不同受体结构染料共敏化对染料敏化太阳电池性能的影响

为了拓宽染料敏化太阳电池对太阳光谱的响应范围,提高电池的光电转换效率,将两种含有不同受体结构（绕丹宁-3-乙酸基（RA）和氰基丙烯酸基（CA））的三苯胺染料（TR1和TC1）进行共敏化。TR1染料平伏吸附在TiO₂表面,而TC1染料直立吸附在TiO₂表面。将两种染料按照不同摩尔比共敏化TiO₂后,TC1占据TR1的部分位置,拓展光谱的同时也抑制了电荷复合,电子寿命较TR1敏化的太阳电池长。在TR1与TC1摩尔比为5：5的共敏剂溶液敏化的共敏电池器件中,短路光电流密度（J_sc）为11.7 mA/cm²,开路电压（V_oc）为704 mV,填充因子（FF）为0.73,光电转换效率（η）为6.03%。该结果明显优于单一染料敏化的电池器件。     

离子层气相反应法(ILGAR)制备CuInS_2薄膜的研究

0引言Ⅰ-Ⅲ-Ⅵ2族半导体薄膜太阳能电池具有价格低廉、性能优良和工艺简单等优点,已成为最有希望的光电转换器件,是当前国际光伏电池研究领域的热点之一。在Ⅰ-Ⅲ-Ⅵ2族半导体中,CuInS2因其光学禁带宽度适中(1.50eV),可见光区域吸收系数较高(6×105cm-1),化学稳定性好等特点而成为人们最为关注的薄膜太阳能电池材料之一[1~5]。目前,CuInS2薄膜太阳能电池的最高转换效率约为11%[6,7],距理论转换效率(27%~32%)[8]还有很大的差距,而改善CuInS2薄膜质量是提高其光电转换效率的关键。研究表明,CuInS2薄膜的制备技术及工艺条件对薄膜的结构…     

掺P25水热法制备纳晶多孔TiO2薄膜电极

以水热法为基础,向其溶胶中掺入适量的P25(二氧化钛粉体),来制备纳晶TiO₂胶体,以纳晶TiO₂为电子传输体组装染料敏化太阳能电池.通过XRD、SEM、UV-vis和电池的光电性能测试,来分析掺入P25对染料敏化太阳能电池性能的影响.结果表明,加入适量P25([P25]/[Ti]=0.2)后,染料敏化太阳能电池性能达到最佳值,在100 mW/cm²光照条件下,光电转换效率达到5.4%.     

反式p-i-n结构钙钛矿太阳能电池

近年来,有机无机杂化金属卤化物钙钛矿太阳能电池的光电转换效率从最初3.8%提升到现在的21.0%.快速的效率提升主要得益于钙钛矿材料本身的光电特性—适宜的直隙半导体禁带宽度、较低的激子束缚能、较高的摩尔消光系数、优良的载流子双极性扩散特性.然而,高效率钙钛矿太阳能电池的器件稳定性和迟滞效应现象仍未得到很好的改善,是当前急需要解决的挑战性难题.本文首先回顾了钙钛矿太阳能电池的发展历程和器件结构的演变,结合本课题组在反式p-i-n结构钙钛矿太阳能电池方面的研究进展,试图阐明一些由电池结构带来的本质性差异和一些设计实现钙钛矿太阳能电池高效率、高稳定性、消除迟滞效应的普遍规律.着重总结了基于聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)(PEDOT:PSS)基与NiO基两类p型空穴传输材料的反式结构钙钛矿电池方面的代表性研究进展.     

含二级供电基团的三苯胺类光敏染料合成及太阳能电池中的应用

以N,N-二甲基苯胺作为二级给电子单元, 合成两种具有不同长度共轭链的三苯胺类光敏染料XS19和XS22. 研究了它们的光物理与光电化学性质, 并将它们用作TiO₂纳米晶电极的光敏化剂引入太阳电池, 结果表明, N,N-二甲基苯胺的引入能够抑制染料敏化太阳能电池中的电子复合, 提高电池的光电转换效率. XS22表现出更好的光伏性能, 在AM1.5 (100 mW•cm^－2)的光强下, XS22敏化电池的开路电压(V_OC)为685 mV, 短路电流密度(J_SC)为9.6 mA•cm^－2, 填充因子(FF)为0.72, 总光电转换效率为4.7%.     

基于有机二硫化物氧化还原电对的非碘系染料敏化太阳能电池

相比较于硅太阳能电池而言, 染料敏化太阳能电池具有成本低廉、制备简单的特点. 在目前研究中, 普遍采用碘离子作为氧化还原电对, 然而碘元素本身具有腐蚀性, 长期使用会腐蚀对电极从而影响器件寿命, 而且此类电解液在可见光区内有很强的吸收, 也不利于光能向电能的转换. 本文采用了一种新型有机二硫化物, 2,5-二硫基-1,3,4-噻二唑, 作为氧化还原介质, 其不仅能够利用其自身自均聚/自解聚反应来实现光电转换过程, 降低对电极的腐蚀, 而且在可见光区内的吸收很低, 也有利于制作背入射式的染料敏化太阳能电池体系. 通过器件的优化, 可以分别实现1.6% (100 mW·cm^-2)和2.6% (13 mW·cm^-2)的光电转换效率.     

不同结构的氧化钛纳米金复合薄膜的光伏特性

具有表面等离子体共振效应的金属和氧化物复合纳米结构被应用在染料敏化太阳能电池（DSSC）中以提高电池的光电转换效率,金属纳米粒子和氧化物薄膜的复合结构对于等离子体共振器件在电池上的效果有巨大的影响. 我们研究了不同氧化钛薄膜和纳米金复合体系（纳米金分别修饰在氧化钛薄膜的表面和下表面）的光电转换效果,其中当纳米金修饰在氧化钛薄膜表面时薄膜的紫外可见吸收增加最大. 然而,经过染料敏化之后,该体系的光电转换效率比未修饰的薄膜有所降低,而纳米金修饰在氧化钛薄膜下表面时,光电转换效率比未修饰时提高了37%,同时入射单色光子-电子转化效率（IPCE）也有相应提高. 为了进一步研究纳米金在复合薄膜中的作用,我们引入了TiO₂-Au-TiO₂的三明治体系,该体系的光电转换效率比未修饰的参比氧化钛薄膜仍有所提高. 上述研究结果表明等离子体共振器件的结构设计对于染料敏化太阳能电池的改善具有重要意义. 同时,我们对于纳米金的等离子体共振效应做了离散偶极子近似（Dipole Discrete Approximation）模拟计算,其结果支持了实验数据. 该研究对于未来太阳能电池中表面等离子体共振器件的设计具有一定指导意义.     

有机太阳能电池用聚合物给体材料的研究进展

有机太阳能电池由于质轻、价廉、柔性,受到人们的广泛关注.开发性能优异的聚合物给体材料,是近期有机太阳能电池研究的主流方向之一.迄今为止,已经成功开发出各种各样具有优秀的给体性质的共轭聚合物.基于这些材料制备的有机太阳能电池器件,已经突破9%的光电转换效率.按照聚合物给体材料的主链结构分类,综述了近年来这方面的研究进展.对一些受到普遍关注的材料,从设计思想、性能剖析到器件制备和性能,做了详细的介绍,以期能够深层次理解材料的化学结构-凝聚态结构-性能间的基本规律,为今后的材料研发提供有价值的参考.     

表面修饰的TiO_2太阳能电池界面特性研究

用水热法制备了具有典型锐钛矿晶型的TiO2纳米材料,采用Cr(NO3)3对TiO2薄膜电极进行修饰改性。用X射线衍射(XRD)、扫描电子显微镜(SEM)和光电子能谱(XPS)测试电极的物相及表面结构,结果显示TiO2薄膜表面包覆一层粒径较大的氧化铬颗粒,整个电极仍保持均匀的多孔结构。电流-电压(I-V)曲线测试结果显示,改性后最佳电极的短路电流和光电转换效率分别比改性前提高了31.1%和40.4%。用电化学阻抗谱(EIS)测试电池的界面特性,从测试结果可以看出,相同偏压下,改性后电池的TiO2/染料/电解质界面电阻更大,说明氧化铬包覆层在一定程度上抑制了界面的电子复合,改善了电池的光电输出特性。     

高相转变温度的离子凝胶电解质基准固态染料敏化太阳电池

染料敏化太阳电池(DSC)以其低价、高效等优势, 成为学术界和工业界的研究热点. 传统液态电解质由于易挥发、易泄漏等问题, 导致基于液态电解质的电池难以保持长期稳定, 影响光伏技术的应用. 本文合成了N,N'-1,5-戊二基双月桂酰胺, 将其作为有机小分子胶凝剂(LMOG)胶凝离子液体电解质(ILE)制备了离子凝胶电解质(IGE)并组装成准固态电池(QS-DSCs). 差示扫描量热测试显示该凝胶电解质的相转变温度(T_gel)为104.7℃, 具有良好的本征热稳定性.利用循环伏安法、电化学阻抗谱、调制光电压/光电流谱分别研究了液态电池和准固态电池内部电子传输和复合动力学过程. 结果表明, 凝胶电解质的三维网络结构加速了TiO₂光阳极/电解质界面电子与电解质中I₃^-的复合过程, 使电子寿命降低, 导致准固态电池的光电转换效率略低于液态电池. 在AM1.5 (100 mW·cm^-2)及50℃条件下的加速老化测试结果显示, 持续老化1000 h后其光电转换效率(η)无衰减,而液态电池的光电转换效率衰减为初始值的86%, 表明准固态电池具有良好的光热稳定性.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.