一种简单的化学气相沉积法制备大尺寸单层二硫化钼

最近单层二硫化钼以其直接带隙的性质及在电子器件、催化、光电等领域中的潜在应用而备受关注.化学气相沉积法能够制备出高质量、大尺寸且性能优良的单层二硫化钼,但其制备工艺比较复杂.本文采用简化的化学气相沉积法在蓝宝石衬底上制备出了大尺寸的单晶二硫化钼.清洗衬底时,只需要简单的清洁,不需要用丙酮、食人鱼溶液(H_2SO_4/H_2O_2=3:1)等处理,这样既减少了操作步骤,又避免了潜在的危险.升温时直接从室温加热到生长的温度,不必分段升温,并且采用常压化学气相沉积法,不需要抽真空等过程,使得实验可以快捷方便地进行.光学显微镜、拉曼光谱和光致发光谱的结果表明,生长的二硫化钼为规则的三角形单层,边长为50μm左右,远大于机械剥离的样品.     

缺陷单层和双层石墨烯的拉曼光谱及其激发光能量色散关系

拉曼光谱作为一种无破坏性、快速且敏锐的测试技术已经成 为表征石墨烯样品和研究其缺陷的最重要的实验手段之一. 本论文用离子注入在单层和双层石墨烯中产生缺陷, 并利用拉曼光谱研究了存在缺陷时单层和双层石墨烯的一阶和二阶拉曼模, 单层石墨烯的D模为双峰结构, 而双层石墨烯的D模具有四峰结构. 同时, 利用四条激光线系统地研究了本征和缺陷单层和双层石墨烯的拉曼峰频率的激发光能量依赖关系, 并基于石墨材料的双共振拉曼散射机理指认了离子注入后样品各拉曼峰的物理根源. 关键词： 石墨烯 缺陷 拉曼光谱 能量色散关系     

单层单晶石墨烯与柔性基底界面性能的实验研究

单晶石墨烯具有更优异的力学及电学性能,有望成为新一代柔性电子器件的核心材料.因此,有必要从实验的角度精细分析化学气相沉积法制得的大尺度单晶石墨烯与柔性基底复合结构的界面力学行为.本文通过显微拉曼光谱实验方法测量了不同长度的单层单晶石墨烯/PET(聚对苯二甲酸乙二醇酯)基底的界面力学性能参数及其在长度方向上界面边缘的尺度效应.实验给出了石墨烯在PET基底加载过程中与基底间黏附、滑移、脱黏三个界面状态的演化过程与应力分布规律.实验发现,单晶石墨烯与柔性基底间由范德瓦耳斯力控制的界面应变传递过程存在明显的边缘效应,并且与石墨烯的长度有关.界面的切应力具有尺度效应,其值随石墨烯长度的增加而减小,而石墨烯界面传递最大应变以及界面脱黏极限则不受试件尺度的影响.     

石墨烯在强激光作用下改性的拉曼研究

采用化学气相沉积法制备了不同层数的石墨烯样品.根据石墨烯透过率曲线分析石墨烯样品层数与550 nm处透过率关系的同时,利用拉曼光谱法分析了不同层数石墨烯样品在强激光辐照下的损伤特性.结果表明:单层石墨烯样品经强激光辐照后,G带和2D带均向高频移动;多层石墨烯样品经强激光辐照后只有G带发生了略微的频移;石墨烯样品拉曼光谱G带与2D带强度比值表征了石墨烯的层数,此比值随激光辐照时间的增加而减小,这表明强激光对石墨烯样品具有明显的剥离现象.     

Br掺杂对石墨烯带隙影响的实验研究

石墨烯独特的结构和性能使其在纳米电子、半导体器件等领域成为研究的热点,但其零带隙的特性严重限制了其应用.采用化学气化沉积法制备了多层石墨烯,并使用溴蒸汽对制备的多层石墨烯进行掺杂,分析研究了溴蒸汽化学掺杂对石墨烯带隙的影响.为了对比溴蒸汽掺杂对石墨烯带隙的影响,使用633 nm He-Ne光分别测量了石墨烯掺杂前和掺杂后的拉曼光谱,根据拉曼光谱计算了石墨烯费米能级移动与掺杂溴蒸汽之间的关系.实验结果表明:溴蒸汽掺杂对石墨烯拉曼光谱G带产生影响;随着掺杂溴蒸汽体积的增加,拉曼光谱G带向高频移动并逐渐趋于稳定;G带和2D带强度比也迅速增加,并最终趋于稳定.费米能级的移动与G峰位置成线性关系,利用G峰峰值位置与费米能级实验关系式计算了溴掺杂后石墨烯的费米能级,分析了化学掺杂对石墨烯带隙的影响.     

二维层状晶体材料层间剪切模和层间呼吸模的拉曼光谱研究

我们将四片布拉格体光栅技术集成到单光栅拉曼光谱仪中,并且成功地探测到2至19层二硫化钼(MoS2)的层间剪切模和层间呼吸模。我们根据对称性分析和偏振拉曼的结果对所有观察到的模式进行了指认。同时,我们利用简单的"单原子线性链"模型得到了适用于任何二维层状晶体材料层间振动模的频率随层数变化关系的解析形式。根据此模型,我们发现层间弱范德瓦耳斯力作用决定了剪切模和呼吸模的频率随层数的变化。我们将此结果推广到ABC堆垛的多层石墨烯材料,发现光学衬度方法无法鉴别的AB和ABC型石墨烯可以利用能否观察到剪切模来加以鉴别。此研究结果也提供了准确地确定二维层状材料的厚度的一种新方法,为一般二维层状材料基本性质和器件应用方面的研究奠定了基础。     

高质量单层二硫化钼薄膜的研究进展

作为一种新型的二维半导体材料,单层二硫化钼薄膜由于其优异的特性,在电子学与光电子学等众多领域具有潜在的应用价值.本文综述了我们课题组在过去几年中针对单层二硫化钼薄膜的研究所取得的进展,具体包括:在二硫化钼薄膜的制备方面,通过氧辅助化学气相沉积方法,实现了大尺寸单层二硫化钼单晶的可控生长和晶圆级单层二硫化钼薄膜的高定向外延生长;在二硫化钼薄膜的加工方面,发展了单层二硫化钼薄膜的无损转移、洁净图案化加工、可控结构相变与局域相调控的方法,为场效应晶体管等电子学器件的制备与性能优化提供了基础;在二硫化钼异质结方面,研究了二硫化钼薄膜与其他二维材料形成的异质结的电学以及光电性质,为二维材料异质结的构筑和器件特性研究提供了实验参考;在二硫化钼薄膜功能化器件与应用方面,构筑了全二维材料、亚5 nm超短沟道场效应晶体管器件,验证了单层二硫化钼对短沟道效应的有效抑制及其在5 nm工艺节点器件中的应用优势;此外,利用制备的高质量单层二硫化钼和发展的器件洁净加工技术,实现了高性能柔性薄膜晶体管的集成,获得了超高灵敏度与稳定性的非接触型湿度传感器.我们在二硫化钼薄膜的制备、加工以及器件特性研究方面所取得的进展对于二硫化钼及其他二维过渡金属硫属化合物的基础和应用研究均具有指导意义.     

三层石墨烯及其n型和p型插层化合物的制备和拉曼光谱表征

我们利用微机械剥离方法制备了三层石墨烯.在此基础上,利用两室气体传输法,以三氯化铁和钾为化学掺杂剂,成功合成了三层石墨烯的一阶p型和n型插层化合物.三层石墨烯的高分辨率拉曼光谱具有独特的2D谱峰线形,该线形可以用作指纹来鉴别三层石墨烯.三层石墨烯一阶插层化合物的拉曼光谱表明,三氯化铁和钾的插层掺杂使得三层石墨烯的层间耦...     

胶体二硫化钼的高压拉曼散射研究

 测量了平均直径为4 μm的胶体二硫化钼粉剂的高压拉曼光谱。实验结果表明,高压下胶体二硫化钼拉曼峰位随压力增大向高波数方向移动,而峰强随压力增大而减小且峰宽展宽。通过对拉曼峰位移随压力变化的曲线分析,得到了胶体二硫化钼的两个振动模式E¹_2g和A_1g的模式格林爱森常数值。     

转角多层石墨烯层间耦合的共振拉曼光谱研究

我们通过共振拉曼光谱测量了转角多层石墨烯的层间振动模式:剪切模和呼吸模。根据改进的线性模型,我们发现在转角多层石墨烯界面处的层间呼吸耦合与正常Bernal堆垛多层石墨烯的强度相当。此结果明显不同于层间剪切耦合,后者在转角多层石墨烯界面处的层间剪切耦合减弱到了正常Bernal堆垛多层石墨烯的20%。另外,我们首次发现层间呼吸耦合存在着次近邻原子层之间的相互作用,其强度为最近邻的9%。我们发现当采用与界面层间旋转角度相对应的激发光时,转角多层石墨烯的拉曼信号得到极大的增强。为此,我们引入光学跃迁允许的电子联合态密度的概念,通过理论计算,我们发现这种联合态密度的极大值决定了拉曼信号共振线型的激发光能量极值。本研究表明,层间振动模式是探测二维层状异质层间耦合的有效手段,为其在器件应用方面的研究奠定了基础。     

Graphene versus MoS2: A short review

Graphene and MoS₂ are two well-known quasi two-dimensional materials. This review presents a comparative survey of the complementary lattice dynamical and mechanical properties of graphene and MoS₂, which facilitates the study of graphene/MoS₂ heterostructures. These hybrid heterostructures are expected to mitigate the negative properties of each individual constituent and have attracted intense academic and industrial research interest.     

MoS_2溶液的波长选择性光限幅效应研究

采用N,N-二甲基甲酰胺(DMF)和四氢呋喃(THF)为溶剂,用离散法制备二硫化钼(MoS2)悬浮溶液,并用开孔Z扫描方法研究其在可见和近红外区域的非线性光学特性.结果显示,在强激光照射下,MoS2(in THF)悬浮溶液在可见波段(530 nm)透过率增强为常光透过率的1.54倍,表现为饱和吸收;在近红外波段(790 nm)透过率减弱为常光透过率的0.6倍,表现为反饱和吸收,具有很好的波长选择性光限幅效应.而作为对比的MoS2(in DMF)悬浮溶液在全波段透过率降低,呈现反饱和吸收特性,波长选择性不明显.机理解释可能为饱和吸收和热效应导致的自衍射两种机制联合作用.     

The thermal stability of graphene in air investigated by Raman spectroscopy

The thermal stability in air of graphene synthesized by either chemical vapor deposition or mechanical cleavage is studied. It is found that single layer graphene prepared by both methods starts to show defects at ~500 °C, indicated by the appearance of a disorder‐induced Raman D peak. The defects are initially sp³ type and become vacancy like at higher temperature. On the other hand, bilayer graphene shows better thermal stability, and the D peak appears at ~600 °C. These results are quite different from those annealing in vacuum and controlled atmosphere. Raman images show that the defects in chemical vapor deposition graphene are not homogeneous, whereas those in mechanical cleavage graphene are uniformly distributed across the whole sample. The factors that affect the thermal stability of graphene are discussed. Our results could be important for guiding the future electronics process and chemical decoration of graphene. Copyright © 2013 John Wiley & Sons, Ltd.     

快重离子辐照对MoS2热导率的影响研究

利用0.97 GeV的209Bi离子辐照二硫化钼（MoS₂）晶体,辐照注量范围为1×1010～1×1012 ions/cm2,结合原子力显微镜（AFM）观测和Raman光谱分析研究了快重离子辐照对MoS₂热导率的影响。实验结果显示,快重离子辐照在MoS₂中产生了潜径迹,较高激光功率下的Raman测试使样品局部温度升高,导致E_1/2g和A_1g峰随注量增加向低波数方向移动,且峰形展宽。引入了通过改变激光功率测量Raman光谱得到MoS₂热导率的计算方法,获得了不同辐照注量下MoS₂的热导率的定量分析结果,随注量增加,热导率不断降低,从未辐照样品的563 W/mK下降到1×1012 ions/cm2辐照时的132 W/mK。Molybdenum disulphide (MoS₂) was irradiated by 0.97 GeV 209Bi ions with the fluence of 1×1010 to 1×1012 ions/cm2. The irradiation effect on the thermal conductivity of MoS₂ was analyzed by atomic force microscope (AFM) and Raman spectroscopy. The experimental results show that hillock-like latent tracks are observed on irradiated MoS₂ by AFM. The measurement of MoS₂ by Raman spectrometer with high laser power results in the increase of local temperature of MoS₂, which cause the downshift of peaks position and broadening of E_1/2g and A_1g peak. Furthermore, according to Raman spectra measured at different laser power, thermal conductivity of MoS₂ before and after irradiation was calculated, which show that the thermal conductivity of MoS₂ decreases with increasing fluence, from 563 to 132 W/mK for pristine and 1×1012 ions/cm2 irradiated MoS₂, respectively.     

Phonon spectra of La0.5Ca2MnO3

This paper presents a microscopic theory to explain different Raman modes of La0.5Ca0.5MnO3 based on the electronic Hamiltonian of the Kondo lattice model,which adds phonon interaction to the hybridization between the conduction electrons of the system and the l-electrons.The spectral density is calculated by the Green function technique of Zubarev at zero wave vector and in the low temperature limit.It finds that there are three Raman-active modes and the spectral densities of these modes are substantially influenced by model parameters such as the position of l-level(εJT),the effective electron-phonon coupling strength(g) and the hybridization parameter(v).Finally,the intensity changes of those peaks are investigated.     

Raman scattering of the MoS2 and WS2 single nanotubes

We report here the results of the first resonance Raman study on single MoS₂ and WS₂ nanotubes and microtubes synthesized by chemical transport reaction. These multiwall tubes represent the longest known inorganic nanotubes grown up to several millimetre lengths with diameters ranging from less than ten nanometers to several micrometers. The nanotubes grown at nearly equilibrium conditions contain extremely low density of structural defects. The selected area diffraction on the thick-wall nanotubes revealing the rhombohedral (3R) stacking, otherwise stable at elevated pressure above 4 GPa, provides indirect evidence of the presence of strain incorporated into the nanotube wall. Results are compared with phonon spectra of plate-like crystals of the same compound. The observed up-shift of Raman peaks in the tubes spectra is explained by the presence of strain. Well preserved crystal structure of tubes is confirmed by comparison with phonon spectra of nanostructured materials from literature.     

Direct growth of graphene on gallium nitride using C2H2 as carbon source

Growing graphene on gallium nitride (GaN) at temperatures greater than 900°C is a challenge that must be overcome to obtain high quality of GaN epi-layers. We successfully met this challenge using C₂H₂ as the carbon source. We demonstrated that graphene can be grown both on copper and directly on GaN epi-layers. The Raman spectra indicated that the graphene films were about 4–5 layers thick. Meanwhile, the effects of the growth temperature on the growth of the graphene films were systematically studied, and 830°C was found to be the optimum growth temperature. We successfully grew high-quality graphene films directly on gallium nitride.     

W doping-dependent structural and ferroelectric properties of SrBi2Nb2O9 ferroelectric ceramics

The structural and ferroelectric characteristics of SrBi₂(Nb_1−xW_x)₂O₉ (x=0–0.12) ferroelectric ceramics were investigated. SrBi₂(Nb_1−xW_x)₂O₉ ceramics consisted of a single-phase layered perovskite structure when x was less than 0.06. Uniform microstructure and grain size reduction were observed after the introduction of W. The maximum remanent polarization of 16 μC/cm² appeared at x=0.03, and the coercive field decreased with increasing concentration of W. The ferroelectric behavior of SrBi₂(Nb_1−xW_x)₂O₉ ceramics is interpreted based on the Raman measurement.     

Thermal stability of HfO2 nanotube arrays

Thermal stability of highly ordered hafnium oxide (HfO₂) nanotube arrays prepared through an electrochemical anodization method in the presence of ammonium fluoride is investigated in a temperature range of room temperature to 900 °C in flowing argon atmosphere. The formation of the HfO₂ nanotube arrays was monitored by current density transient characteristics during anodization of hafnium metal foil. Morphologies of the as-grown and post-annealed HfO₂ nanotube arrays were analyzed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Although monoclinic HfO₂ is thermally stable up to 2000 K in bulk, the morphology of HfO₂ nanotube arrays degraded at 900 °C. A detailed X-ray photoelectron spectroscopy (XPS) study revealed that the thermal treatment significantly impacted the composition and the chemical environment of the core elements (Hf and O), as well as F content coming from the electrolyte. Possible reasons for the degradation of the nanotube at high temperature were discussed based on XPS study and possible future improvements have also been suggested. Moreover, dielectric measurements were carried out on both the as-grown amorphous film and 500 °C post-annealed crystalline film. This study will help us to understand the temperature impact on the morphology of nanotube arrays, which is important to its further applications at elevated temperatures.