To construct efficient low band gap polymers,increasing the Quinone structure of the polymer backbone could be one desirable strategy.In this work,two D–Q–A–Q polymers P1 and P2 were designed and synthesized with t...To construct efficient low band gap polymers,increasing the Quinone structure of the polymer backbone could be one desirable strategy.In this work,two D–Q–A–Q polymers P1 and P2 were designed and synthesized with thiophenopyrrole diketone(TPD)and benzothiadiazole(BT)unit as the core and ester linked thieno[3,4-b]thiophene(TT)segment as π-bridging,and the main focus is to make a comparative analysis of different cores in the influence of the optical,electrochemical,photochemical and morphological properties.Compared with the reported PBDTTEH–TBTTHD-i,P1 exhibited the decreased HOMO energy level of-5.38 e V and lower bandgap of 1.48 e V.Furthermore,when replaced with BT core,P2 showed a red-shifted absorption profile of polymer but with up-shifted HOMO energy level.When fabricated the photovoltaic devices in conventional structure,just as expected,the introduction of ester substituent made an obvious increase of VOC from 0.63 to 0.74 V for P1.Besides,due to the deep HOMO energy level,higher hole mobility and excellent phase separation with PC71 BM,a superior photovoltaic performance(PCE=7.13%)was obtained with a short-circuit current density(JSC)of 14.9 m A/cm^2,significantly higher than that of P2(PCE=2.23%).Generally,this study highlights that the strategy of inserting quinoid moieties into D–A polymers could be optional in LBG-polymers design and presents the importance and comparison of potentially competent core groups.展开更多
Design and synthesis of low bandgap(LBG) polymer donors is inevitably challenging and their processability from a non-halogenated solvent system remains a hurdle to overcome in the area of highperformance polymer sola...Design and synthesis of low bandgap(LBG) polymer donors is inevitably challenging and their processability from a non-halogenated solvent system remains a hurdle to overcome in the area of highperformance polymer solar cells(PSCs).Due to a high aggregation tendency of LBG polymers,especially diketopyrrolopyrrole(DPP)-based polymers coupled with bithiophenes in the polymer backbones,their widespread adoption in non-ha logena ted solvent-processed PSCs has been limited.Herein,a novel LBG DPP-based polymer,called PDPP4 T-1 F with asymmetric arrangement of fluorine atom,has been successfully synthesized and showed an outstanding power conversion efficiency(PCE) of 10.10% in a singlejunction fullerene-based PSCs.Furthermore,an impressive PCE of 13.21% has been achieved in a tandem device from a fully non-halogenated solvent system,which integrates a wide bandgap PDTBTBz-2 F polymer in the bottom cell and LBG PDPP4 T-1 F polymer in the top cell.The achieved efficiency is the highest value reported in the literature to date in fullerene-based tandem PSCs.We found that a uniformly distributed interpenetrating fibril network with nano-scale phase separation and anisotropy of the polymer backbone orientation for efficient charge transfer/transport and suppressed charge recombination in PDPP4 T-1 F-based PSCs led to outstanding PCEs in single and tandem-junction PSCs.展开更多
In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for t...In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for the first time. In these polymers, fluorene, 2,7-carbazole, phenothiazine and thiophene are employed as electron-donating groups and PD as electron-withdrawing group. TGA measurements demonstrated that these polymers possess good thermal stability（all above 377 °C）. Very broad absorption spectrum was also obtained from the polymer THTDT（300？850 nm）. CV characterization found that these polymers owned low highest occupied molecular orbital（HOMO） energy levels（？5.39 e V for THTDT, ？5.49 e V for CZTDT and ？5.78 e V for PFTDT） except for PHTDT（？5.17 e V）. The geometry and electronic properties of PFTDT, CZTDT, PHTDT and THTDT were investigated by means of theoretical calculation. All the above advantages demonstrate that PD based polymers could be candidates for electronic devices.展开更多
基金the National Natural Science Foundation of China (21604092, 51573205 and 51773220)China Postdoctoral Science Foundation (2017M610453+1 种基金the Youth Innovation Promotion Association CAS (2016194) for financial supportthe CAS-TWAS President’s Fellowship Program for Ph.D
文摘To construct efficient low band gap polymers,increasing the Quinone structure of the polymer backbone could be one desirable strategy.In this work,two D–Q–A–Q polymers P1 and P2 were designed and synthesized with thiophenopyrrole diketone(TPD)and benzothiadiazole(BT)unit as the core and ester linked thieno[3,4-b]thiophene(TT)segment as π-bridging,and the main focus is to make a comparative analysis of different cores in the influence of the optical,electrochemical,photochemical and morphological properties.Compared with the reported PBDTTEH–TBTTHD-i,P1 exhibited the decreased HOMO energy level of-5.38 e V and lower bandgap of 1.48 e V.Furthermore,when replaced with BT core,P2 showed a red-shifted absorption profile of polymer but with up-shifted HOMO energy level.When fabricated the photovoltaic devices in conventional structure,just as expected,the introduction of ester substituent made an obvious increase of VOC from 0.63 to 0.74 V for P1.Besides,due to the deep HOMO energy level,higher hole mobility and excellent phase separation with PC71 BM,a superior photovoltaic performance(PCE=7.13%)was obtained with a short-circuit current density(JSC)of 14.9 m A/cm^2,significantly higher than that of P2(PCE=2.23%).Generally,this study highlights that the strategy of inserting quinoid moieties into D–A polymers could be optional in LBG-polymers design and presents the importance and comparison of potentially competent core groups.
基金support granted by the National Research Foundation(NRF)(NRF2020M3H4A3081813)by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)(No.20183010013820)by the Korea Research Institute of Chemical Technology(KRICT)(No.KS2022-00)of the Republic of Korea。
文摘Design and synthesis of low bandgap(LBG) polymer donors is inevitably challenging and their processability from a non-halogenated solvent system remains a hurdle to overcome in the area of highperformance polymer solar cells(PSCs).Due to a high aggregation tendency of LBG polymers,especially diketopyrrolopyrrole(DPP)-based polymers coupled with bithiophenes in the polymer backbones,their widespread adoption in non-ha logena ted solvent-processed PSCs has been limited.Herein,a novel LBG DPP-based polymer,called PDPP4 T-1 F with asymmetric arrangement of fluorine atom,has been successfully synthesized and showed an outstanding power conversion efficiency(PCE) of 10.10% in a singlejunction fullerene-based PSCs.Furthermore,an impressive PCE of 13.21% has been achieved in a tandem device from a fully non-halogenated solvent system,which integrates a wide bandgap PDTBTBz-2 F polymer in the bottom cell and LBG PDPP4 T-1 F polymer in the top cell.The achieved efficiency is the highest value reported in the literature to date in fullerene-based tandem PSCs.We found that a uniformly distributed interpenetrating fibril network with nano-scale phase separation and anisotropy of the polymer backbone orientation for efficient charge transfer/transport and suppressed charge recombination in PDPP4 T-1 F-based PSCs led to outstanding PCEs in single and tandem-junction PSCs.
基金financially supported by the Research Program of 973 Program(No.2014CB643506)the National Natural Science Foundation of China(No.21401053)+2 种基金Project of Scientific Research and Development of Xiangyang(Year of 2013)Open Foundation of Hubei Key Laboratory of Low Dimensional Optoelectronic Materials and Devices(HLOM141003)Opening Project of Guangxi Colleges and Universities Key Laboratory of Beibu Gulf Oil and Natural Gas Resource Effective Utilization(No.2014KLOG03)
文摘In this article, we designed and synthesized a series of 5-（2,6-dimethyl-4H-pyran-4-ylidene）-1,3-diethyl-2-thioxodihydropyrimidine-4,6（1H, 5H）-dione（PD） unit based polymers（PFTDT, CZTDT, PHTDT and THTDT） for the first time. In these polymers, fluorene, 2,7-carbazole, phenothiazine and thiophene are employed as electron-donating groups and PD as electron-withdrawing group. TGA measurements demonstrated that these polymers possess good thermal stability（all above 377 °C）. Very broad absorption spectrum was also obtained from the polymer THTDT（300？850 nm）. CV characterization found that these polymers owned low highest occupied molecular orbital（HOMO） energy levels（？5.39 e V for THTDT, ？5.49 e V for CZTDT and ？5.78 e V for PFTDT） except for PHTDT（？5.17 e V）. The geometry and electronic properties of PFTDT, CZTDT, PHTDT and THTDT were investigated by means of theoretical calculation. All the above advantages demonstrate that PD based polymers could be candidates for electronic devices.
