本文通过无需催化剂的亲核取代反应获得了一种具有高度扭曲结构的多咔啉热激活延迟荧光(TADF)材料2,3,5,6-四(9H-吡啶并[2,3-b]吲哚-9-基)对苯二甲腈(4CbTPN)。该化合物在溶液和薄膜状态下的光致发光曲线的峰值分别在493和501nm处。较...本文通过无需催化剂的亲核取代反应获得了一种具有高度扭曲结构的多咔啉热激活延迟荧光(TADF)材料2,3,5,6-四(9H-吡啶并[2,3-b]吲哚-9-基)对苯二甲腈(4CbTPN)。该化合物在溶液和薄膜状态下的光致发光曲线的峰值分别在493和501nm处。较小的ΔEST,适度的光致发光量子产率(PLQY)和快速的反向隙间窜越速率(kRISC)实现了优秀的器件性能。基于26DCzppy主体的绿光TADF器件,可实现32.6 cd A^-1的电流效率(CE),25.6 lm W^-1的功率效率(PE)和12.9%的外量子效率(EQE),比之前报道基于4CzTPN的器件要高得多。这项研究表明,N-杂原子修饰可能会极大地影响能级分布和器件性能。展开更多
Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully con...Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA （2,7-dihromo-9-（heptadecan-9-yl）-9H- carbazole） and BB （4,7-bis（5-（trimethylstannyl）thiophen-2-yl）benzo[c][1,2,5]thiadiazole, TBT） type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT- b-PCDTBT block copolymers are verified via IH-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT：PC61BM blends, polymer solar ceils with an 8% increase of short circuit current （Jse） and 10% increase of power conversion efficiency （PCE） are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer： fullerene bulk heterojunction solar cells.展开更多
A series of novel hyperbranched polymers （HBPs） consisting ofa 2,7-subsituted 9-（heptadecan-9-yl）-9H-carbazole unit （A2＋A2＇） and a tetra-substituted green thermally activated delayed fluorescence （TADF） dye ...A series of novel hyperbranched polymers （HBPs） consisting ofa 2,7-subsituted 9-（heptadecan-9-yl）-9H-carbazole unit （A2＋A2＇） and a tetra-substituted green thermally activated delayed fluorescence （TADF） dye of 2,3,5,6-tetra（9H- carbazol-9-yl）-4-pyridinecarbonitrile （4CzCNPy, B4） have been synthesized via Suzuki cross-coupling reaction following an ＂Az＋A2＇＋B4＂ method. The polymers are named according to the polymerization ratio of 4CzCNPy monomer （5 mol%, 10 mol% and 15 mol% for HBPs of P2-P4 respectively, and 0 mol% for the control linear polymer P1）. Their thermal, optoelectronic and electrochemical properties have been characterized by a combination of techniques. All the polymers exhibit high thermal stability with the decomposition temperatures （Ta） above 400 ℃ and glass transition temperatures （Tg） up to 98℃. Unfortunately, the incorporation of TADF moiety into these HBP materials induced non-TADF characteristics. However, when the HBPs functionalized as the host for our previously developed 4CzCNPy TADF dopant in solution processed devices, maximum external quantum efficiency of 5.7% and current efficiency of 17.9 cd/A have been achieved in P3-based device, which is significantly higher than those of 1.5% and 4.2 cd/A for the linear polymer P1.展开更多
基金supported by the National Key Basic Research Program of China(973)(2015CB932202,2012CB933301)National Natural Science Foundation of China(61274065,51173081,61136003,BZ2010043,21373114,21573111,21003076,61505086,21304047)+6 种基金Science Fund for Distinguished Young Scholars of Jiangsu Province,China(BK20160039)Ministry of Education of China(IRT1148)Natural Science Foundation of Jiangsu Province,China(BM2012010,BK20141424)Priority Academic Program Development of Jiangsu Provincial Higher Education Institutions,China(YX030001)Ordinary University Graduate Student Practical Innovation Projects of Jiangsu Province,China(SJLX15_0390)Pandeng Project of Nanjing University of Posts and Telecommunications,China(NY214085)Open Foundation from Jilin University,China(IOSKL2015KF32)~~
基金supported by the National Key Basic Research Program of China(973)(2015CB932202,2012CB933301)National Natural Science Foundation of China(61274065,51173081,61136003,BZ2010043,51372119,51172110,21304047,21373114,21003076)+7 种基金Innovation Team of the Ministry of Education of China(IRT1148)Ministry of Education Humanities and Social Science Research Projects,China(13YJCZH091)Natural Science Foundation of Jiangsu Province,China(BK20141424)Priority Academic Program Development of Jiangsu Provincial Higher Education Institutions,China(YX030001)Ordinary University Graduate Student Practical Innovation Projects of Jiangsu Province,China(SJLX15_0390)Pandeng Project of Nanjing University of Posts and Telecommunications,China(NY214085)Open Foundation from Jilin UniversityChina(IOSKL2015KF32)~~
基金supported by the National Key R&D Program (No.2018YFA0208700 and No.2016YFA0200602)the National Natural Science Foundation of China (No.21688102 and No.21403222)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB17000000)the Youth Innovation Promotion Association of Chinese Academy of Sciences (No.2017224)
文摘本文通过无需催化剂的亲核取代反应获得了一种具有高度扭曲结构的多咔啉热激活延迟荧光(TADF)材料2,3,5,6-四(9H-吡啶并[2,3-b]吲哚-9-基)对苯二甲腈(4CbTPN)。该化合物在溶液和薄膜状态下的光致发光曲线的峰值分别在493和501nm处。较小的ΔEST,适度的光致发光量子产率(PLQY)和快速的反向隙间窜越速率(kRISC)实现了优秀的器件性能。基于26DCzppy主体的绿光TADF器件,可实现32.6 cd A^-1的电流效率(CE),25.6 lm W^-1的功率效率(PE)和12.9%的外量子效率(EQE),比之前报道基于4CzTPN的器件要高得多。这项研究表明,N-杂原子修饰可能会极大地影响能级分布和器件性能。
基金financially supported by the National Natural Science Foundation of China(No.21304047)Natural Science Foundation of Jiangsu Province(No.13KJB430017)+1 种基金Research Fund for the Doctoral Program of Higher Education(No.20133221120015)Synergetic Innovation Center for Organic Electronics and Information Displays
文摘Donor-acceptor （D-A） type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA （2,7-dihromo-9-（heptadecan-9-yl）-9H- carbazole） and BB （4,7-bis（5-（trimethylstannyl）thiophen-2-yl）benzo[c][1,2,5]thiadiazole, TBT） type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT- b-PCDTBT block copolymers are verified via IH-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT：PC61BM blends, polymer solar ceils with an 8% increase of short circuit current （Jse） and 10% increase of power conversion efficiency （PCE） are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer： fullerene bulk heterojunction solar cells.
基金financially supported by the National Natural Science Foundation of China(No.21304047)Natural Science Foundation of Jiangsu Province(No.BK2016042)Research Fund for the Doctoral Program of Higher Education(No.20133221120015)
文摘A series of novel hyperbranched polymers （HBPs） consisting ofa 2,7-subsituted 9-（heptadecan-9-yl）-9H-carbazole unit （A2＋A2＇） and a tetra-substituted green thermally activated delayed fluorescence （TADF） dye of 2,3,5,6-tetra（9H- carbazol-9-yl）-4-pyridinecarbonitrile （4CzCNPy, B4） have been synthesized via Suzuki cross-coupling reaction following an ＂Az＋A2＇＋B4＂ method. The polymers are named according to the polymerization ratio of 4CzCNPy monomer （5 mol%, 10 mol% and 15 mol% for HBPs of P2-P4 respectively, and 0 mol% for the control linear polymer P1）. Their thermal, optoelectronic and electrochemical properties have been characterized by a combination of techniques. All the polymers exhibit high thermal stability with the decomposition temperatures （Ta） above 400 ℃ and glass transition temperatures （Tg） up to 98℃. Unfortunately, the incorporation of TADF moiety into these HBP materials induced non-TADF characteristics. However, when the HBPs functionalized as the host for our previously developed 4CzCNPy TADF dopant in solution processed devices, maximum external quantum efficiency of 5.7% and current efficiency of 17.9 cd/A have been achieved in P3-based device, which is significantly higher than those of 1.5% and 4.2 cd/A for the linear polymer P1.
