二维原子晶体的低电压扫描透射电子显微学研究

二维原子晶体材料,如石墨烯和过渡金属硫族化合物等,具有不同于其块体的独特性能,有望在二维半导体器件中得到广泛应用.晶体中的结构缺陷对材料的物理化学性能有直接的影响,因此研究结构缺陷和局域物性之间的关联是当前二维原子晶体研究中的重要内容,需要高空间分辨率的结构研究手段.由于绝大部分二维原子晶体在高能量高剂量的电子束辐照下容易发生结构损伤,利用电子显微方法对二维原子晶体缺陷的研究面临诸多挑战.低电压球差校正扫描透射电子显微(STEM)技术的发展,一个主要目标就是希望在不损伤结构的前提下对二维原子晶体的本征结构缺陷进行研究.在STEM下,多种不同的信号能够被同步采集,包括原子序数衬度高分辨像和电子能量损失谱等,是表征二维原子晶体缺陷的有力工具,不但能对材料的本征结构进行单原子尺度的成像和能谱分析,还能记录材料结构的动态变化.通过调节电子束加速电压和电子辐照剂量,扫描透射电子显微镜也可以作为电子刻蚀二维原子晶体材料的平台,用于加工新型纳米结构以及探索新型二维原子晶体的原位制备.本综述主要以本课题组在石墨烯和二维过渡金属硫族化合物体系的研究为例,介绍低电压扫描透射电子显微学在二维原子晶体材料研究中的实际应用.     

二维平面和范德瓦耳斯异质结的可控制备与光电应用

自石墨烯被发现以来,二维材料因其优异的特性获得了持续且深入的探索与发展,以石墨烯、六方氮化硼、过渡金属硫化物、黑磷等为代表的二维材料相关研究层出不穷.随着二维新材料制备与应用探索的不断发展,单一材料性能的不足逐渐凸显,研究者们开始考虑采用平面拼接和层间堆垛所产生的协同效应来弥补单一材料的不足,甚至获得一些新的性能.利用二维材料晶格结构的匹配构建异质结,实现特定的功能化,或利用范德瓦耳斯力进行堆垛,将不同二维材料排列组合,从而在体系里引入新的自由度,为二维材料的性质研究和实际应用打开了新的窗口.本文从原子制造角度,介绍了二维平面和范德瓦耳斯异质结材料的可控制备和光电应用.首先简要介绍了应用于异质结制备的常见二维材料的分类及异质结的相关概念,然后从原理上分类列举了常用的表征方法,随后介绍了平面和垂直异质结的制备方法,并对其光电性质及器件应用做了简要介绍.最后,对领域内存在的问题进行了讨论,对未来发展方向做出了展望.     

氧化石墨烯纳米剪裁方法

石墨烯纳米剪裁先进方法的研究对于基于石墨烯的电子和光学设备非常重要。本文利用模板法制作反蛋白石结构,并借助反蛋白石纳米网结构,利用光催化还原氧化石墨烯,对氧化石墨烯进行纳米剪裁,形成具有纳米尺度的石墨烯。对还原后的氧化石墨烯表面进行扫描电子显微镜表征和红外光谱表征,并研究剪裁后石墨烯的电学性质。实验表明,反应时间、胶粒大小都会对剪裁后氧化石墨烯的周期和颈宽有影响,进而影响还原后氧化石墨烯的电学性质。利用纳米网状结构对石墨烯进行纳米剪裁是一种可行的方法,通过控制模板尺寸和反应条件可以控制裁剪后的性质。     

Modulation of the second-harmonic generation in MoS_2 by graphene covering

Nonlinear optical frequency mixing,which describes new frequencies generation by exciting nonlinear materials with intense light field,has drawn vast interests in the field of photonic devices,material characterization,and optical imaging.Investigating and manipulating the nonlinear optical response of target materials lead us to reveal hidden physics and develop applications in optical devices.Here,we report the realization of facile manipulation of nonlinear optical responses in the example system of MoS₂ monolayer by van der Waals interfacial engineering.We found that,the interfacing of monolayer graphene will weaken the exciton oscillator strength in MoS₂ monolayer and correspondingly suppress the second harmonic generation(SHG)intensity to 30%under band-gap resonance excitation.While with off-resonance excitation,the SHG intensity would enhance up to 130%,which is conjectured to be induced by the interlayer excitation between MoS₂ and graphene.Our investigation provides an effective method for controlling nonlinear optical properties of two-dimensional materials and therefore facilitates their future applications in optoelectronic and photonic devices.     

氧化石墨烯的多色发光及其在荧光成像中的应用

氧化石墨烯作为石墨烯的一种带隙打开的衍生物,极大地丰富了其光学性质,并拓展了它在传感和成像方面的应用,特别是氧化石墨烯限域的π共轭结构对构建发光碳材料提供了十分便利的条件。目前,有大量的研究工作报道了氧化石墨烯及其衍生物能够产生多种颜色的荧光信号,然而,系统地总结这些研究去揭示氧化石墨烯发光机理的相关工作还比较少。本文总结了关于发光氧化石墨烯纳米材料的合成及其在光学成像方面应用的大量研究工作,为进一步开发新型的发光氧化石墨烯材料提供一些建设性意见。     

Two‐Dimensionally Ordered Plasmonic and Magnetic Nanostructures on Transferable Electron‐Transparent Substrates

Discovery of new plasmonic behaviors from nanostructured materials can be greatly accelerated by the ability to prepare and characterize their near‐field behaviors with high resolution in a rapid manner. Here, an efficient and cost‐effective way is reported to make 2D periodic nanostructures on electron‐transparent substrates for rapid characterization by transmission electron microscopy. By combining nanosphere lithography with a substrate float‐off technique, large areas of electron‐transparent periodic nanostructures can be achieved. For this study, the synthesis of plasmonic nanostructures of Ag, magnetic nanostructures of Co, and bimetallic nanostructures of Ag–Co are investigated. Characterization of the materials by a combination of transmission electron microscopy, far‐field optical spectroscopy, and magnetization measurements reveals that this new approach can yield useful nanostructures on transparent, flexible, and transferable substrates with desirable plasmonic and/or magnetic properties.     

Toplayer-dependent crystallographic orientation imaging in the bilayer two-dimensional materials with transverse shear microscopy

Nanocontact properties of two-dimensional (2D) materials are closely dependent on their unique nanomechanical systems, such as the number of atomic layers and the supporting substrate. Here, we report a direct observation of toplayer-dependent crystallographic orientation imaging of 2D materials with the transverse shear microscopy (TSM). Three typical nanomechanical systems, MoS₂ on the amorphous SiO₂/Si, graphene on the amorphous SiO₂/Si, and MoS₂ on the crystallized Al₂O₃, have been investigated in detail. This experimental observation reveals that puckering behaviour mainly occurs on the top layer of 2D materials, which is attributed to its direct contact adhesion with the AFM tip. Furthermore, the result of crystallographic orientation imaging of MoS₂/SiO₂/Si and MoS₂/Al₂O₃ indicated that the underlying crystalline substrates almost do not contribute to the puckering effect of 2D materials. Our work directly revealed the top layer dependent puckering properties of 2D material, and demonstrate the general applications of TSM in the bilayer 2D systems.     

SnO2量子点/石墨烯复合结构的合成及其光催化性能研究

本文以SnCl₄·5H₂O和氧化石墨烯为先驱物, 乙醇水溶液为溶剂, 采用一种简单的水热法一步合成了具有可见光催化活性的SnO₂量子点(约3–5 nm)与石墨烯复合结构, 利用透射电子显微镜(TEM), 高分辨透射电子显微镜(HRTEM), X射线衍射仪(XRD), 傅里叶变换红外光谱(FT-IR)等技术对其结构进行了表征, 利用紫外可见吸收光谱(UV-vis)分析了其光学性能, 罗丹明-B染料为目标降解物研究了SnO₂量子点/石墨烯复合结构可见光催化性能. 结果表明: 与纯SnO₂、纯石墨烯相比, 复合结构显示出了很高的可见光催化活性. 通过对其结构进行分析, 我们提出了SnO₂量子点/石墨烯复合结构的形成机制及其可见光催化活性机理.     

Preparation and electrochemical properties of LiFePO<Subscript>4</Subscript>/graphene composites from tailoring graphene oxides

LiFePO₄/graphene composites have been prepared by using tailoring graphene oxide (GO) nanosheets as precursors. The structure and electrochemical properties of the composites were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), Raman microscopy, and a variety of electrochemical testing techniques. The decrease in graphene size reduces the contact resistance between activated materials, and enhances the lithium-ion transport in LiFePO₄/graphene composites. With low weight fractions of small-size graphene sheets, the composites show better electrochemical performance than those with large size graphene sheets.     

Low energy electron microscopy and photoemission electron microscopy investigation of graphene

Low energy electron microscopy (LEEM) and photoemission electron microscopy (PEEM) are two powerful techniques for the investigation of surfaces, thin films and surface supported nanostructures. In this review, we examine the contributions of these microscopy techniques to our understanding of graphene in recent years. These contributions have been made in studies of graphene on various metal and SiC surfaces and free-standing graphene. We discuss how the real-time imaging capability of LEEM facilitates a deeper understanding of the mechanisms of dynamic processes, such as growth and intercalation. Numerous examples also demonstrate how imaging and the various available complementary measurement capabilities, such as selected area or micro low energy electron diffraction (μLEED) and micro angle resolved photoelectron spectroscopy (μARPES), allow the investigation of local properties in spatially inhomogeneous graphene samples.     

Raman spectroscopy characterization of two-dimensional materials

Two-dimensional(2D) materials have become a hot study topic in recent years due to their outstanding electronic,optical, and thermal properties. The unique band structures of strong in-plane chemical bonds and weak out-of-plane van der Waals(vdW) interactions make 2D materials promising for nanodevices and various other applications. Raman spectroscopy is a powerful and non-destructive characterization tool to study the properties of 2D materials. In this work, we review the research on the characterization of 2D materials with Raman spectroscopy. In addition, we discuss the application of the Raman spectroscopy technique to semiconductors, superconductivity, photoelectricity, and thermoelectricity.     

SiP monolayers: New 2D structures of group IV–V compounds for visible-light photohydrolytic catalysts

Because of graphene and phosphorene, two-dimensional (2D) layered materials of group IV and group V elements arouse great interest. However, group IV–V monolayers have not received due attention. In this work, three types of SiP monolayers were computationally designed to explore their electronic structure and optical properties. Computations confirm the stability of these monolayers, which are all indirect-bandgap semiconductors with bandgaps in the range 1.38–2.21 eV. The bandgaps straddle the redox potentials of water at pH = 0, indicating the potential of the monolayers for use as watersplitting photocatalysts. The computed optical properties demonstrate that certain monolayers of SiP 2D materials are absorbers of visible light and would serve as good candidates for optoelectronic devices.     

Thermal properties of two-dimensional materials

Two-dimensional(2D) materials, such as graphene, phosphorene, and transition metal dichalcogenides(e.g., Mo S2 and WS2), have attracted a great deal of attention recently due to their extraordinary structural, mechanical, and physical properties. In particular, 2D materials have shown great potential for thermal management and thermoelectric energy generation. In this article, we review the recent advances in the study of thermal properties of 2D materials. We first review some important aspects in thermal conductivity of graphene and discuss the possibility to enhance the ultra-high thermal conductivity of graphene. Next, we discuss thermal conductivity of Mo S2 and the new strategy for thermal management of Mo S2 device. Subsequently, we discuss the anisotropic thermal properties of phosphorene. Finally, we review the application of 2D materials in thermal devices, including thermal rectifier and thermal modulator.     

二维量子片及其光学研究进展

以石墨烯为代表的二维材料因其独特的结构和优异性能而受到广泛关注。随着二维材料在无限小的方向不断发展,二维(材料)量子片逐渐引起人们极大的兴趣。二维量子片不仅保留了二维材料的本征特性,而且表现出量子限域和突出的边缘效应,为二维材料的潜在应用带来全新机遇。本文详细介绍了二维量子片的基本概念,制备现状与光学性能的研究进展,特别强调了二维量子片本征、普适和规模制备的实现及其重大意义。此外,重点关注了二维量子片的光致发光特性以及在非线性光学、固态发光器件等领域的应用。最后,分析了二维量子片的发展趋势以及面临的主要挑战。     

金属衬底上石墨烯的红外近场光学

对石墨烯/铜体系开展了系统性的近场光学实验研究,成功观测到了区别于铜衬底的、来自石墨烯的近场光学响应信号,发现在表面台阶几何参数相同的铜衬底上的不同石墨烯样品表现出了截然不同的近场光学响应.     

Local probe of the interlayer coupling strength of few-layers SnSe by contact-resonance atomic force microscopy

The interlayer bonding in two-dimensional (2D) materials is particularly important because it is not only related to their physical and chemical stability but also affects their mechanical, thermal, electronic, optical, and other properties. To address this issue, we report the direct characterization of the interlayer bonding in 2D SnSe using contact-resonance atomic force microscopy (CR-AFM) in this study. Site-specific CR spectroscopy and CR force spectroscopy measurements are performed on both SnSe and its supporting SiO₂/Si substrate comparatively. Based on the cantilever and contact mechanic models, the contact stiffness and vertical Young’s modulus are evaluated in comparison with SiO₂/Si as a reference material. The interlayer bonding of SnSe is further analyzed in combination with the semi-analytical model and density functional theory calculations. The direct characterization of interlayer interactions using this non-destructive methodology of CR-AFM would facilitate a better understanding of the physical and chemical properties of 2D layered materials, specifically for interlayer intercalation and vertical heterostructures.     

A high-voltage lithium-ion battery prepared using a Sn-decorated reduced graphene oxide anode and a LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode

This paper describes the preparation and characterization of a high-voltage lithium-ion battery based on Sn-decorated reduced graphene oxide and LiNi_0.5Mn_1.5O₄ as the anode and cathode active materials, respectively. The Sn-decorated reduced graphene oxide is prepared using a microwave-assisted hydrothermal synthesis method followed by reduction at high temperature of a mixture of (C₆H₅)₂SnCl₂ and graphene oxide. The so-obtained anode material is characterized by thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and electron diffraction spectroscopy. The LiNi_0.5Mn_1.5O₄ is a commercially available product. The two materials are used to prepare composite electrodes, and their electrochemical properties are investigated by galvanostatic charge/discharge cycles at various current densities in lithium cells. The electrodes are then used to assemble a high-voltage lithium-ion cell, and the cell is tested to evaluate its performance as a function of discharge rate and cycle number.     

Two-dimensional materials for ultrafast lasers

As the fundamental optical properties and novel photophysics of graphene and related two-dimensional(2D) crystals are being extensively investigated and revealed, a range of potential applications in optical and optoelectronic devices have been proposed and demonstrated. Of the many possibilities, the use of 2D materials as broadband, cost-effective and versatile ultrafast optical switches(or saturable absorbers) for short-pulsed lasers constitutes a rapidly developing field with not only a good number of publications, but also a promising prospect for commercial exploitation. This review primarily focuses on the recent development of pulsed lasers based on several representative 2D materials. The comparative advantages of these materials are discussed, and challenges to practical exploitation, which represent good future directions of research, are laid out.     

Field-effect transistors based on two-dimensional materials for logic applications

Field-effect transistors （FETs） for logic applications, graphene and MoS2, are discussed. These materials have based on two representative two-dimensional （2D） materials, drastically different properties and require different consider- ations. The unique band structure of graphene necessitates engineering of the Dirac point, including the opening of the bandgap, the doping and the interface, before the graphene can be used in logic applications. On the other hand, MoS2 is a semiconductor, and its electron transport depends heavily on the surface properties, the number of layers, and the carrier density. Finally, we discuss the prospects for the future developments in 2D material transistors.     

NMR microscopy of polyurethane foams

NMR microimaging has been applied to the characterization of foam materials, in order to understand their properties and gain deeper insight into their structures. The structure of "open cell" foams can be visualized with sufficient resolution to obtain the size and shape of cells, as well as their spatial distribution within specimens. Statistics of cell sizes have been calculated from NMR microscopy and are in good agreement with results obtained from electron microscopy. We demonstrate that the local density of foams, which are parameters largely inaccessible by other analytical methods, readily can be determined by NMR microscopy.