A Cyano-Substituted Organoboron Electron-deficient Building Block for D-A Type Conjugated Polymers

The development of donor-acceptor(D-A)type conjugated polymers depends largely on the design of novel A building blocks.Herein,we report a novel A building block based on the cyano-substituted organoboron unit(SBN-3).Compared with the most common fluorine-substituted B←N unit,SBN-3 displays a significantly downshifted LUMO energy level because of the strong electron-withdrawing ability of cyano groups.In addition,due to the greater impact of cyano substitution on LUMO than on HOMO,SBN-3 exhibits a reduced band gap,nearinfrared absorption and fluorescence properties.The D-A type conjugated polymers based on the cyano-substituted B←N unit with thiophene-based units show narrow optical band gaps of ca.1.3 e V as well as distinctive electronic structures,i.e.,delocalized LUMOs and localized HOMOs.This work thus provides not only an effective approach to design strong A units but also a new electron-deficient building block for D-A type conjugated polymers.

Manipulating molecular aggregation and crystalline behavior of A-DA’D-A type acceptors by side chain engineering in organic solar cells

Alkyl chains engineering plays an important role in photovoltaic materials for organic solar cells.Herein,three A-DA’D-A(acceptor–donor–acceptor’–donor–acceptor)type acceptors named Y6,Y6-C4,and Y6-C5 with different branching position on the pyrrole motif are discussed and the relationship between molecular aggregation,crystalline,and device performance are systematically investigated.The distance between the branching position and the main backbone affects their optical absorption and energy levels.Y6-C4 and Y6-C5 with the branching position at the fourth and fifth carbon of the alkyl chain show blue-shifted absorption and increased electrochemical bandgaps,compared with Y6 with the branching position at the second carbon of the alkyl side chain.In addition,this distance influences the molecular aggregation and crystalline behavior of the donor/acceptor blends.Compared with Y6-C4,Y6-C5 possesses a stronger crystalline and aggregate ability in the blends with a lower non-radiative energy loss,which results in a higher open circuit voltage(Voc)of 0.88 V.Finally,Y6-C5-based binary device achieved a high power conversion efficiency up to 16.73%with afill factor(FF)of 0.78.These results demonstrate that the side chain engineering is an effective strategy for tuning the molecular aggregation and crystalline to improve photovoltaic performance of the A-DA’D-A type acceptors.

18.55% Efficiency Polymer Solar Cells Based on a Small Molecule Acceptor with Alkylthienyl Outer Side Chains and a Low-Cost Polymer Donor PTQ10

The development of A-DA′D-A type small molecule acceptors(SMAs)has promoted the rapid progress of polymer solar cells(PSCs)in recent years.The outer side chains on the terminal thiophene ring and inner side chains on nitrogen atoms of the pyrrole ring of the DA′D fused ring play important roles in the photovoltaic performance of the SMAs.Here,we synthesized two new SMAs,2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(4-(2-ethylhexyl)thiophen-2-yl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(T2EH)and 2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(3-(2-ethylhexyl)phenyl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)(P2EH),with 2-ethylhexylβ-substituted thienyl or phenyl as the outer side chains,respectively,to improve the photovoltaic properties of the SMAs.Compared with P2EH,T2EH exhibits closerπ−πstacking,slightly red-shifted absorption,and higher electron mobility.Moreover,the active layer of T2EH blended with the low-cost polymer donor poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)](PTQ10)possesses higher mobilities,a longer lifetime,and less recombination of the charge carriers in comparison with that of the PTQ10:P2EH active layer.Eventually,the PTQ10:T2EH-based PSCs showed an outstanding power conversion efficiency(PCE)of 18.55%,while the PSC based on PTQ10:P2EH displayed a PCE of 17.50%.Importantly,18.55%is the highest PCE in the PTQ10-based binary PSCs so far.The results indicate that T2EH is one of the best SMAs for the PTQ10-based PSCs and is a promising SMA for the application of PSCs.