化学气相沉积法生长石墨烯的研究

以甲烷为碳源,原铜箔和用过硫酸铵清洗过的铜箔为衬底,对比研究了铜的表面结构、生长温度及冷却速率对石墨烯CVD法生长的影响.研究发现经过处理的铜箔表面粗糙度小,显微结构精细,化学活性高,更有利于石墨烯的快速形核与生长.而原铜箔因表面粗糙度大,存在大量粗大纹理结构,化学活性低,使得石墨烯的形核生长需要更高的温度.因而,对于不同衬底,选择合适的生长温度至关重要.而提高冷却速率有利于获得大尺寸、高质量并具有原生生长形貌的石墨烯.     

基于抛光基材的热蒸镀铜箔生长高平整单层石墨烯薄膜

在石墨烯的化学气相沉积工艺中,铜箔是决定石墨烯薄膜质量的重要因素。传统铜箔由于制备工艺的限制,存在大量的缺陷,导致石墨烯薄膜的成核密度较高。本工作选用抛光铝板、抛光不锈钢板、微晶玻璃和SiO₂/Si作为基材,用热蒸镀法制备了不同粗糙度的铜箔,并详细讨论了以该系列铜箔生长高平整度石墨烯薄膜的条件及铜箔对石墨烯薄膜品质的影响。实验结果表明,铜箔以(111)取向为主,与基材分离后,表面具有纳米级平整度。在生长石墨烯后,从SiO₂/Si剥离的铜箔成核密度是4种基材中最小的。同时,从SiO₂/Si剥离的铜箔晶体结构变化最不明显,具有良好的结晶性,表面几乎不存在铜晶界缺陷。当压强为3 000 Pa,氢气和甲烷流速分别为300 mL/min和0.5 mL/min时,可以获得约1 mm横向尺寸的石墨烯单晶晶畴。     

反应离子刻蚀制备石墨烯纳米盘阵列

采用化学气相沉积法以乙醇为碳源在铜箔生长的单层高质量的石墨烯并将其转移到SiO2/Si基底上。然后在通过自组装的方法在石墨烯表面覆盖一层单层的PS微球阵列。采用反应离子刻蚀的方法在一定的刻蚀条件下对其进行刻蚀,随着刻蚀的时间增加,PS微球的会被逐渐刻蚀掉,石墨烯也会在这个过程中随着被刻蚀。将残留的PS微球杂质去掉后,会在 SiO2/Si基底上呈现出排列规整的石墨烯纳米盘阵列。通过场发射扫描电子显微镜( SEM)、拉曼光谱对石墨烯纳米盘及其形成过程进行表征和分析,为后续制备高质量石墨烯纳米带、石墨烯纳米点、石墨烯纳米盘提供参考。     

低熔点合金衬底上CVD法生长石墨烯

以CH4为气态碳源,不同组分的In基合金为衬底,用CVD法进行石墨烯生长的研究结果.用光学显微镜,拉曼光谱,场发射扫描电镜对生长的薄层进行了表征.结果显示在熔融态金属Cu-In合金上成功制备了石墨烯薄膜,“表面催化”型金属Cu的加入In使金属表面形核点增多,合金表面石墨烯的生长速度提高,但石墨烯质量下降;“溶解析出”型金属Ni与低熔点金属In组成的合金催化性能有明显的增强,在极短的时间内堆积成石墨“块”;金属Sn不具备明显的催化生长石墨烯的能力,导致了Sn-In合金衬底上石墨烯的生长与纯In类似,Sn的影响作用较弱.     

填隙法在抛光铜衬底上制备高质量石墨烯薄膜

本文对在抛光铜衬底上通过填隙法制备的高质量石墨烯薄膜进行了详细研究。在电化学机械抛光后的铜衬底上制备石墨烯晶畴,降低了晶畴的成核密度。利用光学显微镜和扫描电子显微镜对抛光铜衬底和未抛光铜衬底上制备的石墨烯晶畴进行测试,测试结果表明,铜衬底的表面形态对于降低石墨烯的成核密度,增大石墨烯晶畴的尺寸起到了至关重要的作用。利用拉曼面扫描证明了所制备的石墨烯晶畴为单层、均匀的石墨烯晶畴。然后,通过填隙法在抛光铜衬底上制备出由大尺寸单层的六边形石墨烯晶畴组成的石墨烯连续薄膜,并且通过流程示意图解释了填隙法制备高质量石墨烯薄膜的过程。本文所提出的在抛光铜衬底上通过填隙法制备石墨烯薄膜的技术,能够有效提高石墨烯薄膜的质量,进而有效改善石墨烯基电子器件的性能。     

SiC籽晶表面状态对晶体质量的影响

为了研究表面状态对晶体质量的影响,本文分别采用腐蚀后抛光与未抛光的晶片作为籽晶,利用金相显微镜对所得晶体进行了显微观察,结果表明:经过腐蚀后抛光的籽晶生长出的晶体质量高于未抛光籽晶所得晶体;生长前端的位错尺寸以及数量小于未抛光籽晶,说明抛光去除了部分表面浅的缺陷腐蚀坑,同时减小深腐蚀坑的尺寸,使得籽晶生长表面的缺陷密度和尺寸大大降低,有助于减少后期生长的晶体中的缺陷密度,提高结晶质量.     

石墨烯保护层对铜电化学腐蚀行为的影响研究

以铜箔为基底通过常压化学气相沉积法制备了高质量、连续的少层石墨烯.采用极化曲线和电化学阻抗谱对纯铜箔及石墨烯/铜样品在0.1 mol/L NaCl溶液中的抗腐蚀性能进行了研究.结果表明,石墨烯/铜样品的自腐蚀电位比纯铜箔的高0.114 V,腐蚀电流密度较纯铜箔的低1个数量级,极化电阻较纯铜箔的高4.4倍,阻抗模值比纯铜箔的提高了约1个数量级.因此,石墨烯可以作为铜表面的保护层,抑制铜在NaCl溶液中发生电化学反应,从而增强铜的抗腐蚀性能.     

CVD金刚石薄膜表面的缺陷研究

用SEM方法观察分析了CVD金刚石薄膜表面的缺陷形貌和结构,直观的两种缺陷为孪晶和孔洞.孪晶反映了晶粒的不完整性,它的产生取决于气相中活性分子的浓度与生长表面活性位数目的比值,孪晶比率随碳源浓度升高和衬底温度的降低而增大;孔洞反映了膜的不致密性,其产生与膜生长速率和衬底表面初始成核密度切相关,孔洞密度随碳源浓度升高和衬底温度的升高而增大.     

氮化镓籽晶的表面损伤处理及氨热生长研究

籽晶的表面损伤会导致后续生长的晶体位错增多.为了降低籽晶表面的损伤,通常采用粗磨-精磨-抛光的多步过程处理的晶片作为籽晶,工艺步骤多、复杂,成本高.本文采用磷酸去除表面损伤层的粗磨GaN与化学机械抛光的GaN分别作为籽晶,对比了两种籽晶氨热生长后晶体表面、生长速率、结晶质量、应力状况.光学显微镜表明两种籽晶生长后晶体的表面具有相似的丘状表面.氨热法生长速率较慢,化学机械抛光籽晶生长速率略高于粗磨籽晶.X射线单晶衍射(XRD) (002)和(102)的摇摆曲线半高宽显示抛光籽晶与粗磨籽晶生长得到GaN结晶质量基本一致.Raman E2(high)频移表明抛光籽晶生长的GaN晶体接近无应力状态,粗磨籽晶生长的晶体存在较小的压应力.     

气相捕获腔对石墨烯低压化学气相沉积形核生长的影响

基于石墨烯低压化学气相沉积技术,通过调控甲烷流量对比研究了传统生长腔和气相捕获腔中石墨烯在铜箔衬底上的形核生长特点.结果 表明,与传统生长腔相比,气相捕获腔能够将石墨烯的形核密度降低3个数量级,并促使石墨烯晶核快速长大.同时,气相捕获腔能够为石墨烯提供一个稳定的生长环境,有利于制备晶格完美的石墨烯晶畴,并为石墨烯晶畴的融合提供更多的有效活性碳原子,加速石墨烯晶畴之间的融合,提高石墨烯薄膜的质量.在此基础上分析了气相捕获腔对石墨烯低压化学气相沉积形核生长的影响机理.     

Structure and chemical composition of LiB3O5 surfaces

The electronic and structural properties of LiB₃O₅ (LBO) surfaces have been studied by X‐ray photoemission spectroscopy (XPS) and reflectance high‐energy electron diffraction (RHEED). The as‐grown (110) crystal face and mechanically polished (001) surfaces have been investigated comparatively. Electronic structure of LBO has been determined on as‐grown (110) crystal face previously cleaned by chemical etching with RHEED control. The correlation of valence band structure and measured binding energies with earlier reported results has been discussed. Core‐level spectroscopy reveals strong enriching of mechanically polished LBO surface with carbon, when nanodiamond powder is used as an abrasive. So high carbon level as C:B = 0.7 has been observed at the surface while the ratio Li:B:O remains according to LBO chemical composition. The association of LBO Kikuchi‐lines with strong background has been shown by RHEED analysis of the surface. Thus, the polished LBO surface constitutes a high structure quality LBO with the inclusions of some amorphous carbon compound. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of ZnO buffer layer on structural and optical properties of ZnO nanorods

A low‐temperature synthetic route was used to prepare oriented arrays of ZnO nanorods on ITO conducting glass substrate coated with buffer layer of ZnO seeds in an aqueous solution. The corresponding growth behavior and optical properties of ZnO nanorod arrays were studied. It was found that the nature of the buffer layer had effect on the microstructures and optical properties of the resultant ZnO nanorod arrays. X‐ray diffraction (XRD) results showed the nanorods were preferentially grown along (002) direction, but the diameter of the nanorods prepared with the buffer layer was much smaller than the without one, which can be clearly seen from the scanning electron microscopy (SEM) results. And it also found that the buffer layer was not only enhanced the density of overall coverage but also beneficial to grown the oriented arrays. Photoluminescence spectroscopy (PL) results indicated that the all the samples had the better optical behaviors. By computation, the relative PL intensity ratio of ultraviolet emission (I_UV) to deep level emission (I_DLE) of ZnO nanorods grown with the pure substrate was much higher than that of the sample with the buffer layer. The defects on the surface increased with the size reduction of nanorods caused by the buffer layer may be the main reason for it. And the small shift in the UV emission was caused by the rapid reduction in crystal size and compressive stress from Raman spectra results. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An electrolytic method to grow copper dendrites and single crystals in gels

A new electrolytic method for the growth of any metallic crystal in gel by using gel as a medium for controlled growth, is reported. Different types of large dendrites and single crystals of copper were grown by electrolytic method in the gel medium. It is found that pH of the gel medium, the concentration of the supernatant solution, the current density and the electrode material used, have considerable influence on the habits of the dendrites and the single crystals thus grown. The surface features and morphology of crystals and dendrites were studied by optical and scanning electron microscopy. Compared to other conventional electrolytic growth techniques, the present method has a number of additional parameters that can be varied, and hence a more effective controlled growth of crystals is possible.     

电沉积制备金属锡薄膜负极材料及其电化学性能研究

通过电沉积法,控制电流密度在铜箔上得到不同形貌的金属锡薄膜,采用扫描电子显微镜、X射线衍射、恒流充放电测试、循环伏安、交流阻抗法对其进行物理和电化学性能表征。结果表明:当电流密度为2 mA/cm²,所得金属锡薄膜表面最为致密,结晶度最高;将其作为负极材料组装成CR2025扣式电池,首次放电比容量为752 mAh/g,库伦效率为81.65%;30个循环后,放电比容量仍然维持在350 mAh/g。此外,该金属锡薄膜电极具有较高的电子导电性和锂离子扩散能力,其电荷转移电阻和锂离子扩散系数分别为113.3Ω和8.968×10^-17 cm²/s。     

Investigation on growth defects in Pb(Zn1/3Nb2/3)O3‐PbTiO3 crystals

Relaxor ferroelectric crystal (1‐x)Pb(Zn_1/3Nb_2/3)O₃‐xPbTiO₃ (PZNT) with x=0.07 (PZNT93/7) has been grown by the vertical Bridgman method from the high temperature solution of PZNT‐PbO system. The growth defects, such as nucleation core, inclusions, boundaries and particles, were investigated by optical microscope and scanning electron microscope. Sub‐structures were found in the flux inclusions and the lack of ZnO component in PZNT crystals was attributed to the existence of ZnO particles in the inclusions. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)