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三种同分异构的双苯并吩噻嗪材料的合成、理论计算及光物理性质

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物理化学学报 2024年第1期40卷 48-56页

作者：王鹤然陈凯伏硕王晧暄袁加轩胡星奕许文娟密保秀南京邮电大学信息材料与纳米技术研究院有机电子与信息显示国家重点实验室南京210023

吩噻嗪及其衍生物材料是一类重要的多环芳烃材料,在光电子领域有着广泛的应用。其中,基于苯并噻嗪材料的研究相对较少。在本文中,我们分别在吩噻嗪的1,2-、2,3-和3,4-位引入苯基,制备了三种同分异构的双苯并吩噻嗪化合物D-PTZa、D-PTZb... 详细信息

吩噻嗪及其衍生物材料是一类重要的多环芳烃材料,在光电子领域有着广泛的应用。其中,基于苯并噻嗪材料的研究相对较少。在本文中,我们分别在吩噻嗪的1,2-、2,3-和3,4-位引入苯基,制备了三种同分异构的双苯并吩噻嗪化合物D-PTZa、D-PTZb和D-PTZc,研究了它们的构效关系,并与双吩噻嗪化合物(D-PTZ)进行了对比。研究发现,D-PTZb和D-PTZc的HOMO和LUMO分布与D-PTZ的类似;对于D-PTZa,其1,2-位引入的苯基与中间的苯环空间张力较大,造成空间结构极度扭曲,性质比较特殊。并苯的引入可以有效增加分子的共轭长度,使得最大吸收波长发生红移;在2,3-位引入苯基可以有效地稳定HOMO能级,使基于π→π*跃迁的能隙稍有增大,呈现蓝光发射,溶液的荧光量子产率为1.7%;而在3,4-位引入苯基使LUMO分布更加趋向于线型,从而使LUMO更加稳定,使基于π→π*跃迁的能隙降低,其最大发射峰位于520 nm处,呈现黄绿光发射,溶液荧光量子产率为13%。此外并入苯环之后,空间张力增大,化合物的分解温度降低。我们的分子设计和结构–性质关系的研究可以为设计新的吩噻嗪材料提供基础指导。

关键词：苯并吩噻嗪有机光电材料密度泛函理论空穴-电子分析前线轨道分布光物理性质

Recent progress in the numerical modeling for organic thin film solar cells

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Science China(Physics,Mechanics & Astronomy) 2011年第3期54卷 375-387页

作者： ZHAO XinYan mi baoxiu GAO ZhiQiang HUANG Wei Key Laboratory for Organic Electronics & Information Displays (KLOEID) Institute of Advanced Materials (IAM) Nanjing University of Posts & Telecommunications Nanjing 210046 China Jiangsu Engineering Centre for Flat-Panel Displays & Solid-State Lighting School of Materials Science & Engineering Nanjing University of Posts & Telecommunications Nanjing 210046 China

Device modeling is constructive in finding the dependency of devices efficiency on structure parameters and material properties. For the sake of looking into the physics mechanism of organic solar cells (OSCs), as well as predicting their maximum attainable efficiency, numerical modeling is widely utilized to simulate the behavior of OSCs. Although some indispensable parameters are neglected or hypothesized because of inexplicitness in simulation models for OSCs, numerical modeling can describe the kinetic process in OSCs intuitively. This paper summarizes the optical/electrical models in the BHJ solar cell, as well as addresses their corresponding development in recent years on the basis of device physics and its working principle. Applications of numerical modeling and comments on modeling results are summarized. Meanwhile, precision and open questions about every model are discussed.

关键词：薄膜太阳能电池数值模拟有机太阳能电池设备效率器件建模动力学过程材料特性结构参数

Fabrication of Cr-doped SrTiO3/Ti-dopedα-Fe_(2)O_(3) photoanodes with enhanced photoelectrochemical properties

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Journal of Materials Science & Technology 2020年第21期56卷 189-195页

作者： Dapeng Cao Jingbo Zhang Anchen Wang Xiaohui Yu baoxiu mi Key Laboratory for Organic Electronics&Information Displays(KLOEID) Jiangsu Engineering Centre for Plate Displays&Solid State Lightingand Institute of Advanced Materials(IAM)Nanjing University of Posts&TelecommunicationsNanjing 210023China Key Laboratory of Flexible Electronics Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM)School of Material Science and EngineeringNanjing University of Posts&TelecommunicationsNanjing 210023China

Cr-doped Sr TiO_(3)/Ti-dopedα-Fe_(2)O_(3) heterojunction has been constructed by an ingenious way,*** segregation titanium oxide on the surface of the Ti-dopedα-Fe_(2)O_(3) electrode to in situ prepare Cr-doped SrTiO_(3).After construction of the heterojunction,the photocurrent onset potential for water oxidation on a Ti4+dopedα-Fe_(2)O_(3) cathodically shifts by about 100 ***,the cathodic shift of the onset potential can be preserved well even after a long time *** results indicate the effectiveness and credibility of the fabricated *** order to make clear the reason for the onset potential shift,the asprepared Ti-dopedα-Fe_(2)O_(3) and Cr-doped SrTiO_(3)/Ti-dopedα-Fe_(2)O_(3) samples were investigated by X-ray photoelectron spectroscopy,electrochemical impedance spectroscopy,X-ray diffraction spectroscopy,*** on the experimental evidences,it is proposed that cathodic shift of the onset potential is mainly due to the enhanced charge separation at the photoanode *** strategy can offer a reference to construct heterojunction on other films especially for those with surface segregation.

关键词： Photoelectrochemical Water splitting α-Fe_(2)O_(3) Cr-doped SrTiO_(3) Heterojunction Charge separation

Label-Free DNA Sensors Based on Field-Effect Transistors with Semiconductor of Carbon Materials

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Chinese Journal of Chemistry 2015年第8期33卷 828-841页

作者： Lu Zhao Dapeng Cao Zhiqiang Gao baoxiu mi Wei Huang Key Laboratory for Organic Electronics and Information Displays & Institute of A dvanced Materials Jiangsu National Synergetic Innovation Center for Advanced Materials Nanjing University of Posts & Telecommunications Nanjing Jiangsu 210023 China Key Laboratory of Flexible Electronics & Institute of Advanced Materials Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM) Nanjing Tech University Nanjing Jiangsu 211816 China

Over one decade, various DNA sensors of carbon material-based field-effect transistors （FETs） have been inten- sively developed into an inspiring area of research and technology to substitute for the traditional method, for in- stance, fluorescence labeling detection. These FET DNA sensors have advantages of： directly read-out electrical signal, no need to label DNA molecule with fluorescer, high sensitivity, facility of miniaturization, simple device preparation process, high signal-to-noise ratio （SNR） and wide detection range. This review gives a comprehensive description on the state-of-the-art carbon-based FET DNA sensors from the aspect of both semiconductor material and structure of device. Several essential points in this research field, including sensitivity, selectivity, stability and challenges are addressed. Optimization of sensing performance and application of these devices are also discussed.

关键词： DNA carbon-based FET immobilization hybridization sensitivity

Convenient and inexpensive determination of optical constants and film thickness of blended organic thin film

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Science China(Physics,Mechanics & Astronomy) 2015年第2期58卷 26-32页

作者： LIANG QiYing CHEN Jie LI Xin GAO ZhiQiang mi baoxiu YANG ZhenHua Jiangsu Engineering Centre for Flat-panel Displays & Solid-state Lighting and College of Materials Science & Engineering Nanjing University of Posts & Telecommunications Key Laboratories for Organic Electronics & Information Displays (KLOEID) and Institute of Advanced Materials (IAM) Nanjing University of Posts & Telecommunications College of Science Nanjing University of Posts & Telecommunications

This work presents the study of optical constants and film thickness of blended organic thin films, emphasizing on the modeling procedure with modified genetic algorithm aided by absorption or transmittance spectra of both pure materials and the blends. Taking the blending of copper phthalocyanine(Cu Pc) and fullerene(C60) as an example, a simple, convenient and low-cost method for the determination of the optical constants and film thickness of blended organic thin films was demonstrated. New scheme for optical modeling of blended organic thin film was proposed by introducing peak energies of Cody-Lorentz oscillators of the pure materials, which were determined by fitting the film absorption of pure materials. These oscillators of pure materials could be recognized in the transmittance spectrum of their blends, and were further used as the initial searching ranges in the simulation of blended films. As a result, the constraint bounds of the unknown parameters were significantly reduced and modeling efficiency as well as fitting accuracy was improved. For instance, the fitting of the transmittance curves of blended films with different blending ratios reached reliable results in comparison with extinction coefficients obtained from experiment.

关键词：有机薄膜光学常数混合比例膜厚度测定透射光谱建模效率消光系数比

Influences of fluorination on homoleptic iridium complexes with C^N=N type ligand to material properties, ligand orientation and OLED performances

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Science China Chemistry 2015年第4期58卷 640-649页

作者： Chen Liu Le Mao Haoxin Jia Zhangjin Liao Hongjiao Wang baoxiu mi Zhiqiang Gao Key Laboratory for Organic Electronics & Information Displays (KLOEID) Jiangsu Engineering Centre for Plate Displays & Solid State Lighting Institute of Advanced Materials (IAM) School of Material Science and EngineeringNanjing University of Posts & Telecommunications

Two new iridium complexes with C^N=N type ligand(i.e., Ir(BFPPya)3{tris[3,6-bis(4-fluorophenyl)pyridazine]iridium(III)} and Ir(BDFPPya)3{tris[3,6-bis(2,4-di-fluorophenyl)pyridazine]iridium(III)}) attaching with fluorine atoms, were synthesized and the effects of fluorination on the material properties and device performance were investigated. Compared with our previously reported fluorine-free analogue material, that is Ir(BPPya)3{tris[3,6-bis(phenyl)pyridazine]iridium(III)}, blue shifts in the emission spectra as well as in the long wavelength region of the absorptions were observed. The photoluminescence quantum yield(PLQY)(0.44 and 0.84 vs. 0.29), phosphoresces lifetime(0.88 and 1.31 vs. 0.66 μs), and oxidation potential(1.10 and 1.37 vs. 0.95 V) increased obviously after fluorinating the ligand. In contrast, the thermal stability of the iridium complexes decreased slightly(Td: 435 and 402 vs. 440 °C). In the density functional theory(DFT) calculations, by comparing the steric shape of the three ligands within one optimized molecule, orientational differences among the complexes were observed. In OLED device studies, bluish green electroluminescence with peak emission of 500 nm, using the electron-transporting host of TPBI [2,2',2''-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole)] and the most fluorinated dopant of Ir(BDFPPya)3, was achieved with maximum efficiency of 20.3 cd/A. On one hand this efficiency is not satisfactory considering a high PLQY of 0.84. On the other hand with the similar device structure, that the(HOMO-LUMO)s of all the dopants are wrapped within that of the host TPBI, and all the triplet energies of the dopants are smaller than that of the host TPBI, it is abnormal that the ordering of device efficiencies is contradictory to that of PLQY. Assisting with the phosphorescent spectrum of TPBI and the absorption spectra of the dopant, the contradiction was interpreted reasonably.

关键词：铱配合物材料特性器件性能氟化配体 OLED N型二氟苯基

Heat revolution on photophysical properties and electroluminescent performance of Ir(ppy)_3-doped bipolar host of oxadiazole derivatives attaching with inert group of tert-butyl moiety

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Science China Chemistry 2014年第6期57卷 849-856页

作者： WANG HongJiao LIU Chen mi baoxiu SANG Jie LI Xin GAO ZhiQiang Jiangsu Engineering Centre for Flat-Panel Displays & Solid-state Lighting College of Materials Science & EngineeringNanjing University of Posts & Telecommunications Key Laboratory for Organic Electronics & Information Displays (KLOEID) Institute of Advanced Materials (IAM)Nanjing University ofPosts & Telecommunications

Two bipolar materials,2,5-bis(2-(9H-carbazole-9-yl)phenyl)-1,3,4-oxadiazole(o-CzOXD)and 2,5-bis(2-(3',6'-di-tert-butyl-9H-carbazole-9-yl)phenyl)-1,3,4-oxadiazole(tBu-o-CzOXD),were synthesized according to reported *** parallel study,it was demonstrated that introduction of inert tert-butyl group improved material thermal stability,even though this modification only had a slight influence to the photophysical and electrochemical properties of these materials.A comparative study focusing on effects of heat treatment was carried out on the quartz glass substrates with vacuum deposited films containing one of the bipolar host doped with 6 wt%fac-tris(2-phenylpyridinato-N,C2’)iridium(Ir(ppy)3).Results show that when the two samples were heated,the absorption,emission,and photo images of the host:dopant system changed,with the o-CzOXD suffering more severe degradation under high temperature,which is consistent with their thermal *** addition,it was proved that the high temperature-annealed host:dopant system can enhance the emission of the *** finding was used as a guideline to improve our device *** fabricated two types of phosphorescent organic light-emitting devices(PhOLEDs),one was based on o-CzOXD,the other was based on *** had analogous *** investigated the effect of heat on device performance by selectively *** these two freshly prepared devices exhibited similar performance,when annealed at 90°C for 10 min,the OLEDs based on tBu-o-CzOXD showed significant performance enhancement,which can be attributed to the observation that annealing Ir(ppy)3 doped host can change film morphology and enhance the dopant *** maximum efficiencies of the freshly prepared tBu-o-CzOXD device were 25.8 cd A-1,23.1lm W-1,and 9.3%;whereas those for annealed device were 47.0 cd A-1,42.2 lm W-1,and 13.4%.

关键词：光物理特性掺杂剂叔丁基主机双极电致发光惰性衍生物

A thermal stable cathode buffer based on an inexpensive tetranuclear zinc(Ⅱ) complex for organic photovoltaic devices

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Science China Chemistry 2012年第12期55卷 2562-2566页

作者： LI ZhiGang GAO ZhiQiang WANG HaiShan ZHANG Hui ZHAO XinYan mi baoxiu HUANG Wei Jiangsu Engineering Centre for Flat-Panel Displays&Solid-state Lighting and School of Materials Science&Engineering Nanjing University of Posts&Telecommunications Nanjing 210046China Key Laboratory for Organic Electronics&Information Displays(KLOEID)and Institute of Advanced Materials(IAM) Nanjing University of Posts&TelecommunicationsNanjing 210046China

An inexpensive material,i.e.,tetranuclear zinc(Ⅱ) complex,(Zn4O(AID)6) [AID = 7-azaindolate],was utilized as a cathode buffer in organic photovoltaic(OPV) devices,leading to the improvement of device *** to OPV devices based on a conventional cathode buffer of TPBi(1,3,5-tris(2-N-phenylbenzimidazolyl)benzene),although the freshly prepared devices showed similar performance,when heated to a series of high temperatures under air,the short circuit current and the open circuit voltage of the Zn4O(AID)6 devices dropped more slowly,indicating the superiority of using Zn4O(AID)6 as a cathode buffer over TPBi in OPV devices.

关键词：光伏器件缓冲阴极四核热稳定苯并咪唑基设备利用锌

Pure aromatic hydrocarbons with meta-linked phenyl-core and perihedral fluorene substitutions with/without inert groups of tert-butyl： bipolar hosts for blue phosphorescence

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Science China Chemistry 2017年第2期60卷 223-230页

作者： Gaowen Liu Chuanjun Wang baoxiu mi minjie Zhuo Changjin Ou Jie Wang Shuchao Zheng Juan Song Zhiqiang Gao Dapeng Cao Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM) Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM) Nanjing University of Posts & Telecommunications Nanjing 210023 China. School of Material Science and Engineering Jiangsu Engineering Centre for Flat-Panel Displays & Solid-state Lighting Nanjing University of Posts &Telecommunications Nanjing 210023 China

Two pure hydrocarbon molecules of l,3,5-tris(9-phenyl-9H-fluoren-9-yl)benzene(mTPFB)and l,3,5-tris(2-tert-butyl-9-phenyl-9H-fluoren-9-yl)benzene(tBu-mTPFB)were *** to the conjugation blocked connection mode and rigid/bulky substitutions,these two materials possess high triplet energy,enabling them as good hosts for blue phosphor in *** studying their thermal,electrochemical,electronic absorption and photoluminescent properties,it was found that the influence of the inert tert-butyl group on material photoelectrical properties is *** instance,mTPFB and tBu-mTPFB showed very similar absorption and emission profiles,with almost the same bandgap,triplet energy and energy ***,the encapsulation of tert-butyl on the 2-position of 9-phenylfluorene enhanced material thermal *** importantly,carrier transport properties were improved dramatically,as proved by the mono carrier *** phosphorescent OLEDs hosted by tBu-mTPFB showed external quantum efficiency of 15.2%and current efficiency of 23.0 cd/A,which were much higher than that of the OLEDs based on mTPFB with the analogous structure.

关键词：磷光OLED 联苯基叔丁基惰性组蓝色电子吸收光谱主机双极