钙钛矿太阳电池吸光层材料研究进展

近年来,有机-无机卤化铅钙钛矿太阳电池的研究取得了突破性进展,公证记录电池效率22.1%,与CdTe薄膜电池（认证记录电池效率22.1%）和CuInGaSn（CIGS）（认证记录电池效率22.3%）薄膜电池技术相媲美,已经接近于市场上主导地位的晶体硅太阳电池（约25%）。有机卤化铅钙钛矿太阳电池器件的长期效率输出稳定性和含毒性Pb严重制约其实际应用。本文将讨论有机卤化铅钙钛矿太阳电池不稳定性因素和相应的解决方案,并对钙钛矿材料中Pb元素的取代工作和无机非铅钙钛矿材料及其太阳电池的研究进行了阐述与展望。     

无机铅卤钙钛矿纳米晶的合成、性能及应用

无机铅卤钙钛矿CsPbX₃(X=Cl,Br,I)纳米晶因具有较高荧光量子效率(~90%)、发光波长覆盖整个可见光谱(400~700 nm)、半高宽相对较窄(12~42 nm)等诸多优点而备受关注,这些性能使之成为当前最具有潜在应用价值的发光材料之一。 因此,近年来对该类无机铅卤钙钛矿材料的报道越来越多。 本文主要介绍了无机铅卤钙钛矿发光材料的发展历程、结构、制备方法、生长机理及当前的主要应用领域等,最后概括了无机铅卤钙钛矿发光材料在当前研究背景下所面临的问题并展望了下一阶段的发展方向,为进一步提高其光学性能及开发新型高效的无机铅卤钙钛矿发光材料奠定基础。     

铅卤钙钛矿敏化型太阳能电池的研究进展

铅卤钙钛矿太阳能电池由于其低廉的成本, 简易的制备工艺和具有商业化潜力的效率等优点, 在最近两年里成为太阳能领域广受关注的新星. 铅卤钙钛矿太阳能电池的结构, 材料合成和制作工业在短时期内发生多项革命性的变化. 铅卤钙钛矿敏化型太阳能电池从最初使用液体电解液的敏化电池, 演变为固态敏化电池. 铅卤钙钛矿也从最初沉积在介孔膜的空隙的传统敏化结构, 演变为介孔空隙填充和致密覆盖层结合的混合型敏化结构. 通过这些结构的演化和材料制备的进步, 敏化型铅卤钙钛矿太阳能电池具备了较高的稳定性和高效率的两大优点. 对铅卤钙钛矿敏化型太阳能电池的研究进展进行简要综述.     

激光作用铅卤钙钛矿的机理与应用

近年来,铅卤钙钛矿纳米晶因其易制备,低成本,高性能等特性引起了人们极大的关注。钙钛矿纳米晶的光电性能优越应用潜力巨大,然而稳定性问题制约着它进一步发展,使其无法与已经商业化的应用相匹敌。针对钙钛矿材料的稳定性问题,人们展开了很多研究,其中一个方面就是光照稳定性。该方面的研究可以为制备高稳定性钙钛矿材料和器件奠定基础,还可以利用光照(特别是激光)来调控钙钛矿的结构和性能,拓展其在光电领域的全方位应用。本文专注于激光照射下钙钛矿的变化及其相关应用,首先综述了激光辐照铅卤钙钛矿时出现的变化现象以及微观机理;其次,基于这些变化机理,介绍了最近研究人员如何使用激光技术对钙钛矿薄膜和器件进行性能调控,以及激光直写钙钛矿技术的相关应用。     

全无机钙钛矿太阳电池的制备及稳定性

全无机钙钛矿太阳电池因其热稳定性好、载流子迁移率高,可用于制备叠层电池等优点备受关注。随着人们对全无机钙钛矿太阳电池的深入研究和制备工艺的持续优化,全无机钙钛矿太阳电池的光电转换效率已经突破19%。然而,全无机钙钛矿材料相稳定性较差,这使得实现全无机钙钛矿太阳电池在空气环境下制备和长期使用面临巨大挑战。众多科研工作者通过分析全无机钙钛矿材料的相变机制,有针对性地提出了包括添加剂工程、界面工程和开发全无机钙钛矿量子点电池等多种方式来改善全无机钙钛矿太阳电池的长期稳定性。本综述从全无机钙钛矿材料与电池的结构、活性层制备方法和稳定性研究三个方面总结了近年来关于全无机钙钛矿太阳电池的研究进展。     

少铅钙钛矿CH3NH3SrxPb(1-x)I3的合成及其在全固态薄膜太阳能电池中的应用

近年来, 有机-无机杂化铅卤化物钙钛矿太阳能电池(PSCs)得到了迅猛发展, 其最高光电转换效率已经达到19.3%. 该类型太阳能电池使用的钙钛矿型吸光材料为含Pb的有机-无机杂化铅卤钙钛矿, 从长远来看,Pb的毒性将制约其大规模应用. 本文从减少吸光材料中Pb的含量出发, 尝试用Sr 部分取代Pb制备一系列少铅钙钛矿CH₃NH₃Sr_xPb_(1-x)I₃, 并将其应用于钙钛矿太阳能电池进行光电性能的研究. 研究结果表明, 相比于全Pb 钙钛矿(CH₃NH₃PbI₃)材料, Sr 取代量为30% (x=0.3)时, 所形成的CH₃NH₃Sr_0.3Pb_0.7I₃光谱吸收大范围增强,但基于此材料制备的电池器件性能明显下降.     

ABX3型钙钛矿光伏材料的结构与性质调控

近年来,钙钛矿太阳能电池由于其效率高、制造成本低、工艺简单等特点受到广泛关注,成为目前太阳能电池领域的研究热点。在钙钛矿太阳能电池中,无机-有机杂化ABX₃材料非常重要。它既作为光吸收材料,同时又作为载流子传输材料,因此它的光电性质直接影响到太阳能电池的效率。本文综述了调控无机有机金属卤化物ABX₃型钙钛矿光伏材料结构和性质的几种途径。     

钙钛矿ABX3型材料的结构与性质调控

近年来,钙钛矿太阳能电池由于其效率高、制造成本低、工艺简单等特点受到广泛关注,成为目前太阳能电池领域的研究热点。在钙钛矿太阳能电池中,无机-有机杂化ABX₃材料非常重要。它既作为光吸收材料,同时又作为载流子传输材料,因此它的光电性质直接影响到太阳能电池的效率。本文综述了调控钙钛矿型无机有机金属卤化物ABX₃结构和性质的几种途径。     

钙钛矿同质结太阳电池研究进展

钙钛矿太阳电池制备工艺简单,效率提升迅速,被认为是最具应用潜力的新一代光伏技术之一。近年来,大量研究表明,钙钛矿光电材料可以通过自掺杂或外源掺杂的方式实现薄膜导电类型(p型或n型)的定向调控;而具有双层薄膜结构的钙钛矿p-n同质结可以通过薄膜双沉积技术制备,这为钙钛矿同质结太阳电池的设计与制备提供了技术基础。新型钙钛矿同质结太阳电池摒弃传统的电子传输层和空穴传输层,可简化电池结构,不仅有利于提升电池工作稳定性,降低成本,更能进一步释放钙钛矿太阳电池在柔性和半透明应用中的潜力,推动钙钛矿电池的实用化进程。本文围绕钙钛矿同质结太阳电池,综述了钙钛矿光电材料p/n特性掺杂和钙钛矿同质结的研究进展,讨论了钙钛矿同质结太阳电池的基本结构和工作原理,并对其当前存在的技术问题和应用前景进行了总结与展望。     

铋基钙钛矿(CH3NH3)3Bi2I9薄膜的制备及在光伏电池中的应用

铋基钙钛矿由于稳定性强及毒性低,被认为是未来极具发展潜力的环保型钙钛矿材料。(CH₃NH₃)₃Bi₂I₉(MBI)因具有优异的光吸收性能而引起人们的普遍关注。本文介绍了MBI钙钛矿晶体的结构及性能,总结了其薄膜的制备方法,并重点叙述了不同方法制备的MBI钙钛矿薄膜在光伏电池中的应用情况。MBI钙钛矿与铅基钙钛矿的效率相比还有很大差距,如何提高其光电转换效率仍是今后研究的主要方向。     

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.