二维半导体材料纳米电子器件和光电器件

近年来,随着各领域对微电子器件集成度及性能要求的不断提高,发展基于二维半导体材料的新型高性能功能性器件成为了突破当前技术瓶颈的重要环节和关键方向。目前,作为新型二维半导体材料的代表,二维过渡金属二硫化物、二维黑磷以及范德瓦尔斯异质结凭借其在电学、热学、机械、光学等方面的优异性能已经成为了发展高性能纳米电子器件和光电器件的最具潜力的材料之一。在本综述中,首先概述了几种用于纳米器件的常见二维材料,分析了材料的结构、性能及其在纳米器件中的应用,其次重点对基于过渡金属二硫化物、黑磷以及由其衍生的范德瓦尔斯异质结的纳米电子器件和光电器件的最新研究进展进行讨论,最后对目前二维半导体纳米器件所面临的挑战以及未来的发展方向进行总结及分析,从而为未来发展高性能功能性纳米器件提供支持。     

石墨烯-量子点复合材料的制备与应用

石墨烯因其独特的物理化学性质以及潜在的巨大应用价值引起了越来越多的研究兴趣,但其特殊的零带隙结构却限制了它在光电领域的应用。半导体量子点因其特有的量子尺寸效应而表现出迷人的光学性能,已成功应用于生物标记及电化学等领域,但电子-空穴对易复合湮灭,导致电子迁移率较低,限制了其在光电转换方面的应用。石墨烯独特的结构和电子特性使其成为优秀的导电支架,可从量子点中捕获并输运电子,实现了电子空穴对的有效分离。石墨烯-量子点复合材料不仅具有石墨烯的高电子传输性能,而且具备量子点特殊结构产生的量子尺寸效应和边缘效应,二者复合后在纳米器件和光电器件等领域极具应用潜力。本文详细总结了近年来石墨烯-量子点复合材料的制备方法,包括相转移法、静电复合、水热和溶剂热法以及电化学法和微波辅助法等,并简要介绍了相关应用领域的研究进展,以期为石墨烯基纳米复合材料的发展研究提供相关的参考与依据。     

《化学通报》网络版(Chemistry Online)2005年第11期论文摘要

[w123]具有纳米结构的有机发光材料研究进展**Progress in Research on Organic Nanomaterials for Luminescence赵雷黄维*(复旦大学先进材料研究院上海200433)对有机纳米发光材料制备方法以及材料的性能作了较为全面的综述。有机纳米发光材料由于存在分子间作用力(范德华力)或氢键以及具有小的Frenkel激子半径,与无机半导体纳米微粒以及纳米金属有着很大的区别,具有自己独特的光电性能,同时又兼具了有机发光材料响应速度快、可进行分子设计和纳米材料的尺寸效应等优点,在新型光电器件方面具有潜在应用前景。综合研究现状,本文也提出了该…     

量子尺寸氧化锌颗粒的表面光电压谱研究

氧化锌是极少数几个可以实现量子尺寸效应的氧化物半导体材料[1 ] .传统上 ,这种材料广泛用于陶瓷、压电传感器、催化剂以及发光器件等领域 .随着量子尺寸氧化锌颗粒制备工艺日臻成熟 ,这类材料的应用进一步拓展到光电转换 [2 ] 、光催化[3] 以及化学传感器 [4] 领域 .而在这些领域中的应用都与颗粒的表面性质密切相关 .本工作中制备了两种不同粒径的氧化锌纳米微粒 ,利用表面光电压谱以及电场诱导表面光电压谱对颗粒的表面性质进行了研究 ,并对颗粒的表面态进行了具体指认 .1　实验部分氧化锌纳米微粒参照文献 [5 ,6 ]方法制备 .将 5 .49g…     

非“三明治”结构的分子基光电器件

传统的分子材料光电器件如太阳能电池和有机发光二极管通常采用"三明治"型垂直结构.器件通常由透明底电极、薄膜活性层和顶接触电极构成.该结构优化了光与半导体的相互作用以及载流子的注入和收集,实际应用广泛.近些年,为了降低透明电极的使用成本以及更好地实现非薄膜形态纳米半导体材料的器件构筑,一些非"三明治"结构的有机光电器件也取得了很大进展:发展出了具有微米、纳米电极结构的光伏器件、光电导器件、光晶体管器件、纳米间隙电极器件等,拓展了分子基光电材料的应用研究,与传统夹心型二极管器件相互补充、相互完善.本文主要聚焦在各种非"三明治"结构有机光电器件的构筑与功能化,对有代表性的研究成果进行了总结与评述,并对其未来的发展进行了展望.     

扫描探针刻蚀技术可控构建牛血清白蛋白纳米结构

利用Dip-pen纳米刻蚀技术(简称DPN技术)在云母基底上构建出形状、尺寸可控的牛血清白蛋白(BSA)纳米结构.考察了针尖接触基底时间及针尖下行距离对构建的牛血清白蛋白纳米结构的影响.较长的针尖-基底接触时间及较深的下行距离可以沉积更多的牛血清白蛋白分子,构建牛血清白蛋白纳米结构的形状除了与墨水分子的本身性能有关,还与墨水-基底的相互作用有关.这些形状及尺寸可控的蛋白质纳米结构可以作为模板,进行金属、半导体等其它材料的组装,有望用于制造光电纳米器件及生物纳米器件.     

高质量尺寸可调CuFeS2纳米晶的合成与光电性质

制备了单分散性良好且尺寸可调的具有荧光性质的CuFeS2纳米晶,利用紫外-可见吸收光谱(UVVis)、荧光光谱、透射电子显微镜(TEM)、X射线粉末衍射(XRD)、元素分析和光电流测试等技术对其组分和结构进行了表征,分析了CuFeS2纳米晶尺寸变化对吸收光谱和光电响应行为的影响规律.随着CuFeS2纳米晶尺寸增大,其吸收峰位表现出符合量子尺寸效应的相应红移;具有荧光性质的CuFeS2纳米晶可控制备预示其在生物医学成像和光电器件等领域具有应用前景.     

D-π-A-π-D型非掺杂小分子空穴传输材料的合成及其在反向钙钛矿太阳能电池中的应用

设计合成了三种以（甲氧基）三苯胺为给体（Donor,D）,苯环为共轭π桥,羰基（或双氰基乙烯基）为受体（Acceptor,A）的D-π-A-π-D型有机小分子空穴传输材料1-T、1-OT和1-OTCN.对三个化合物的热稳定性、光物理以及电化学性质进行表征,并将它们作为空穴传输材料运用至钙钛矿太阳能电池中,研究其光伏特性.实验结果表明,通过引入具有不同给（吸）电子能力的基团,可对材料的光电性质进行有效调控.基于小分子空穴传输材料1-T、1-OT和1-OTCN的非掺杂反向钙钛矿太阳能电池器件光电转化效率（PCE）分别为13.0%、14.4%以及16.8%.其中,基于甲氧基和双氰基修饰的1-OTCN电池器件,由于空穴传输层与钙钛矿界面发生更有效的电荷跃迁和收集,电荷复合较少,因此器件性能最佳,1-OTCN的疏水性质使得其对应器件效率和水氧稳定性均优于常用空穴传输材料PEDOT：PSS（PCE：13.0%）.     

TiO2多孔薄膜电极的制备、微结构及光电化学性能研究

近年来,半导体纳晶多孔薄膜作为一类重要的纳米结构材料,其光电化学性质及功能特性的研究受到人们广泛关注。由于量子尺寸效应及介电限域效应,它们的光物理、光电化学性质以及电荷传输机理明显异于多晶及单晶体材料。通过简便快捷的涂敷、浸涂或溅射等方法,半导体纳晶多孔薄膜可以在导电衬底上形成。这些薄膜具有高度多孔性、大比表面,易于用有机功能分子或半导体超微粒进行表面修饰^[1-2],在太阳能转换^[2]、光电子器件或电子变色器件^[3]及光催化治理环境污染^[4]等方面具有潜在的应用前景。因此,在光电化学、半导体物理及材料科学领域里研究十分活跃。本文采用涂敷及浸涂提拉方法制备了四种具有不同多孔率及比表面的TiO₂薄膜电极,并对其晶型、表面形貌微结构及光电化学性能进行了研究。     

Ⅰ-Ⅲ-Ⅵ族半导体纳米晶

半导体纳米晶是近年来发展起来的一类新型功能材料,因其独特的量子限域效应和光电性质,在太阳电池、发光二极管、光电探测器、生物标记、非线性光学等领域中具有潜在的应用。与目前研究比较多的Ⅱ-Ⅵ和Ⅳ-Ⅵ族纳米晶相比,Ⅰ-Ⅲ-Ⅵ族半导体纳米晶,不含镉和铅等重金属元素,具有毒性小、带隙窄、光吸收系数大、Stokes位移大、自吸收小以及发光波长在近红外区等特点,有望成为新一代低成本太阳电池和低毒荧光量子点生物标记材料, 还可用于发光二极管和光电探测等领域。因此,Ⅰ-Ⅲ-Ⅵ族半导体纳米晶的合成、性质及应用研究成为近期纳米晶研究领域的热点之一。本文将综述Ⅰ-Ⅲ-Ⅵ族半导体纳米晶的研究进展,着重介绍其制备方法、光学性质及其在生物标记、太阳电池等领域的应用。     

多孔硅的光电化学特性研究

研究了多孔硅的光电化学特性和溶液中的光致电荷转移机一，由Ｐ型单晶硅制备的多孔硅具有Ｐ型半导体的光电性质，且光电流响应高于单晶硅，由于多孔硅表面态能级对光致电荷的陷阱作用，多孔硅呈现了独特的光电流响应和光致电荷转移性质。     

Photoinduced Charge Separation in Molecular Silicon

Interest in molecular silicon semiconductors arises from the properties shared with bulk silicon like earth abundance and the unique architectures accessible from a structure distinctly different than rigid π‐conjugated organic semiconductors. We report ultrafast spectroscopic evidence for direct, photoinduced charge separation in molecular silicon semiconductors that supports the viability of molecular silicon as donor materials in optoelectronic devices. The materials in this study are σ–π hybrids, in which electron‐deficient aromatic acceptors flank a σ‐conjugated silicon chain. Transient absorption and femtosecond‐stimulated Raman spectroscopy (FSRS) techniques revealed signatures consistent with direct, optical charge transfer from the silane chain to the acceptor; these signatures were only observed by probing excited‐state structure. Our findings suggest new opportunities for controlling charge separation in molecular electronics.     

A Perspective on Studying Electronic Structure of Batteries through Soft X-ray Spectroscopy

Understanding electronic structure is crucial to enhance the battery performance. Soft X-ray spectroscopy(SXS) is one of the most effective methods to provide direct probe of electronic states. Here, spectroscopic measurements of transition metal 3 d and oxygen 2 p states are simply reviewed. Then, we mainly focus on the perspective of the development direction of modern SXS techniques. Although the true power of recently developed high efficiency mapping of resonant inelastic X-ray scattering(m RIXS) has been apparent for materials and chemistry studies, great challenges remain for mRIXS spectroscopic interpretation, and the understanding of the battery materials on novel redox activities remains elusive.     

Multi-domain High-Resolution Platform for Integrated Spectroscopy and Microscopy Characterizations

In recent decades, materials science has experienced rapid development and posed increasingly high requirements for the characterizations of structures, properties, and performances. Herein, we report on our recent establishment of a multi-domain (energy, space, time) high-resolution platform for integrated spectroscopy and microscopy characterizations, offering an unprecedented way to analyze materials in terms of spectral (energy) and spatial mapping as well as temporal evolution. We present several proof-of-principle results collected on this platform, including in-situ Raman imaging (high-resolution Raman, polarization Raman, low-wavenumber Raman), time-resolved photoluminescence imaging, and photoelectrical performance imaging. It can be envisioned that our newly established platform would be very powerful and effective in the multi-domain high-resolution characterizations of various materials of photoelectrochemical importance in the near future.     

Non-radiative deactivation pathways of subphthalocyanine and subnaphthalocyanine dyes and of their mixture

Subphthalocyanine and subnaphthalocyanine dyes and their mixture were investigated by means of the spectroscopic and photoelectric methods. Absorption, fluorescence, steady-state and time-resolved photothermal measurements for the dyes and their mixture were done in order to get information about the radiative and non-radiative deactivation processes as competetive processes to charge separation. It was shown that energy transfer between the dyes improved the photocurrent generation in photoelectrochemical cells (PEC) based on In(2)O(3) and SnO(2) as an electrode. The possible participation of the dye triplet states in non-radiative processes was discussed.     

有机自旋光电子学的基本过程

有机自旋光电子学的研究方向分为磁场效应和自旋注入两个方面.研究表明,外加低磁场能够显著改变非磁性有机半导体材料的光致发光、注入电流、电致发光和光电流.这称为有机半导体材料的磁场效应.近年来,非磁性有机半导体材料的磁场效应引起了广泛的关注和研究兴趣.首先,有机半导体材料的磁场效应是强有力的实验手段,用以研究有机电学、光学和光电器件中电荷传输和激发态中的有用和无用过程,为解决电荷传输和激发态过程中的瓶颈问题提供有效的实验手段,为实现磁-光-电多功能集成提供科学原理,尤其是磁场效应能够为提高能量转换效率、探测和传感光电子学器件的响应频谱范围和灵敏度提供新思路.同时利用磁电极,有机半导体材料和器件中自旋注入及其对电荷传输和激发态过程的调控可以用于发展新型功能化的自旋光电子学器件.本文综述并讨论了有机半导体材料和器件中的磁场效应和自旋注入的光电子学效应.     

Regulating Phase Junction and Oxygen Vacancies of TiO2 Nanoarrays for Boosted Photoelectrochemical Water Oxidation

In this study, we have provided a facile solution to synthesize well-aligned titanium dioxide nanorods by using hydrothermal reaction. By calcining the materials under different atmospheres and temperatures, a batch of titanium dioxides with excellent oxygen evolution reaction(OER) catalytic efficiency were obtained. This new structured TiO₂ photoanode material yields a high photocurrent density of 5.69 mA/cm² at 1.23 V vs. reversible hydrogen electrode(RHE) under simulated solar light(100 mW/cm²). Surface photovoltage techniques and other measurements were carried out to confirm that the enhanced photoelectrochemical performances were attributed to the synergistic effect of the phase junction and a certain content of surface states, which accelerate the separation and transmission of the photogenerated charges. This material with phase junction and surface states promises a potential application in the field of photoelectric catalysis under solar light.     

DNA/CdS纳米粒子复合体系的光谱和光电化学性质

在水溶液中以DNA作为模板和稳定剂, 构筑了DNA与CdS纳米粒子复合体系(DNA/CdS NPC), 研究DNA的含量, 单双链等对复合体系光电响应的影响, 并综合TEM, UV-Vis, IR和荧光光谱等对其形貌和光谱性质进行表征. 结果表明, CdS纳米粒子(CdS NPs)与DNA链之间主要通过静电作用结合; DNA模板对CdS NPs的禁带宽度没有影响; 以DNA模板合成的CdS NPs具有较高的表面态密度, 其对CdS NPs的荧光有增强作用, 而对光电流响应有抑制作用, 并且DNA在复合体系中的含量影响荧光增强和光电流减弱的程度. 该复合体系在荧光标记检测和DNA的定量分析方面可能具有应用前景.     

基于计算谱学的纳米材料结构表征及其在石墨烯氧化物中的应用

从理论上对材料结构进行表征一般是基于第一性原理电子结构计算对可能的结构模型进行能量分析, 从而得到材料的基态构型. 而经过复杂路径合成的纳米材料并不总是处于基态能量构型. 因此, 对可能的结构模型进行计算谱学模拟, 然后直接与实验谱图对比, 可以提供更为可靠的结构信息. 本文简单介绍了谱学模拟的理论背景, 以石墨烯氧化物为例展示了计算谱学在复杂纳米材料结构表征中的关键作用.     

Controlling optical properties and electronic energy structure of I–III–VI semiconductor quantum dots for improving their photofunctions

I–III–VI multinary semiconductors, which have low toxicity, are attracting much attention as quantum dot (QD) materials for replacing conventional binary semiconductors that contain highly toxic heavy metals, Cd and Pb. Recently, the inherent design flexibility of multinary QDs has also been attracting attention, and optoelectronic property control has been demonstrated in many ways. Besides size control, the electronic and optical properties of multinary QDs can be changed by tuning the chemical composition with various methods including alloying with other semiconductors and deviation from stoichiometry. Due to significant progress in synthetic methods, the quality of such multinary QDs has been improved to a level similar to that of Cd-based binary QDs. Specifically, increased photoluminescence quantum yield and recently narrowed linewidth have led to new application fields for multinary QDs. In this review, a historical overview of the solution-phase synthesis of I–III–VI QDs is provided and the development of strategies for better control of optoelectronic properties, i.e., electronic structures, energy gap, optical absorption profiles, and photoluminescence feature, is discussed. In addition, applications of these QDs to luminescent devices and light energy conversion systems are described. The performance of prepared devices can be improved by controlling the optical properties and electronic structures of QDs by changing their size and composition. Clarification of the unique features of I–III–VI QDs in detail will be the base for further development of novel applications by utilizing the complexity of multinary QDs.