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     

Active Layer Morphology Engineering of All-polymer Solar Cells by Systematically Tuning Molecular Weights of Polymer Donors/Acceptors

In all-polymer solar cells (APSCs),number-average molecular weights (Mns) of polymer donors and polymer acceptors play an important role in active layer morphology and photovoltaic performance.In this work,based on a series of APSCs with power conversion efficiency of approaching 10％,we study the effect of Mns of both polymer donor and polymer acceptor on active layer morphology and photovoltaic performance of APSCs.We select poly[4-(5-(4,8-bis(5-((2-butyloctyl)thio)thiophen-2-yl)-6-methylbenzo[1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-5,6-difluoro-2-(2-hexyldecyl)-7-(5-methylthiophen-2-yl)-2H-benzo[d][1,2,3]triazole](CD1) as the polymer donor and poly[4-(5-(5,10-bis(2-dodecylhexadecyl)-4,4,g,9-tetrafluuoro-7-methyl-4,5,9,10-tetrahydro3a,5,8,10-tetraaza-4,g-diborapyren-2-yl)thiophen-2-yl)-7-(5-methylthiophen-2-yl)benzo[c][1,2,5]thiadiazole](PBN-14) as the polymer acceptor.The Mns of polymer donor CD1 are 14.0,35.5 and 56.1 kg/mol,respectively,and the Mns of polymer acceptor PBN-14 are 32.7,72.4 and 103.4 kg/mol,respectively.To get the desired biscontinueous fibrous network morphololgy of the polymer donor/polymer acceptor blends,at least one polymer should have high or medium Mn.Moreover,when the Mn of polymer acceptor is high,the active layer morphology and APSC device performance are insensitive to the Mn of polymer donor.The optimal APSC device performance is obtained when the Mn of both the polymer donor and the polymer acceptor are medium.These results provide a comprehensive and deep understanding on the interplay and the effect of Mn of polymer donors and polymer acceptors in high-performance APSCs.     

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%.     

Recent developments of di-amide/imide-containing small molecular non-fullerene acceptors for organic solar cells

Non-fullerene organic solar cells have received increasing attentions in these years, and great progresses have been made since 2013. Among them, aromatic di-amide/imide-containing frameworks have shown promising applications. The outstanding properties of them are highly associated with their unique electronic and structural features, such as strong electron-withdrawing nature, broad absorption in UV-visible region, tunable HOMO/LUMO energy levels, easy modifications, and excellent chemical, thermal and photochemical stabilities. In this review, we give an overview of recent developments of aromatic diamide/imide-containing small molecules used as electron acceptors for organic solar cells.     

Ethynyl-linked perylene bisimide based electron acceptors for non-fullerene organic solar cells

Star-shaped electron acceptors based on perylene bisimide as end groups and spiro-aromatic core linked with ethynyl units were developed for nonfullerene solar cells. Ethynyl linkers are able to improve the planarity of conjugated backbone, resulting in enhanced electron mobility and power conversion efficiency in solar cells.     

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.     

Small molecular non-fullerene electron acceptors for P3HT-based bulk-heterojunction solar cells

Three small molecules with the same arms and different cores of perylene diimide(PDI)or indaceno[2,1-b:6,5-b']dithiophene(IDT)were designed and synthesized as the acceptor materials for P3HT-based bulk-heterojunction(BHJ)solar cells.The impacts of the different cores on the optical absorption,electrochemical properties,electron mobility,film morphology,photoluminescene characteristics,and solar cell performance were thoroughly studied.The three compounds possess a broad absorption covering the wavelength range of 400–700 nm and relatively low lowest unoccupied molecular orbital(LUMO)energy levels of?3.86,?3.81 and?3.99 eV.The highest power conversion efficiency of 0.82%was achieved for the BHJ solar cells based on SM3 as the acceptor material,the compound with a PDI core.     

An Alternating Polymer of Two Building Blocks Based on B←N Unit:Non-fullerene Acceptor for Organic Photovoltaics

B←N coordination bond can be used to develop polymer electron acceptors for efficient all-polymer solar cells(all-PSCs). Here, we report a new alternating conjugated polymer containing two building blocks based on B←N unit. The polymer exhibits strong light absorption in the visible range, low-lying LUMO/HOMO energy levels and moderate electron mobility. The resulting all-PSC devices exhibit power conversion efficiencies of 1.50%–2.47%.     

Graphene-based materials for polymer solar cells

Due to the remarkable electronic, optical, thermal, and mechanical properties, graphene-based materials have shown great potential in a wide range of technique applications. Particularly, the high transparency, conductivity, flexibility, and abundance make graphene materials highly attractive for polymer solar cells (PSCs). Graphene-based materials have been regarded as one promising candidate used in various parts in PSCs not only as electrodes, but also as interfacial layers and active layers with an aim to boost the power conversion efficiency of the devices. In this review, we summarize the recent progress about the design and synthesis of graphene-based materials for efficient PSCs along with the related challenges and future perspectives.     

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     

Rationally pairing photoactive materials for high-performance polymer solar cells with efficiency of 16.53%

The emergence of non-fullerene acceptors(NFA) offers a promising opportunity to develop high-performance donor/acceptor pairs with high power conversion efficiency,as NFAs offer tunable energy levels,broad absorption and suitable aggregation property.In order to enhance light-harvesting capability of active layers,we choose a wide bandgap polymer PTQ10 as the donor to blend with a narrow bandgap NFAY6 as the acceptor.In comparison with PTQ10:IDIC blend,~130 nm red-shifted absorption spectrum is observed in the PTQ10:Y6 blend,which potentially enhance the short-circuit current density(Jsc) for the PSCs.In addition,the optimal PTQ10:Y6 blend shows higher photoluminescence quenching efficiency and more efficient charge separation,higher charge mobilities,as well as weaker bimolecular recombination over the PTQ10:IDIC blend,which leads to an outstanding power conversion efficiency(PCE) of 16.53%,with a notable Jsc of 26.65 mA cm^-2 and fill factor(FF) of 0.751.     

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.     

Synthesis and applications of low‐bandgap conjugated polymers containing phenothiazine donor and various benzodiazole acceptors for polymer solar cells

A series of soluble donor‐acceptor conjugated polymers comprising of phenothiazine donor and various benzodiazole acceptors (i.e., benzothiadiazole, benzoselenodiazole, and benzoxadiazole) sandwiched between hexyl‐thiophene linkers were designed, synthesized, and used for the fabrication of polymer solar cells (PSC). The effects of the benzodiazole acceptors on the thermal, optical, electrochemical, and photovoltaic properties of these low‐bandgap (LBG) polymers were investigated. These LBG polymers possessed large molecular weight (M_n) in the range of 3.85?5.13 × 10⁴ with high thermal decomposition temperatures, which demonstrated broad absorption in the region of 300?750 nm with optical bandgaps of 1.80?1.93 eV. Both the HOMO energy level (?5.38 to ?5.47 eV) and LUMO energy level (?3.47 to ?3.60 eV) of the LBG polymers were within the desirable range of ideal energy level. Under 100 mW/cm² of AM 1.5 white‐light illumination, bulk heterojunction PSC devices containing an active layer of electron donor polymers mixed with electron acceptor [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) in different weight ratios were investigated. The best performance of the PSC device was obtained by using polymer PP6DHTBT as an electron donor and PC₇₁BM as an acceptor in the weight ratio of 1:4, and a power conversion efficiency value of 1.20%, an open‐circuit voltage (V_oc) value of 0.75 V, a short‐circuit current (J_sc) value of 4.60 mA/cm², and a fill factor (FF) value of 35.0% were achieved. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

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.     

Self-assembled monolayers for interface engineering in polymer solar cells

Polymer solar cell (PSC) has been developed vastly in the past decade due to the advantages of low cost, lightweight, mechanical flexibility, versatility of chemical design and synthesis, semitransparency, and solution processing. The performance and lifetime of PSCs are highly dependent on the properties of both active materials and their interfaces. The combination of the versatility of organic chemistry and the multitude of well-understood ligand–metal interactions allows self-assembled monolayers (SAMs) of organic molecules to direct control over the electronic and chemical properties at the inorganic–organic interfaces. Thus, SAMs are an attractive pathway to reconcile interfaces with tunable interface properties in PSCs. Hence, this review describes the application of SAMs in PSCs at different interfaces. First, SAMs as alternatives of traditional transporting materials to reduce the barrier at indium tin oxide (ITO)/active layer interface due to the ability of tuning work function of ITO electrode are discussed. Second, the modifications of metal oxide by SAMs to control the electrical contacts at transporting layer/active layer interface are described. Third, tailoring the properties of the donor/acceptor interface by SAMs to improve the performance of PSCs are summarized. Finally, perspectives and challenges are pointed out for developing highly stable and high-performance PSCs by applying SAMs.     

Acceptor–acceptor conjugated copolymers based on perylenediimide and benzothiadiazole for all‐polymer solar cells

Donor–acceptor (D–A) conjugated copolymers are one of known classes of organic optoelectronic materials and have been well developed. However, less attention has been paid on acceptor–acceptor (A–A) conjugated analogs. In this work, two types of A–A conjugated copolymers, namely P1‐Cn and P2‐Cn (n is the carbon number of their alkyl side chains), were designed and synthesized based on perylenediimide ( PDI ) and 2,1,3‐benzothiadiazole ( BT ). Different from P1‐Cn , P2‐Cn polymers have additional acetylene π‐spacers between PDI and BT and thus hold a more planar backbone configuration. Property studies revealed that P2‐Cn polymers possess a much red‐extended UV–vis absorption spectrum, stronger π–π interchain interactions, and one‐order larger electron mobility in their neat film state than P1‐Cn . However, all‐polymer solar cells using P1‐Cn as acceptor component and poly(3‐hexyl thiophene) or poly(2,7‐(9,9‐didodecyl‐fluoene)‐alt?5,5′‐(4,7‐dithienyl‐2‐yl‐2,1,3‐benzothiadiazole) as donor component exhibited much better performance than those based on P2‐Cn . Apart from their backbone chemical structure, the side chains were found to have little influence on the photophysical, electrochemical, and photovoltaic properties for both P1‐Cn and P2‐Cn polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1200–1215     

A chlorinated non-fullerene acceptor for efficient polymer solar cells

After additive and thermal annealing treatment, the PM6:Y15 based device obtains a high power conversion efficiency of 14.13%.     

Side chain engineering of quinoxaline-based small molecular nonfullerene acceptors for high-performance poly(3-hexylthiophene)-based organic solar cells

Poly(3-hexylthiophene)(P3HT)is one of the most used semiconducting polymers for organic photovoltaics because it has potential for commercialization due to its easy synthesis and stability.Although the rapid development of the small molecular non-fullerene acceptors(NFAs)have largely improved the power conversion efficiency(PCE)of organic solar cells(OSCs)based on other complicated p-type polymers,the PCE of P3HT-based OSCs is still low.In addition,the design principle and structure-properties correlation for the NFAs matching well with P3HTare still unclear and need to be investigated in depth.Here we designed a series of NFAs comprised of acceptor(A)and donor(D)units with an A2-A1-D-A1-A2 configuration.These NFAs are abbreviated as Qx3,Qx3 b and Qx3c,where indaceno[1,2-b:5,6-b′]dithiophene(IDT),quinoxaline(Qx)and 2-(1,1-dicyanomethylene)rhodanine serve as the middle D,bridged A1 and the end group A2,respectively.By subtracting the phenyl side groups appended on both IDT and Qx skeletons,the absorption spectra,energy levels and crystallinity could be regularly modulated.When paired with P3 HT,three NFAs show totally different photovoltaic performance with PCEs of 3.37%(Qx3),6.37%(Qx3b)and 0.03%(Qx3 c),respectively.From Qx3 to Qx3b,the removing of phenyl side chain in the middle IDT unit results in the increase of crystallinity and electron mobility.However,after subtracting all the grafted phenyl side groups on both IDT and Qx units,the final molecule Qx3 c exhibits the lowest PCE of only 0.03%,which is mainly attributed to the serious phase-separation of the blend film.These results demonstrate that optimizing the substituted position of phenyl side groups for A2-A1-D-A1-A2 type NFAs is vital to regulate the optoelectronic property of molecule and morphological property of active layer for high performance P3HT-based OSCs.     

Side chain engineering of naphthalene diimide–bithiophene‐based polymer acceptors in all‐polymer solar cells

Two novel polymeric acceptors based on naphthalene diimide (NDI) and 2.2′‐bithiophene, named as P(NDI2THD‐T2) and P(NDI2TOD‐T2), were designed and synthesized for all polymer solar cells application. The structural and electronic properties of the two acceptors were modulated through side‐chain engineering of the NDI units. The optoelectronic properties of the polymers and the morphologies of the blend films composed of the polymer acceptors and a donor polymer PTB7‐Th were systemically investigated. With thiophene groups introduced into the side chains of the NDI units, both polymers showed wider absorption from 350 nm to 900 nm, compared with the reference polymer acceptor of N2200. No redshift of absorption spectra from solutions to films indicated reduced aggregation of the polymers due to the steric hindrance effect of thiophene rings in the side chains. The photovoltaic performance were characterized for devices in a configuration of ITO/PEDOT:PSS/PTB7‐Th:acceptors/2,9‐bis(3‐(dimethylamino)propyl)anthra[2,1,9‐def:6,5,10‐def]diisoquinoline‐1,3,8,10(2H,9H)‐tetraone (PDIN)/Al. With the addition of diphenyl ether as an additive, the power conversion efficiencies (PCEs) of 2.73% and 4.75% for P(NDI2THD‐T2) and P(NDI2TOD‐T2) based devices were achieved, respectively. The latter showed improved J_sc, Fill Factor (FF), and PCE compared with N2200 based devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3679–3689