氟代苝酰亚胺掺杂PVK薄膜的结构特性和光电导性能

采用一种新型的有机电子受体N，N’-二(五氟代苯基)-3，4，9，10-菲四羧基二酰亚胺(DFPP)．与空穴传输材料聚乙烯基咔唑(PVK)掺杂复合．制备了单层有机光电导体．发现无论是在充正电还是在充负电情况下．该复合光电导体均表现出十分优异的光电导性能。结合DSC、UV—Vis吸收、XPS和循环伏安等测试手段研究了DFPP掺杂的PVK薄膜的凝聚态、光学和电学性质．发现DFPP与PVK形成了给体-受体(D—A)复合物，而且DFPP分子可在薄膜中形成电子传输通通道，由此使DFPP掺杂PVK薄膜具有高的光致激子分离效率和良好的电子传输能力。     

新型有机电子受体氟代苝酰亚胺的合成与表征

设计和合成了一种新型有机电子受体N,N′-二(五氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(DFPP),利用傅里叶红外光谱和核磁共振谱等方法表征了DFPP的分子结构,用紫外-可见吸收光谱、循环伏安法和电子自旋共振谱等手段证明了DFPP中极低的最低未占有轨道(LUMO)能级为-4.37eV.另外,还发现了DFPP薄膜的独特聚集态结构,五氟代苯基正好处于相邻分子苝环的正上方或正下方.     

基于铝离子掺杂二氧化钛薄膜的染料敏化太阳能电池的光电性能

采用水热法制备出Al3+掺杂二氧化钛薄膜,通过玻璃棒涂于导电玻璃上,在450°C的温度下烧结并将其用N3染料敏化制成染料敏化太阳能电池(DSSCs).通过X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电镜(SEM)及DSSCs测试系统对其进行了测试表征,研究了Al3+掺杂对TiO2晶型及染料敏化太阳能电池的光电性能影响.XPS数据显示Al3+成功掺杂到了TiO2晶格内,由于Al3+的存在,对半导体内电子和空穴的捕获及阻止电子/空穴对的复合发挥重要作用.莫特-肖特基曲线显示掺杂Al3+后二氧化钛平带电位发生正移,并导致电子从染料注入到TiO2的驱动力提高.DSSCs系统测试结果表明,Al3+掺杂的TiO2薄膜光电效率达到6.48%,相对于无掺杂的纯二氧化钛薄膜光电效率(5.58%),其光电效率提高了16.1%,短路光电流密度从16.5mA·cm-2提高到18.2mA·cm-2.     

石墨烯-氧化钨复合薄膜的制备及界面电子传输特性

以偏钨酸铵为钨源、聚乙烯吡咯烷酮为连接剂,采用浸渍提拉法制备了石墨烯-氧化钨复合薄膜,利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及Raman光谱等方法对复合结构材料进行了表征,并利用光电流测试、交流阻抗谱(EIS)、瞬态光电流谱和强度调制光电流谱等方法,研究复合薄膜电极在光电作用下界面上的载流子转移过程和电荷传输行为.结果表明,组成薄膜的氧化钨纳米颗粒与石墨烯充分复合,光电性能显著提高;与石墨烯复合后,薄膜的瞬态时间常数增大,电子-空穴对寿命延长;电子传输时间减少,为纯氧化钨薄膜的47.5%.     

内含C_(60)掺杂空穴传输层的量子点电致发光器件

聚乙烯咔唑(PVK)中掺入富勒烯(C60)的重量比从0%到10%变化,以研究在空穴传输层中掺杂C60后对量子点电致发光器件性能的影响。掺入C60后的PVK薄膜在氧化铟锡(ITO)基底上均方根粗糙度从3 nm降至1.6 nm。另外,掺入C60后有利于空穴的注入和传输,改善器件中电子和空穴的平衡,提高了器件的效率。     

ClInPc-(TPD-PVK)光电导体性能的研究

本文以氯化酞菁铟(ClInPc)为载流子发生层(CGL),四苯基联苯胺(TPD)与聚乙烯咔唑(PVK)复合为载流子传输层(CTL),形成双层结构的功能分离型有机光电导体(P/R),研究了它的静电感光性能。结果表明,ClInPc/PMMA(30%)与TPD/PVK(1:1)两者匹配时的P/R具有良好的光电导性能,其电荷接受能力V_max≈800V,光电导率△V_t(ls)>70%,暗衰小(<50V/s),残余电位低(30V/s).由真空蒸镀成膜(CGL)所研制的P/R的光电导性能更为优异。     

Au掺杂对TiO_2薄膜表面态及电荷传输性能的影响

采用两步法合成了不同Au掺杂量的TiO_2薄膜材料,并通过循环伏安(CV)和电化学阻抗谱(EIS)探究了不同Au掺杂量TiO_2薄膜的表面态数量及其在禁带中的分布情况.借助强度调制光电流/电压谱(IMPS/IMVS)研究了薄膜内电子传输时间和寿命及界面电荷转移性能等.结果表明,适量Au(摩尔分数0.2%)的掺入可有效降低薄膜的表面态数量,优化表面态分布情况,提高电子在TiO_2/染料/电解质界面的电阻,从而改善电子的传输性能,提升太阳电池的光电转换效率.     

还原石墨/氧化锌复合薄膜的制备及其光电转换性能

本工作研究不同过程还原的氧化石墨rGO/ZnO(reduced graphiteoxide/ZnO)复合膜的可见光激发光电转换性能。氧化石墨(GO)经KOH还原处理或NaBH4还原处理后,和氧化锌溶胶混合,通过旋涂法和热处理在F掺杂SnO2薄膜导电玻璃(FTO)衬底上形成复合薄膜。采用XRD、FTIR、FE-SEM、XPS、UV-Vis等方法对复合薄膜的晶相结构、微观形貌等进行表征,并测试了复合薄膜在可见光照射下的光电转换性能。GO的预处理过程对复合薄膜的结构影响显著,采用NaBH4对GO处理更有利于形成均匀薄膜。光电流测试结果表明不同复合薄膜均能实现可见光照射下产生光电流,其原理为rGO的光激发电子跃迁到ZnO,而空穴在rGO中迁移,在rGO与ZnO界面实现光生载流子分离。其中NaBH4处理后的rGO/ZnO复合薄膜光电流密度最大,达6×10-7A·cm-2。     

染料分子结构对光伏器件性能的影响

制备了铜酞菁衍生物和二酰亚胺衍生物为工作物质的双染料有机光伏体系,讨论了工作物质分子结构对体系中载流子(电子和空穴)传输过程的影响,认为带有吸电子侧基的给体分子与带有推电子侧基的受体分子组合成的有机光伏体系可能更有利于载流子的转移和传输,从而在一定程度上提高体系的光电转换性能。最后,尝试从量子化学的角度对体系的光电转换性能进行了解释。     

二嗪类有机光电功能材料的应用进展

在过去的几十年里,有机电子学作为一个新兴领域迅猛发展,为科学技术的进步作出了巨大的贡献.有机材料被应用在各种电子器件中,并取得了卓越的成效.作为使用在电子器件中最基本的组分,有机光电材料更是备受瞩目.二嗪类化合物具有优异的光电性能,是光电材料领域最活跃的研究方向之一.两个N原子相对位置的不同,可以构成三种异构体,分别为哒嗪(1,2-二嗪)、嘧啶(1,3-二嗪)和吡嗪(1,4-二嗪),从而有效地调控材料的电子结构,且可以影响二嗪化合物不同位置的修饰,从而得到了广泛关注.本文对近年来二嗪类化合物在光伏材料、薄膜半导体材料、液晶材料、传感材料和电致发光材料等领域的研究进展进行了较全面的总结和评述,指出目前基于二嗪类化合物的光电材料所面临的困难以及未来的发展方向,最后展望了二嗪类化合物作为杂环类有机光电功能材料的应用前景.     

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.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.