Utilizing 3,4-ethylenedioxythiophene(EDOT)-bridged non-fullerene acceptors for efficient organic solar cells

A rational design of efficient low-band-gap non-fullerene acceptors(NFAs)for high-performance organic solar cells(OSCs)remains challenging;the main constraint being the decrease in the energy level of the lowest unoccupied molecular orbitals(LUMOs)as the bandgap of A-D-A-type NFAs decrease.Therefore,the short current density(J_sc)and open-circuit voltage(V_oc)result in a trade-off relationship,making it difficult to obtain efficient OSCs.Herein,three NFAs(IFL-ED-4 F,IDT-ED-4 F,and IDTT-ED-2 F)were synthesized to address the above-mentioned issue by introducing 3,4-ethylenedioxythiophene(EDOT)as aπ-bridge.These NFAs exhibit relatively low bandgaps(1.67,1.42,and 1.49 eV,respectively)and upshifted LUMO levels(-3.88,-3.84,and-3.81 eV,respectively)compared with most reported low-band-gap NFAs.Consequently,the photovoltaic devices based on IDT-ED-4 F blended with a PBDB-T donor polymer showed the best power conversion efficiency(PCE)of 10.4%with a high J_sc of 22.1 mA cm^-2 and Voc of 0.884 V among the examined NFAs.In contrast,IDTT-ED-4 F,which was designed with an asymmetric structure of the D-p-A type,showed the lowest efficiency of 1.5%owing to the poor morphology and charge transport properties of the binary blend.However,when this was introduced as the third component of the PM6:BTP-BO-4 Cl,complementary absorption and cascade energy-level alignment between the two substances could be achieved.Surprisingly,the IDTT-ED-4 F-based ternary blend device not only improved the Jscand Voc,but also achieved a PCE of 15.2%,which is approximately 5.3%higher than that of the reference device with a minimized energy loss of 0.488 eV.In addition,the universality of IDTT-ED-2 F as a third component was effectively demonstrated in other photoactive systems,specifically,PM6:BTPe C9 and PTB7-Th:IEICO-4 F.This work facilitates a better understanding of the structure–property relationship for utilizing efficient EDOT-bridged NFAs in high-performance OSC applications.     

Simple non-fullerene electron acceptors with unfused core for organic solar cells

Two simple unfused-cores based electron acceptors with different side units were developed for application in non-fullerene solar cells, in which the side chains have the significant effect on their absorption spectra and photovoltaic performance.     

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 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.     

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.     

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%.     

Asymmetric molecular engineering in recent nonfullerene acceptors for efficient organic solar cells

Nonfullerene acceptors (NFAs), which usually possess symmetric skeletons, have drawn great attention in recent years due to their pronounced advantages over the fullerene counterparts. Moreover, breaking the symmetry of NFAs could fine tune the molecular dipole, solubility, energy level, intermolecular interaction, molecular packing, crystallinity, etc., and give rise to improved photovoltaic performance. Currently, there are three main strategies for the design of asymmetric NFAs. This review highlights the recent advances of high-performance asymmetric NFAs and briefly outlooks the materials exploration for the future.     

A chlorinated non-fullerene acceptor for efficient polymer solar cells

Improving the performance and reducing the manufacturing costs are the main directions for the development of organic solar cells in the future. Here, the strategy that uses chemical structure modification to optimize the photoelectric properties is reported. A new narrow bandgap (1.30 eV) chlorinated non-fullerene electron acceptor (Y15), based on benzo[d][1,2,3] triazole with two 3-undecyl-thieno[2′,3′:4,5] thieno[3,2-b] pyrrole fused -7-heterocyclic ring, with absorption edge extending to the near-infrared (NIR) region, namely A-DA'D-A type structure, is designed and synthesized. Its electrochemical and optoelectronic properties are systematically investigated. Benefitting from its NIR light harvesting, the fabricated photovoltaic devices based on Y15 deliver a high power conversion efficiency (PCE) of 14.13%, when blending with a wide bandgap polymer donor PM6. Our results show that the A-DA'D-A type molecular design and application of near-infrared electron acceptors have the potential to further improve the PCE of polymer solar cells (PSCs).     

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.     

A new non-fullerene acceptor based on the heptacyclic benzotriazole unit for efficient organic solar cells

正Non-fullerene acceptors (NFAs) become an interesting family of organic photovoltaic materials, and have attracted considerable interest for their great potential in manufacturing large-area flexible solar panels by low cost coating methods [1–5]. Recently, our group proposed in the first time an A-DA’D-A molecular strategy and synthesized a new class of non-fullerene acceptor Y6 with a record efficiency above 15%with single junction organic solar cells (OSCs)[6]. To further improve the photovoltaic performance     

The effect of end-capping groups in A-D-A type non-fullerene acceptors on device performance of organic solar cells

A series of novel wide bandgap small molecules(IFT-ECA, IFT-M, IFT-TH and IFT-IC) based on the A-D-A structure with indenofluorene core, thiophene bridge, and different electron-deficient end-capping groups, were synthesized and used as non-fullerene acceptors in organic solar cells. The influences of end-capping groups on the device performance were studied.The four materials exhibited different physical and chemical properties due to the variation of end-capping groups, which further affect the exciton dissociation, charge transport, morphology of the bulk-heterojunction films and device performance. Among them, IFT-IC-based device delivered the best power conversion efficiency of 7.16% due to proper nano-scale phase separation morphology and high electron mobility, while the devices based on the other acceptors achieved lower device performance(4.14% for IFT-TH, 1% for IFT-ECA and IFT-M). Our results indicate the importance of choosing suitable electron-withdrawing groups to construct high-performance non-fullerene acceptors based on A-D-A motif.     

Over 18% binary organic solar cells enabled by isomerization of non-fullerene acceptors with alkylthiophene side chains

Side-chain engineering has been demonstrated as an effective method for fine-tuning the optical, electrical, and morphological properties of organic semiconductors toward efficient organic solar cells (OSCs). In this work, three isomeric non-fullerene small molecule acceptors (SMAs), named BTP-4F-T2C8, BTP-4F-T2EH and BTP-4F-T3EH, with linear and branched alkyl chains substituted on the α or β positions of thiophene as the side chains, were synthesized and systematically investigated. The results demonstrate that the size and substitution position of alkyl side chains can greatly affect the electronic properties, molecular packing as well as crystallinity of the SMAs. After blending with donor polymer D18-Cl, the prominent device performance of 18.25% was achieved by the BTP-4F-T3EH-based solar cells, which is higher than those of the BTP-4F-T2EH-based (17.41%) and BTP-4F-T2C8-based (15.92%) ones. The enhanced performance of the BTP-4F-T3EH-based devices is attributed to its stronger crystallinity, higher electron mobility, suppressed biomolecular recombination, and the appropriate intermolecular interaction with the donor polymer. This work reveals that the side chain isomerization strategy can be a practical way in tuning the molecular packing and blend morphology for improving the performance of organic solar cells.

     

Impact of end-capped engineering on the optoelectronic characteristics of pyrene-based non-fullerene acceptors for organic photovoltaics

Pyrene-based molecules are being explored as prospective fullerene-free acceptors for organic solar cells (OSCs), due to their easy accessibility, structural planarity, and excellent electron delocalization. In this work, we successfully designed and analyzed pyrene-based acceptor materials (QL1–QL8) to investigate their photophysical and electro-optical parameters. Various geometric parameters were computed at the MPW1PW91/6-31G(d,p). Advanced quantum chemical approaches were employed to characterize the molecules. All the tailored molecules (QL1–QL8) exhibit a lower bandgap than the reference (R), signifying their superiority. Among these, QL8 was found to have a maximum absorption (λ_max) at 791.37 nm and an optical bandgap (E_LUMO − E_HOMO) minimum of 2.11 eV. Redshifted absorption spectra are observed in both gaseous and solvent phases for all the designed (QL1–QL8) molecules in contrast to R. Among these, QL4 exhibits the highest light harvesting efficiency (0.9826), and open-circuit voltage. A detailed donor–acceptor investigation of QL8/PBDB-T revealed the marvelous charge switching at the donor–acceptor interface. The approach used in this study is anticipated to facilitate the manufacturing of highly efficient OSC molecules.     

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.     

Rhodanine flanked indacenodithiophene as non-fullerene acceptor for efficient polymer solar cells

A fused-ring electron acceptor IDT-2BR1 based on indacenodithiophene core with hexyl side-chains flanked by benzothiadiazole rhodanine was designed and synthesized.In comparison with its counterpart with hexylphenyl side-chains(IDT-2BR),IDT-2BR1exhibits higher highest occupied molecular orbital(HOMO)energy but similar lowest unoccupied molecular orbital(LUMO)energy(IDT-2BR1:HOMO=-5.37eV,LUMO=-3.67eV;IDT-2BR:HOMO=-5.52eV,LUMO=-3.69eV),red-shifted absorption and narrower bandgap.IDT-2BR1 has higher electron mobility(2.2×10~(-3)cm~2 V~(-1)s~(-1))than IDT-2BR(3.4×10~(-4)cm~2 V~(-1)s~(-1))due to the reduced steric hindrance and ordered molecular packing.Fullerene-free organic solar cells based on PTB7-Th:IDT-2BRl yield power conversion efficiencies up to 8.7%,higher than that of PTB7-Th:IDT-2BR(7.7%),with a high open circuit voltage of0.95 V and good device stability.     

Selection of side groups on simple non-fullerene acceptors for the application in organic solar cells: From flexible to rigid

The side chains on non-fullerene acceptors (NFAs) can affect greatly the photovoltaic performances of the resulting organic solar cells (OSCs) by regulating the molecular packing and orientation of NFAs. To explore suitable side groups for asymmetric simple NFAs, in this work, we design and synthesize two A-D₁-A′-D₂-A type NFAs, NTC-4Cl, and PhNTC-4Cl, which own flexible alkyloxy and rigid aryloxy side chains on the A′ cores, respectively. Due to the same molecular backbone (A′: benzotriazole; D₁: thiophene; D₂: cyclopentadithiophene; A: dichlorodicyanoindanone), NTC-4Cl and PhNTC-4Cl have similar absorptions and energy levels. However, the PhNTC-4Cl-based OSC gives a higher power conversion efficiency than that of the NTC-4Cl-based one (11.09% vs. 10.82%) because PhNTC-4Cl shows more compact π–π stacking and dominant face-on orientation, enhancing charge transport and mitigating charge recombination. Therefore, this work provides a new insight into the molecular design of high-performance NFAs, especially the rational choice of side groups on asymmetric simple NFAs.     

A major step toward efficient and stable single-material organic solar cells

<正>Organic photovoltaics (OPV) can potentially combine low cost, lightness, flexibility and low environmental impact. In less than two decades, the power conversion efficiency(PCE) of OPV cells has increased from 1 to more than 15%thanks to parallel efforts in material design and device technology. Solution processed bulk heterojunction (BHJ)     

Carbazolebis(thiadiazole)-core based non-fused ring electron acceptors for efficient organic solar cells

Non-fused ring electron acceptors (NFREAs) have a broad application prospect in the commercialization of organic solar cells (OSCs) due to the advantages of simple synthesis and low cost. The selection of intermediate block cores of non-fused frameworks and the establishment of the relationship between molecular structure and device performance are crucial for the realization of high-performance OSCs. Herein, two A-D-A’-D-A type NFREAs namely CBTBO-4F and CBTBO-4Cl, constructed with a novel electron-deficient block unit N-(2-butyloctyl)-carbazole[3,4-c:5,6-c]bis[1,2,5]thiadiazole (CBT) and bridging unit 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene (DTC) coupling with different terminals (IC-2F/2Cl), were designed and synthesized. The two NFREAs feature broad and strong photoresponse from 500 nm to 900 nm due to the strong intramolecular charge transfer characteristics. Compared with CBTBO-4F, CBTBO-4Cl shows better molecular planarity, stronger crystallinity, more ordered molecular stacking, larger van der Waals surface, lower energy level and better active layer morphology, contributing to much better charge separation and transport behaviors in its based devices. As a result, the CBTBO-4Cl based device obtains a higher power conversion efficiency of 10.18% with an open-circuit voltage of 0.80 V and a short-circuit current density of 21.20 mA/cm². These results not only demonstrate the great potential of CBT, a new building block of the benzothiazole family, in the construction of high-performance organic conjugated semiconductors, but also suggest that the terminal chlorination is an effective strategy to improve device performance.