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1.
本文主要是通过分析吸收光谱性质来区分用于体异质结聚合物太阳能电池的两种不同桥联低带隙给受体共聚物PCPDTBT和PSBTBTS的激发态特征,进而通过分析电荷转移态(CT)特征来区分二者实现电荷分离的难易程度. 利用密度泛函理论(DFT/TD-DFT)B3LYP和CAM-B3LYP方法计算PSBTBT和PCPDTBT(n=1~4)的电子结构和光谱性质. 结果表明,从吸收光谱来看,PSBTBT与PCPDTBT的光谱相似,与太阳光谱的匹配能力相当. 而激子解离能表明二者的电荷转移态(CT)电荷分离的难易程度也相当. 然而用Si原子取代C原子后,C-Si键长明显长于C-C键长,降低了噻吩环和烷基链间的空间位阻,从而可能有利于其结晶度的提高,更加有利于载流子的传输,因此从理论上说明PSBTBT也可能具备高效太阳能电池给体材料的潜质.  相似文献   

2.
设计和合成结构新颖的聚合物太阳能电池给体材料是有机电子学的热点研究领域. 首先利用二噻吩取代的苯并二噻吩(DBDT)作为富电子结构单元, 吡咯并吡咯二酮(DPP)作为缺电子单元构筑了一种新的聚合物太阳能电池电子给体材料(PDBDTDPP), 然后以[6,6]-苯基-C61-丁酸甲酯(PC61BM)作为电子受体, 借助密度泛函理论(DFT)方法结合不相干的Marcus-Hush电荷传输模型, 系统研究了PC61BM-DBDTDPPn=1,2,3,∞体系的分子结构、电子性质、光吸收性质、电荷转移的内重组能和外重组能、激子结合能、电荷传输积分、给体-受体界面上激子分离和电荷复合速率等性质, 并利用线性回归方法分析了聚合物重复单元与其光伏性质的关系. 结果表明, 该聚合物具有较好的平面结构, 低的最高占据分子轨道(HOMO)能级, 在紫外-可见区具有宽且强的光学吸收、较大的激子束缚能(1.365 eV), 小的激子分离内重组能(0.152 eV)和电荷复合内重组能(0.314 eV). 在给体-受体界面上, 激子分离速率高达1.073×1014 s-1, 而电荷复合速率仅为1.797×108 s-1. 相比较而言, 激子分离速率比电荷复合速率高约6个数量级, 表明在给体-受体界面上, 光生激子具有很高的分离效率. 总之, 研究证明PDBDTDPP是一个非常有前途的聚合物太阳能电池给体材料, 值得实验上进一步合成及器件化研究. 理论研究不仅有助于更深入理解有机化合物结构与其光学、电子性质之间的关系, 还可以为合理设计聚合物太阳能电池给体材料提供有价值的参考.  相似文献   

3.
设计合成了2种聚芳香炔铂共轭高分子给体(聚合物1, 3)和一种芳香炔铂共轭高分子受体(聚合物2), 并对其光物理特性进行了研究. 聚合物3被激发后, 与聚合物2之间既可以发生激发单重态-单重态的电子转移, 也可以发生激发三重态-三重态的电子转移. 分别对聚芳香炔铂共轭高分子给体和芳香炔铂共轭高分子受体组成的太阳能电池的特性进行了研究. 其弱的光伏特性归因于明显的激发单重态-单重态电子转移过程及此类高分子较低的导电特性. 电致发光实验结果表明, 聚合物3的阳离子自由基主要由其激发三重态决定.  相似文献   

4.
合成了5,8-二溴蒽醌-2,3-二羧酸,进一步制备出相应的酸酐和一个新的电子受体——N-(1-己基庚基)-5,8-二溴蒽醌-2,3-二羧酸酰亚胺.该化合物的活性很高,可通过钯配合物催化的偶联反应与不同的电子给体进行聚合获得相应的给受体型共轭聚合物.在计算机模拟的辅助下,设计合成了2个聚合物.聚合物P1选用苯并双噻吩衍生物作为电子给体基元,而P2在P1的基础上,选用3,4-乙烯二氧噻吩作为连接基元,两个聚合物的吸收波长覆盖整个可见光区.聚合物的LUMO(最低未占分子轨道)能级在-3.85 eV左右,且具有很好的溶解性,可与(6,6)-苯基-C61-丁酸甲酯掺杂制备出体异质结光探测器件.P2制备的光探测器件,在-4 V的偏压下,505 nm处EQE为26%,相应的归一化探测率(D*)为2.2×1011Jones.  相似文献   

5.
近年来,基于给体-受体(D-A)型共轭聚合物的电致变色器件表现出响应速率快、颜色可调、良好的循环稳定性等诸多优点,受到广泛关注.设计了一类以三苯胺为电子给体,喹喔啉衍生物为电子受体的新型给体-受体-给体(D-A-D)型化合物5,8-二(4-(二苯基氨基)苯基)-2,3-二甲基喹喔啉(Q1)和6,9-二(4-(二苯基氨基)苯基)-1,2,3,4-四氢吩嗪(Q2),通过电化学聚合制备了D-A型聚合物聚(5,8-二(4-(二苯基氨基)苯基)-2,3-二甲基喹喔啉)(PQ1)和聚(6,9-二(4-(二苯基氨基)苯基)-1,2,3,4-四氢吩嗪)(PQ2).研究表明,该类新型的D-A型聚合物在中性时为浅黄色,且随着电压的增大呈现多种颜色变化.该类电致变色材料具有响应时间快、着色效率较高、循环稳定性良好等优点,且其在780 nm附近的最大光学对比度均超过70%,具有潜在的应用价值.  相似文献   

6.
设计合成了2种宽带隙聚合物给体,分别命名为PDTz-BDD和PDTz-BDT.其中, PDTz-BDT是一种典型的给-受体(D-A)型共轭聚合物, PDTz-BDD是具有受体1-受体2(A1-A2)型结构的共轭聚合物.采用BTP-e C9作为受体,分别与PDTz-BDD和PDTz-BDT共混构建有机太阳能电池,系统研究了两种给体的光伏性能.研究结果表明,具有A1-A2型结构的PDTz-BDD表现出更强的光吸收能力、更明显的溶液聚集效应与更优良的器件形貌,相应的光伏电池可以实现更高的光电转换效率(10.36%).本文不仅设计合成了2种新型给体,而且为构建A1-A2型共聚物以开发高效聚合物给体提供了参考.  相似文献   

7.
在芴苯结构主链中引入苯并噻唑作为电子受体、侧链上引入N,N-二丁基苯胺作为电子给体,通过Suzuki反应制备了新型交叉共轭聚合物P1,同时合成主链中不含苯并噻唑的芴苯类共聚物P2作为对比;对两者的化学结构和光物理性质进行了表征,并研究了聚合物对离子的光学传感性能.实验和模拟计算结果均表明,P1中存在着强的分子内电荷转移效应;引入电子给体和受体(D-A)能够有效地调控交叉共轭聚合物的光学特性,这种D-A型交叉共轭聚合物是一类潜在的具有荧光增强性能的化学传感材料.  相似文献   

8.
采用密度泛函理论预测了6个萘二酰亚胺(NDI)衍生物电子受体分子An(n=1~6)的几何构型、前线轨道特征及吸收光谱,并分别与选定的3个给体分子Dm(m=1~3)组合,构建给-受体(D-A)界面,从单分子尺度评估了不同D-A界面载流子的复合程度.结果表明,引入N、O、S等杂原子可以改变分子间氢键位点及强度,调节D-A界面分子间的距离与位移,以降低界面载流子复合,通过减小光电压损失获得高的开路电压V_(oc);此外,通过计算给体HOMO~D与受体LUMO~A之间的电子耦合V_(if)发现,平面性均较好的D-A分子组合V_(if)较大,界面载流子易于复合,会引起较大的光电压损失,不利于获得高的V_(oc).将平面性好的受体与非平面型给体材料搭配作为有机太阳能电池光活性层有可能获得高的V_(oc).综合考虑ΔE_L、V_(if)、D-A分子的平面性和光吸收效率等因素,认为D3-A5组合有望成为电子迁移率高、可见光和近红外区吸收宽、界面激子能有效分离且不易复合的理想给-受体分子组合对.  相似文献   

9.
设计并理论预测了一系列A'-π-A-π-A'型苯并噻二唑衍生物电子受体分子的几何构型、前线轨道特征、吸光性质及电子重组能等信息,同时考察了丙酮、氯苯溶剂对其性质的影响. 在此基础上将性能优异的受体分子与特定给体分子组合构建给-受体(D-A)界面,通过计算给体HOMO与受体LUMO之间的电子耦合Vif,评估了D-A界面载流子的复合程度. 结果表明,合理选择取代基对核心受体苯并噻二唑进行修饰是调节LUMO能级和能隙的有效方法. 将平面性好的受体材料与非平面型给体材料搭配作为有机太阳能电池光活性层材料,有可能达到降低界面复合、减小光电压损失和提高开路电压的目的. 综合考虑ΔEL,Vif,光吸收效率及溶剂化效应等因素,D1-1aγ及D1-2aγ组合有望成为电子迁移率高、在可见光和近红外区吸收宽、界面激子可以有效分离且不易复合的理想给-受体分子组合.  相似文献   

10.
姚惠峰  侯剑辉 《高分子学报》2016,(11):1468-1481
高性能聚合物光伏材料对于推动聚合物太阳能电池领域的发展具有十分重要的作用.随着研究的深入,聚合物光伏材料从早期的聚噻吩体系逐步发展到具有推拉电子作用的给体-受体(D-A)交替共聚物,其相应的器件光伏效率也从最初的1%左右提升到如今超过11%.近十年来,种类繁多的给受体单元被开发并应用于聚合物材料的构建中,其中基于苯并二噻吩(BDT)单元的聚合物材料因为具有良好的光伏性能,得到了十分广泛的应用.近年来,非富勒烯受体的迅速发展给聚合物太阳能电池的研究注入了新的活力,BDT类聚合物在基于非富勒烯受体的聚合物太阳能电池中也展现出重要的作用,已经获得了超过11%的光电转化效率.本文简要介绍了我们在高性能聚合物光伏材料的设计与应用中的相关工作,主要分为聚噻吩和苯并二噻吩材料的设计与应用、活性层形貌调控以及非富勒烯聚合物太阳能电池的相关研究.  相似文献   

11.
We report on the electronic structure of poly[2,6‐(4,4‐bis‐ (2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7(2,1,3‐benzothiadiazole)] (PCPDTBT), a promising low‐band‐gap donor material for efficient bulk heterojunction organic solar cells. Electronic properties of interfaces formed between PCPDTBT and prototypical electrodes [Au, indium‐tin‐oxide and poly(ethylene‐dioxythiophene): poly(styrenesulfonate)], obtained from X‐ray photoemission spectroscopy and ultraviolet photoemission spectroscopy, are evaluated. The formation of interface dipoles is observed, and their consequences for device performance are discussed. For the system PCPDTBT/Au chemical interactions occur, which may affect in particular the charge extraction at the corresponding interface.  相似文献   

12.
The dependence of the thin film morphology and excited-state dynamics for the low-bandgap donor-acceptor copolymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) in pristine films and in blends (1:2) with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) on the use of the solvent additive 1,8-octanedithiol (ODT) is studied by solid-state nuclear magnetic resonance (NMR) spectroscopy and broadband visible and near-infrared pump-probe transient absorption spectroscopy (TAS) covering a spectral range from 500-2000 nm. The latter allows monitoring of the dynamics of excitons, bound interfacial charge-transfer (CT) states, and free charge carriers over a time range from femto- to microseconds. The broadband pump-probe experiments reveal that excitons are not only generated in the polymer but also in PCBM-rich domains. Depending on the morphology controlled by the use of solvent additives, polymer excitons undergo mainly ultrafast dissociation (<100 fs) in blends prepared without ODT or diffusion-limited dissociation in samples prepared with ODT. Excitons generated in PCBM diffuse slowly to the interface in both samples and undergo dissociation on a time scale of several tens of picoseconds up to hundreds of picoseconds. In both samples a significant fraction of the excitons creates strongly bound interfacial CT states, which exhibit subnanosecond geminate recombination. The total internal quantum efficiency loss due to geminate recombination is estimated to be 50% in samples prepared without ODT and is found to be reduced to 30% with ODT, indicating that more free charges are generated in samples prepared with solvent additives. In samples prepared with ODT, the free charges exhibit clear intensity-dependent recombination dynamics, which can be modeled by Langevin-type recombination with a bimolecular recombination coefficient of 6.3 × 10(-11) cm(3) s(-1). In samples prepared without ODT, an additional nanosecond recombination of polaron pairs is observed in conjunction with an increased intensity-independent trap-assisted nongeminate recombination of charges. Furthermore, a comparison of the triplet-induced absorption spectra of PCPDTBT with the charge-induced absorption in PCPDTBT:PCBM blends reveals that triplets have a very similar excited-state absorption spectrum compared to the free charge carriers, however, in contrast have a distinct intensity-independent lifetime. Overall, our results suggest that whether free charges or strongly bound CT states are created upon dissociation of excitons at the PCPDTBT:PCBM interface is determined instantaneously upon exciton dissociation and that once formed strongly bound CT states rapidly recombine and thus are unlikely to dissociate into free charges. The observation of a significantly larger bimolecular recombination coefficient than previously determined for poly(3-hexylthiophen-2,5-diyl):PCBM (P3HT:PCBM) and PCDTBT:PCBM samples indicates that nongeminate recombination of free charges considerably competes with charge extraction in PCPDTBT:PCBM photovoltaic devices.  相似文献   

13.
Ye  Linglong  Li  Xueshan  Cai  Yunhao  Ryu  Hwa Sook  Lu  Guangkai  Wei  Donghui  Sun  Xiaobo  Woo  Han Young  Tan  Songting  Sun  Yanming 《中国科学:化学(英文版)》2020,63(4):483-489
Benzo[1,2-b:4,5-b′]dithiophene(BDT) has been widely used to construct donor-acceptor(D-A) copolymers in organic solar cells(OSCs). However, benzo[1,2-b:4,5-b′]difuran(BDF), an analogue of BDT, has received less attention than BDT. The photovoltaic performance of BDF copolymers has lagged behind that of BDT copolymers. Here, we designed and synthesized two BDF copolymers, PBF1-C and PBF1-C-2Cl. PBF1-C-2Cl, which is composed of BDF and benzo[1,2-c:4,5-c′]dithiophene-4,8-dione connected by a chlorinated thiophene π-bridge, displays a low-lying highest occupied molecular orbital energy level,which helps in yielding a high open-circuit voltage(V_(oc)) in OSCs. As a result, when blended with Y6, PBF1-C-2Cl-based devices showed a high V_(oc) of 0.83 V and a power conversion efficiency(PCE) of 13.10%. To the best of our knowledge, the PCE of 13.10% is among the highest efficiency values for OSCs based on BDF copolymers.  相似文献   

14.
Proper functionalization of indolo[3,2-b]carbazole led to a new class of high-performance organic semiconductors suitable for organic thin-film transistor (OTFT) applications. While 5,11-diaryl-substituted indolo[3,2-b]carbazoles without long alkyl side chains provided amorphous thin films upon vacuum deposition, those with sufficiently long alkyl side chains such as 5,11-bis(4-octylphenyl)indolo[3,2-b]carbazole self-organized readily into highly crystalline layered structures under similar conditions. OTFTs using channel semiconductors of this nature exhibited excellent field-effect properties, with mobility up to 0.12 cm(2) V(-1) s(-1) and current on/off ratio to 10(7). As this class of organic semiconductors has relatively low HOMO levels and large band gaps, they also displayed good environmental stability even with prolonged exposure to amber light, an appealing characteristic for OTFT applications.  相似文献   

15.
采用化学浴(CBD)法在TiO2薄膜表面制备结晶性Sb2S3膜层, 获得了TiO2/Sb2S3平板异质结, 并结合聚[2,6-{4,4-双-(2-乙基己基)-4H-环戊并[2,1-b;3,4-b']-二噻吩}-交替-4,7-(2,1,3-苯并噻二唑)](PCPDTBT)空穴传输层和MoO3电极界面修饰层, 制备了FTO/TiO2/Sb2S3/PCPDTBT/MoO3/Au平板结构太阳能电池, 研究了CBD方法中热退火气氛对Sb2S3薄膜的组成、 结构及光伏性能的影响. 结果表明, 在N2气氛下退火时, 所得的Sb2S3膜层不致密且含有Sb2O3杂相, 电池效率仅为0.90%; 而在N2-S气氛下退火时, 硫会与杂相Sb2O3发生反应生成Sb2S3, 进而得到纯净、 致密、 平整的结晶Sb2S3膜层. 在平板结构太阳能电池中, 光生空穴对电池光电流的产生有明显的贡献; 随着Sb2O3杂相的消除, Sb2S3薄膜中载流子的复合减少且传输速率增大, 使太阳能电池器件中电子与空穴的收集效率和短路电流显著提高, 电池效率提高了1.34倍, 达到2.04%.  相似文献   

16.
A novel highly π-extended heteroarene with eight fused aromatic rings, dianthra[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DATT), was selectively synthesized via a newly developed synthetic strategy, fully characterized by means of single crystal X-ray structural analysis, and examined as an organic semiconductor in thin film transistors. Even with its highly extended acene-like π-system, DATT is a fairly air-stable compound with IP of 5.1 eV. Single crystal X-ray structural analysis revealed its planar molecular structure and the lamella-like layered structure with typical herringbone packing. Theoretical calculations of the solid state electronic structure based on the bulk single crystal structure suggest that DATT affords almost comparable intermolecular orbital couplings between HOMOs (t(HOMO)) with those of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT), implying its good potential as an organic semiconductor for organic field-effect transistors. In fact, field-effect mobilities as high as 3.0 cm(2) V(-1) s(-1) were achieved with vapor-processed DATT-based devices, which is comparable with that of DNTT-based devices. The molecular ordering of DATT in the thin film state, however, turned out to be not completely uniform; as elucidated by in-plane and out-of-plane XRD measurements, the face-on molecular orientation was contaminated in the edge-on orientation, the former of which is not optimal for efficient carrier transport and thus could limit the mobility.  相似文献   

17.
The kinetics of photodegradation and the reactivity of different sites of the low‐band‐gap polymers poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] (C‐PCPDTBT) and poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]silole)‐alt‐4,7‐(2,1,3‐benzothiadiazole)] (Si‐PCPDTBT) are investigated as thin films and are compared to those of poly(3‐hexylthiophene) (P3HT). The decay kinetics are monitored with UV/Vis spectroscopy and the reactivity and product evolution are investigated with X‐ray photoelectron spectroscopy (XPS). Both polymers exhibit higher stability than P3HT. The bridging atom in the cyclopentadithiophene (CPDT) subunit has a significant influence on the stability. Varying oxidation rates for the different elements were observed. In the case of Si‐PCPDTBT, the silicon atom is oxidized primarily, whereas the photooxidation rates of the other elements are reduced relative to C‐PCPDTBT. Additionally, XPS experiments with varying excitation energies reveal a significant reaction gradient within a few nanometers of the surface of degraded thin films of C‐PCPDTBT.  相似文献   

18.
A new synthesis of 5α-androstano[3,2-b]pyridin-17β-ol acetate (VIa) and 17-methyl-5α-androstano[3,2-b]pyridin-17β-ol (VIb), first reported by Shimizu, Ohta, Ueno, and Takegoshi, was achieved. The analogous 5α - androstano[17,16-b]pyridin-3β-ol (XII), 5α-androstano[17,16-b]pyridin-3-one (XIVa), and androst-4-eno[17,16-b]pyridin-3-one (XIVb) were also prepared. An illustration of the method follows. Condensation of 3β-hydroxy-5α-androstan-17-one (VIIa) with 3-(2-furyl)acrolein afforded 16-[3-(2-furyl)-2-propenylidene]-3β-hydroxy-5α-androstan-17-one (VIIIa), the oxime (IXa) of which was thermally cyclized to 5α-androstano[17,16-b]-6′-(2-furyl)pyridin-3β-ol (Xa). 3β-Hydroxy-5α-androstano[17,16-b]pyridine-6′-carboxylic acid (XI) was obtained by ozonolysis of Xa. Thermal decarboxylation of XI gave XII. Cinnamaldehyde was used in place of 3-(2-furyl)acrolein to give the corresponding phenylpyridines.  相似文献   

19.
A straightforward synthetic approach that exploits linear- and angular-shaped naphthodithiophenes (NDTs) being potential as new core structures for organic semiconductors is described. The newly established synthetic procedure involves two important steps; one is the chemoselective Sonogashira coupling reaction on the trifluoromethanesulfonyloxy site over the bromine site enabling selective formation of o-bromoethynylbenzene substructures on the naphthalene core, and the other is a facile ring closing reaction of fused-thiophene rings from the o-bromoethynylbenzene substructures. As a result, three isomeric NDTs, naphtho[2,3-b:6,7-b']dithiophene, naphtho[2,3-b:7,6-b']dithiophenes, and naphtho[2,1-b:6,5-b']dithiophene, are selectively synthesized. Electrochemical and optical measurements of the parent NDTs indicated that the shape of the molecules plays an important role in determining the electronic structure of the compounds; the linear-shaped NDTs formally isoelectronic with naphthacene have lower oxidation potentials and more red-shifted absorption bands than those of the angular-shaped NDTs isoelectronic with chrysene. On the contrary, the performance of the thin-film-based field-effect transistors (FETs) using the dioctyl or diphenyl derivatives were much influenced by the symmetry of the molecules; centrosymmetric derivatives tend to give higher mobility (up to 1.5 cm(2) V(-1) s(-1)) than axisymmetric ones (~0.06 cm(2) V(-1) s(-1)), implying that the intermolecular orbital overlap in the solid state is influenced by the symmetry of the molecules. These results indicate that the present NDT cores, in particular the linear-shaped, centrosymmetric naphtho[2,3-b:6,7-b']dithiophene, are promising building blocks for the development of organic semiconducting materials.  相似文献   

20.
本文设计并经由分子内碳-碳偶联反应合成了一系列基于芳并吡喃供电子功能片段的有机功能小分子,包括萘并[2,1-b:6,5-b’]二苯并吡喃4a,萘并[2,1-b:6,5-b’]二萘并吡喃4b,萘并[2,1-b:6,5-b’]二[2-(5-己基噻吩基)]苯并吡喃4c。通过紫外光谱和荧光光谱研究表明,这类化合物在370~400 nm波长范围内具有最大紫外吸收,在417~462 nm波长范围内具有最大荧光发射。说明随着共轭平面的增大或共轭链长度的增加,化合物的吸收和荧光光谱均发生显著的红移,是一类具有丰富光电活性的有机功能分子。  相似文献   

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