvents processed all-PSCs for large-scale manufacturing.     

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%.     

All-polymer solar cells with perylenediimide polymer acceptors

Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor polymers, poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2,6-diyl](PTB7-Th) and poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3′′′-di(2-dodecyltetradecyl)-2,2′;5′,2″;5″,2′′′-quaterthiophen-5,5′′′-diyl)](Pff BT4T-2DT), with suitably complementary absorption spectra and energy levels were applied and examined. Among all different donor-acceptor pairs studied here, the combination of PTB7-Th:poly[N,N′-bis(1-hexylheptyl)-3,4,9,10-perylenediimide-1,6/1,7-diyl-alt-2,5-thiophene](PDI-Th) exhibited the best power conversion efficiency(PCE) of 5.13%, with open-circuit voltage(V_(oc)) = 0.79 V, short-circuit current density(J_(sc)) = 12.35 mA·cm~(-2) and fill-factor(FF) = 0.52. The polymer of PDI-Th acceptor used here had a regio-irregular backbone, conveniently prepared from a mixture of 1,6- and 1,7-dibromo-PDI. It is also noteworthy that neither additive nor posttreatment is required for obtaining such a cell performance.     

Polymerized A-DA'D-A type small-molecule acceptors for high performance all-polymer solar cells: progress and perspective

A-DA’D-A type polymerized small-molecule acceptors(PSMAs) have very recently received wide attention because they possess advantages such as synthetic flexibility, narrowed bandgap, low energy loss, and impressive mechanical properties. With efforts on design and synthesis of PSMAs and polymer donors, significant progress has been made on all polymer solar cells(allPSCs) with power conversion efficiencies exceeding 18%. In this review, we focus on structure-property-performance relationships of ...     

Fullerene derivative acceptors for high performance polymer solar cells

Polymer solar cells (PSCs) are composed of a blend film of a conjugated polymer donor and a soluble fullerene derivative acceptor sandwiched between a PEDOT?:?PSS coated ITO positive electrode and a low workfunction metal negative electrode. The conjugated polymer donor and the fullerene derivative acceptor are the key photovoltaic materials for high performance PSCs. For the acceptors, although [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(60)BM) and its corresponding C(70) derivative PC(70)BM are dominantly used as the acceptors in PSC at present, several series of new fullerene derivatives with higher-lying LUMO energy level and better solubility were reported in recent years for further improving the power conversion efficiency of the PSCs. In this perspective paper, we reviewed the recent research progress on the new fullerene derivative acceptors, including various PC(60)BM-like C(60) derivatives, PC(60)BM bisadduct, PC(70)BM bisadduct, indene-C(60) bisadduct and indene-C(70) bisadduct, trimetallic nitride endohedral fullerenes and other C(60) derivatives with multi side chains. The synthesis and physicochemical properties of PC(60)BM and PC(70)BM were also introduced considering the importance of the two fullerene acceptors.     

Perylene and naphthalene diimide copolymers for all-polymer solar cells: Effect of perylene/naphthalene ratio

We report the synthesis of a series of copolymers, having 2,2′-bithiophene as electron-donating moiety, and perylene diimide (PDI) and/or naphthalene diimide (NDI) as electron-accepting moiety, and employed as non-fullerene acceptors in polymer solar cells (PSCs). All the copolymers show wide absorption varying from 300 to 850 nm in the visible and NIR spectrum. When changing the PDI/NDI ratio in the polymer backbone, The LUMO energy levels vary in the range of −3.90 to −3.80 eV and the HOMO energy levels vary in the range of −6.10 to −5.85 eV. Among PSCs based on PTB7-Th donor and these polymer acceptors, the devices based on PTB7-Th/NDI100 yield the best power conversion efficiency (PCE) of 4.67%, while the PTB7-Th/PDI100-based devices yield a PCE of 1.03%. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 682–689     

A chlorinated polymer promoted analogue co-donors for efficient ternary all-polymer solar cells

The efficient ternary all-polymer solar cells(PSCs) are designed and fabricated, using a polymer acceptor of NDP-V-C7 and analogue co-donors containing a chlorinated polymer PBCl T and classical PTB7-Th. PBCl T and PTB7-Th possess very similar chemical structure and matched energy levels to form the cascade of the co-donors. Meanwhile, benefiting from those analogous polymer structures, there is little influence of the morphology in blend film compared to their pristine polymer films. The binary PBCl T:NDP-V-C7 devices exhibit a high open-circuit voltage(V_(oc)) due to the deep HOMO level of PBCl T. The V_(oc)of all-PSCs could be finely manipulated by adjusting the content of PBCl T in blend film. The ternary all-PSCs have the more balanced charge mobility and prolonged carrier lifetime compared to the binary devices. The PBCl T also help improve the miscibility of ternary blend and suppress crystallization in films, bringing about favorable morphology with appropriate orientation and surface roughness in blend film. With the optimal processing, the champion ternary all-PSCs obtain a high PCE of 9.03%, which is about 10% enhancement compared to that of binary device. The results indicate that the ternary approach using analogue co-donors is a practical method to enhance the performance of all-PSCs.     

Recent advances in phenothiazine-based dyes for dye-sensitized solar cells

Dye-sensitized solar cells(DSSCs) have attracted significant attention as alternatives to conventional silicon-based solar cells owing to their low-cost production,facile fabrication,excellent stability and high power conversion efficiency(PCE).The dye molecule is one of the key components in DSSCs since it significant influence on the PCE,charge separation,light-harvesting,as well as the device stability.Among various dyes,easily tunable phenothiazine-based dyes hold a large proportion and achieve impressive photovoltaic performances.This class of dyes not only has superiorly non-planar butterfly structure but also possesses excellent electron donating ability and large π conjugated system.This review summarized recent developments in the phenothiazine dyes,including small molecule phenothiazine dyes,polymer phenothiazine dyes and phenothiazine dyes for co-sensitization,especially focused on the developments and design concepts of small molecule phenothiazine dyes,as well as the correlation between molecular structures and the photovoltaic performances.     

15.4% Efficiency all-polymer solar cells

We report all-polymer solar cells(All-PSCs) with record-high power conversion efficiency(PCE) through tuning the molecular weights of the polymer donor(PBDB-T) to form optimal active layer morphology. By combining the polymer donors with a newly reported polymer acceptor(PJ1), an unprecedented high PCE of 15.4% and fill factor over 75% were achieved for the AllPSCs with the medium molecular weight polymer donor(PBDB-T_(MW)), which is the highest value for All-PSCs reported so far.Detailed morphology investigation revealed that the proper phase separation in the PBDB-T_(MW):PJ1 blend should account for the superior device performance as PBDB-T_(MW) exhibits appropriate miscibility with the polymer acceptor PJ1. These results demonstrated that the device performance of All-PSCs could be fully comparable to that of small molecular acceptor-based PSCs. The formation of optimized morphology via precise control of molecular weights of polymer donors and acceptors is crucial to achieve this goal.     

Recent advances in high-performance semitransparent perovskite solar cells

Semitransparent perovskite photovoltaics have been developed to realize practical applications, such as windows in buildings/automobiles or the top cells of tandem devices. Among the functional layers constituting solar cell devices, fabricating efficient semitransparent light absorbers is one of the key issues for developing semitransparent devices. This short review describes the recent strategies for structuring semitransparent perovskite layers to achieve high performance in terms of both power conversion efficiency and transmittance.     

High-performance all-polymer solar cells enabled by a novel low bandgap non-fully conjugated polymer acceptor

The non-fully conjugated polymer as a new class of acceptor materials has shown some advantages over its small molecular counterpart when used in photoactive layers for all-polymer solar cells(all-PSCs), despite a low power conversion efficiency(PCE)caused by its narrow absorption spectra. Herein, a novel non-fully conjugated polymer acceptor PFY-2 TS with a low bandgap of~1.40 eV was developed, via polymerizing a large π-fused small molecule acceptor(SMA) building block(namely YBO) with a nonconjugated thioalkyl linkage. Compared with its precursor YBO, PFY-2 TS retains a similar low bandgap but a higher LUMO level.Moreover, compared with the structural analog of YBO-based fully conjugated polymer acceptor PFY-DTC, PFY-2 TS shows a similar absorption spectrum and electron mobility, but significantly different molecular crystallinity and aggregation properties,which results in optimal blend morphology with a polymer donor PBDB-T and physical processes of the device in all-PSCs. As a result, PFY-2 TS-based all-PSCs achieved a PCE of 12.31% with a small energy loss of 0.56 eV enabled by the reduced non-radiative energy loss(0.24 eV), which is better than that of 11.08% for the PFY-DTC-based ones. Our work clearly demonstrated that non-fully conjugated polymers as a new class of acceptor materials are very promising for the development of high-performance all-PSCs.     

New perylene diimide electron acceptors for organic electronics: Synthesis,optoelectronic properties and performance in perovskite solar cells

Two new non-fullerene acceptors based on perylene diimide with acetylenic bridges were designed and synthesized employing Stille and Sonogashira coupling reactions as the key steps. Their optical and electronic properties were explored by UV–VIS spectroscopy and cyclic voltammetry, and energies of frontier molecular orbitals were estimated. Their preliminary studies in perovskite solar cells as electron transport materials showed the best power conversion efficiency for photocells of 14.18% value.     

Cyclometalated Pt complex based random terpolymers as electron acceptors for all polymer solar cells

Various molar ratios of platinum complexes were introduced into the conjugated backbone of the well‐studied poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)](PNDIT2) acceptor polymer through random terpolymer approach. Terpolymers PNDIT2Ptx (x = 1, 2 and 5) exhibited slightly higher melting point (T_m), crystallization temperature, HOMO and LUMO energy levels than the control PNDIT2 copolymer due to the introduction of small amount of weaker electron‐withdrawing bulky rigid Pt complex instead of strong electron‐withdrawing flexible naphthalene diimide. When blended them with poly[[2,6′‐4,8‐di(5‐ethylhexylthienyl)benzo[1,2‐b;3,3‐b] dithiophene] [3‐fluoro‐2[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]] (PTB7‐Th) in all polymer solar cells, enhanced power conversion efficiency of 4.51% (3.74%) was obtained in terpolymer PNDIT2Pt1 based device compared to 3.88% (3.24%) of the control PNDIT2 at the same inverted (conventional) device conditions. The enhancement was probably ascribed to higher hole and electron transport ability and more efficient charge separation. To the best of our knowledge, this is the first example of random terpolymer acceptors based on heavy metal complexes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 105–115     

Recent development of perylene diimide-based small molecular non-fullerene acceptors in organic solar cells

This review summarizes the recent progress of perylene diimide (PDI) derivatives used as the acceptor materials in non-fullerene organic solar cells. The resulting structure-property correlations and design strategies of this type of acceptors are discussed and commented, which will help to constructing high-performance PDI-based acceptor materials in the future. The problems at present and the effort direction are also pointed out in this review.