To clearly show how important the impact of side chains on organic solar cells(OSCs)is,we designed three acceptors IDIC-CxPh(x=4,5,or 6)via subtle side-chain regulation.Despite this small change,significant distinctio...To clearly show how important the impact of side chains on organic solar cells(OSCs)is,we designed three acceptors IDIC-CxPh(x=4,5,or 6)via subtle side-chain regulation.Despite this small change,significant distinctions were detected.IDIC-C4Ph devices achieve an optimal efficiency of 13.94%under thermal annealing,but thermal-assistant solvent-vapor annealing hugely suppresses the efficiencies to 10%.However,the C6Ph side chain endows extremely disordered stacking orientations,generating moderate efficiencies of~12.50%.Excitingly,the IDIC-C5Ph affords an unexpected two-channel p-p charge transport(TCCT)property,boosting the fill factor(FF)by up to 80.02%and efficiency to 14.56%,ranking the best among five-ring fused-ladder-type acceptors.Impressively,the special TCCT behavior of IDIC-C5Ph enables 470 nm thick-film OSC with a high FF of up to 70.12%and efficiency of 13.01%,demonstrating the great promise in fabricating largescale OSCs.展开更多
A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide...A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide（PI） films with different side chain contents was synthesized from biphenyltetracarboxylicdianhydride（BPDA）,4,4＇-oxydianiline（ODA） and C6BBC4,and their thermal properties,optical transparency and liquid crystal alignment property,and so on,were investigated by thermogravimetric analysis（TGA）,differential scanning calorimetry（DSC）,crystal rotation method,polarizing microscopy and UV-Vis spectra.With the content of side chained diamine increasing from 0 to 100%,the η inh of poly（amide acid）（PAA） decreased rapidly from 3.0 to 0.51,the glass transition temperature（T g） of polyimides（PIs） decreased from 274 ℃ to 203 ℃ and the Vis-light transmittance of alignment films substantially increased.As for the alignment properties,the pretilt angle of PI alignment films without rubbing could reach 90° when the content of C6BBC4 was 60% or more.At the same time,the alignment stability could meet the industrial requirements.It was considered that the alkoxy spacer,the biphenyl unit and the alkoxy tail may all play important roles in achieving a large pretilt angle even up to 90°,and the introduction of only the alkoxy spacer or alkoxy tail can also improve the pretilt angle,but not by much.展开更多
A novel diamine 4-[（4＇-butoxyphenoxy）carbonyl]phenyl-3＂,5＂-diaminobenzoate （BCDA） was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a se...A novel diamine 4-[（4＇-butoxyphenoxy）carbonyl]phenyl-3＂,5＂-diaminobenzoate （BCDA） was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a series of polyimides were also synthesized. All the intermediates and the final product were characterized by FTIR and 1H-NMR. The key step in synthesis route is selective hydrolyzation of two ester groups in 4-butoxyphenyl-4＇-acetoxybenzoate, by adjusting the reaction temperature and the concentration of ammonia, shorteding the reaction time. The properties of the novel polyimides, such as the aggregation structures, glass transition temperature, solubility and the pretilt angles, were carded out.展开更多
This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characteri...This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.展开更多
基金The authors are deeply grateful to the National Natural Science Foundation of China(21502205,51773220,51703104,and 51873227)DICP&QIBEBT(UN201805)for financial support.X.C.B.deeply thanks the Youth Innovation Promotion Association CAS(2016194).R.Q.Y.gives thanks to the“Chutian Scholar Program”of Hubei province.The work is also supported by the Dalian National Laboratory for Clean Energy for Clean Energy(DNL),CAS.The authors thanks Prof.Chunming Yang from the Shanghai Synchrotron Radiation Facility for useful discussions.
文摘To clearly show how important the impact of side chains on organic solar cells(OSCs)is,we designed three acceptors IDIC-CxPh(x=4,5,or 6)via subtle side-chain regulation.Despite this small change,significant distinctions were detected.IDIC-C4Ph devices achieve an optimal efficiency of 13.94%under thermal annealing,but thermal-assistant solvent-vapor annealing hugely suppresses the efficiencies to 10%.However,the C6Ph side chain endows extremely disordered stacking orientations,generating moderate efficiencies of~12.50%.Excitingly,the IDIC-C5Ph affords an unexpected two-channel p-p charge transport(TCCT)property,boosting the fill factor(FF)by up to 80.02%and efficiency to 14.56%,ranking the best among five-ring fused-ladder-type acceptors.Impressively,the special TCCT behavior of IDIC-C5Ph enables 470 nm thick-film OSC with a high FF of up to 70.12%and efficiency of 13.01%,demonstrating the great promise in fabricating largescale OSCs.
基金Supported by the National Natural Science Foundation of China(Nos.50773044,50973073)
文摘A novel biphenyl side-chained diamine with alkyloxy spacer and alkyloxy tail,4＇-butoxy-4-（3,5-diaminobenzoyloxy）hexyloxybiphenyl（C6BBC4）,was synthesized and characterized by FTIR and 1 H NMR.A series of polyimide（PI） films with different side chain contents was synthesized from biphenyltetracarboxylicdianhydride（BPDA）,4,4＇-oxydianiline（ODA） and C6BBC4,and their thermal properties,optical transparency and liquid crystal alignment property,and so on,were investigated by thermogravimetric analysis（TGA）,differential scanning calorimetry（DSC）,crystal rotation method,polarizing microscopy and UV-Vis spectra.With the content of side chained diamine increasing from 0 to 100%,the η inh of poly（amide acid）（PAA） decreased rapidly from 3.0 to 0.51,the glass transition temperature（T g） of polyimides（PIs） decreased from 274 ℃ to 203 ℃ and the Vis-light transmittance of alignment films substantially increased.As for the alignment properties,the pretilt angle of PI alignment films without rubbing could reach 90° when the content of C6BBC4 was 60% or more.At the same time,the alignment stability could meet the industrial requirements.It was considered that the alkoxy spacer,the biphenyl unit and the alkoxy tail may all play important roles in achieving a large pretilt angle even up to 90°,and the introduction of only the alkoxy spacer or alkoxy tail can also improve the pretilt angle,but not by much.
基金We are grateful for the financial support from the National Natural Science Foundation of China(No,50433010)Doctoral Fund of Ministry of Eduction of China(No.20040610028),
文摘A novel diamine 4-[（4＇-butoxyphenoxy）carbonyl]phenyl-3＂,5＂-diaminobenzoate （BCDA） was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a series of polyimides were also synthesized. All the intermediates and the final product were characterized by FTIR and 1H-NMR. The key step in synthesis route is selective hydrolyzation of two ester groups in 4-butoxyphenyl-4＇-acetoxybenzoate, by adjusting the reaction temperature and the concentration of ammonia, shorteding the reaction time. The properties of the novel polyimides, such as the aggregation structures, glass transition temperature, solubility and the pretilt angles, were carded out.
基金We are grateful to the National Natural Science Foundation of China for financial support(project No.20274026)
文摘This is a part of our systematic research work on polyimides with mesogenic unit side chain. In this study, a new 4＇-phenylpbenyl 4-（3＂,5＂-diaminobenzoyloxy）benzoate and polyimide were synthesized, and characterized by FTIR, ^1H-NMR, inherent viscosity, mechanical properties, and solubility measurements. The diamine composed with mesogenic unit aryl ester groups and bipbenyl group with longer L/D ratio, was synthesized by two key steps. Firstly, the hydroxy group of 4-hydroxybenzoic acid was protected by acetoxy group for avoiding self- polymerization of 4-hydroxybenzoic acid, and then selectively hydrolyzed after esterification of carboxyl. Secondly, a selective catalysis hydrogenation was adopted to prevent the aryl ester from deoxidation. Based on this diamine, a novel polyimide was prepared by polycondensation of 4＇-phenylphenyl 4-（3＂, 5＂-diaminobenzoyloxy）benzoate and 4-aminophenyl ether（ODA） with 4, 4＇-oxydiphthalic anhydride（ODPA） in N-methyl-2-pyrrolidone （NMP）. The resulting polyimide with longer side chain showed better solubility and more regular structure. Its inherent viscosity is lower than that without side chains, but its modulus and strength not only maintained, even improved.
