单晶金刚石边缘表面倾斜角度对同质外延生长的影响

利用微波等离子体化学气相沉积法,对单晶金刚石(100)晶面边缘进行精细切割抛光处理,形成偏离(100)晶面不同角度的倾斜面,在CH_4/H_2反应气体中进行同质外延生长,研究单晶金刚石边缘不同角度倾斜面对边缘金刚石外延生长的影响.实验结果表明,边缘倾斜面角度对边缘的单晶外延生长质量有影响,随着单晶金刚石边缘倾斜面角度的增大,边缘多晶金刚石数量先减少后增多,在倾斜角3.8°时边缘呈现完整的单晶外延生长特性.分析认为,边缘不同角度的倾斜面会改变周围电场强度和等离子体密度,导致到达衬底表面的含碳前驱物发生改变,倾斜面台阶表面的含碳前驱物浓度低于能形成层状台阶生长的临界浓度是减弱单晶金刚石生长过程中边缘效应的主要原因.     

籽晶尺寸对宝石级金刚石单晶生长的影响

本文在国产六面顶压机上,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用边长0.8, 1.5和2.2 mm三种尺寸的籽晶,系统开展了Ib型宝石级金刚石单晶的生长研究.文中系统考察了籽晶尺寸对宝石级金刚石单晶生长的影响.首先,考察了籽晶尺寸变化对宝石级金刚石单晶裂晶问题带来的影响.研究得到了籽晶尺寸变大,裂晶出现概率增加的晶体生长规律.其次,在25 h的生长时间内,考察了上述三种尺寸籽晶生长金刚石单晶时,生长时间与单晶极限生长速度的关系.得到了选用大尺寸籽晶,可以提高优质单晶合成效率、降低合成成本的研究结论.借助扫描电子显微镜和光学显微镜,对三种尺寸籽晶生长金刚石单晶的表面形貌进行了标定.最后,傅里叶微区红外测试,对三种尺寸籽晶生长宝石级金刚石单晶的N杂质含量进行了表征.研究得到了选用大尺寸籽晶实现快速生长金刚石的同时,晶体的N杂质含量会随之升高的晶体生长规律.     

温度对Ib型和IIa型金刚石大单晶(100)表面特征的影响

本文在5.6 GPa, 1250–1340 ℃的条件下, 利用温度梯度法, 以FeNiMnCo 合金为触媒, 沿籽晶的(100)晶面成功合成了不同晶形的优质Ib型和IIa型金刚石大单晶. 利用激光拉曼附件显微镜, 分别对上述不同温度下合成的两类金刚石样品上表面(100)面的中心区域及棱角区域进行观察分析. 研究发现, Ib型和IIa型金刚石大单晶(100)晶面上从中心到棱角处黑色纹路的分布逐渐变黑变密集; 另外, 随着金刚石合成温度的升高, Ib型金刚石大单晶(100)面上黑色纹路由稀疏逐渐变稠密, 而IIa型金刚石大单晶的黑色纹路较为稀疏; Ib型金刚石大单晶的形貌特征表现为从低温晶体的不规则分布过渡到中温、高温晶体的典型树枝状分布. IIa型金刚石大单晶(100)面特征随温度变化规律与Ib型的类似. 这两类金刚石大单晶表面特征的差异可能是由于IIa 型金刚石具有比Ib型更小的生长速度和更少的氮含量. 最后, 对两类塔状金刚石大单晶进行拉曼光谱测试分析, 结果表明IIa型金刚石大单晶的品质较Ib型金刚石大单晶好.     

Large‐surface‐area diamond (111) crystal plates for applications in high‐heat‐load wavefront‐preserving X‐ray crystal optics

Fabrication and results of high‐resolution X‐ray topography characterization of diamond single‐crystal plates with large surface area (10 mm × 10 mm) and (111) crystal surface orientation for applications in high‐heat‐load X‐ray crystal optics are reported. The plates were fabricated by laser‐cutting of the (111) facets of diamond crystals grown using high‐pressure high‐temperature methods. The intrinsic crystal quality of a selected 3 mm × 7 mm crystal region of one of the studied samples was found to be suitable for applications in wavefront‐preserving high‐heat‐load crystal optics. Wavefront characterization was performed using sequential X‐ray diffraction topography in the pseudo plane wave configuration and data analysis using rocking‐curve topography. The variations of the rocking‐curve width and peak position measured with a spatial resolution of 13 µm × 13 µm over the selected region were found to be less than 1 µrad.     

Investigation of heteroepitaxial diamond films by atomic force and scanning tunneling microscopy

We report on Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) investigations on chemical vapour deposited heteroepitaxial diamond films. Besides the good macroscopic crystal morphology a statistical tilt up to ±5.2° of the oriented crystallites has been found relative to the silicon substrates. By optimizing the process conditions, however, the crystal tilt of the films can be reduced, resulting in an improved film perfection. On crystallite (001)-surfaces a substructure of growth facets or islands has been found and high resolution STM images have established a 2×1 surface reconstruction on these growth facets. AFM and SEM were applied to study the morphology of diamond nuclei initially grown on the silicon substrate. Strong island like (Volmer-Weber) growth has been found, with a nucleus height to diameter ratio of 1:1. While the islands are growing in size with respect to time of nucleation, its aspect ratio does not change, due to the high surface free energy of the diamond relative to silicon.     

Momentum‐resolved resonant inelastic X‐ray scattering on a single crystal under high pressure

A single‐crystal momentum‐resolved resonant inelastic X‐ray scattering (RIXS) experiment under high pressure using an originally designed diamond anvil cell (DAC) is reported. The diamond‐in/diamond‐out geometry was adopted with both the incident and scattered beams passing through a 1 mm‐thick diamond. This enabled us to cover wide momentum space keeping the scattering angle condition near 90°. Elastic and inelastic scattering from the diamond was drastically reduced using a pinhole placed after the DAC. Measurement of the momentum‐resolved RIXS spectra of Sr_2.5Ca_11.5Cu₂₄O₄₁ at the Cu K‐edge was thus successful. Though the inelastic intensity becomes weaker by two orders than the ambient pressure, RIXS spectra both at the center and the edge of the Brillouin zone were obtained at 3 GPa and low‐energy electronic excitations of the cuprate were found to change with pressure.     

Relationship between the spatial position of the seed and growth mode for single-crystal diamond grown with an enclosed-type holder

The relationship between the spatial position of the diamond seed and growth mode is investigated with an enclosed-type holder for single-crystal diamond growth using the microwave plasma chemical vapor deposition epitaxial method. The results demonstrate that there are three main regions by varying the spatial position of the seed. Due to the plasma concentration occurring at the seed edge, a larger depth is beneficial to transfer the plasma to the holder surface and suppress the polycrystalline diamond rim around the seed edge. However, the plasma density at the edge decreases drastically when the depth is too large, resulting in the growth of a vicinal grain plane and the reduction of surface area. By adopting an appropriate spatial location, the size of single-crystal diamond can be increased from 7 mm × 7 mm × 0.35 mm to 8.6 mm × 8.6 mm × 2.8 mm without the polycrystalline diamond rim.     

降温工艺对宝石级金刚石单晶品质的影响

在国产六面顶压机上,采用温度梯度法,在5.6 GPa,1200—1400?C的高压高温条件下,裂晶问题频繁出现的合成周期内,围绕裂晶现象开展了Ib型宝石级金刚石单晶的生长研究,系统考察了降温工艺对宝石级金刚石单晶品质的影响.针对宝石级金刚石单晶常见的裂纹缺陷,借助于扫描电子显微镜,分别对优质金刚石单晶和存在裂纹金刚石单晶的表面形貌进行了表征;利用微区傅里叶转换红外光谱测试手段,对上述两类晶体的N杂质含量分别进行了测试,依据测试结果,对裂晶出现的原因进行了分析;分别采用传统断电降温和缓慢降温工艺,考察了晶体生长结束后的降温工艺对宝石级金刚石单晶品质的影响.结果表明,缓慢降温工艺在很大程度上可以有效抑制裂晶问题出现.另外,从宝石级金刚石单晶品质和单晶受到的外应力两个方面着手,分别对裂晶出现的机理和采用缓慢降温工艺有效解决裂晶问题的机理进行了讨论.     

Growth of nano-crystalline diamond on single-crystalline diamond by CVD method

Nanocrystalline (NC) diamond films are grown by chemical vapor deposition on various single crystal diamond faces. Under conditions of NC diamond growth, the growing filmmorphology is reduced to two planes: {100} and {111}. The {100} planes are smooth and homoepitaxial layerby-layer growth occurs on them, whereas the NC film formed by twin crystalliteswith sizes of several tens and hundreds nanometers grows on {111} planes. Nitrogen impurity sharply increases the diamond growth rate.     

合成腔体尺寸对Ib型六面体金刚石单晶生长的影响

利用液压缸直径为550 mm的大缸径六面顶压机, 在5.6 GPa, 1200-1400 ℃的高压高温条件下, 分别采用单晶种法和多晶种法, 开展了Ib型六面体宝石级金刚石单晶的生长研究, 系统考察了合成腔体尺寸对Ib型六面体金刚石大单晶生长的影响. 首先, 阐述了合成腔体尺寸对合成设备油压传递效率的影响, 研究得到了设备油压与腔体内实际压力的关系曲线; 其次, 选择尺寸为Φ 14 mm的合成腔体, 分别采用单晶种法和多晶种法(5颗晶种), 进行Ib型六面体金刚石大单晶的生长实验, 研究阐述了Φ 14 mm合成腔体的晶体生长实验规律; 再次, 为了解决液压缸直径与合成腔体尺寸不匹配的问题, 将合成腔体尺寸扩大到26 mm, 并开展了多晶种法六面体金刚石大单晶的生长研究, 最多单次生长出14 颗优质3 mm级Ib型六面体金刚石单晶, 研究得到了Φ 26 mm合成腔体生长3 mm级Ib型六面体金刚石单晶的实验规律, 并就两种腔体合成金刚石单晶的总体生长速度与生长时间的关系进行了讨论; 最后, 借助于拉曼光谱, 将合成的优质六面体金刚石单晶与天然金刚石单晶进行对比测试, 对所合成晶体的结构及品质进行了表征.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

Ib型金刚石大单晶的限形生长

金刚石的限形生长有利于其后续加工.对于磨料级金刚石限形生长的研究已经比较透彻,但金刚石大单晶的限形生长尚缺乏全面系统的研究.本文以Fe Ni(64wt%:36wt%)合金为触媒,利用高温高压下的温度梯度法在5.6 GPa时对不同温度下分别沿(100)面和(111)面生长的Ib型金刚石大单晶的晶形进行了研究.研究表明:随着温度的升高,沿(100)晶面生长的金刚石大单晶的晶形分别为板状、塔状直至尖塔状,而沿(111)面生长的金刚石大单晶的晶形则分别为塔状和板状;分析了不同温度下分别沿(100)面和(111)面生长金刚石大单晶不同晶形高径比的变化情况.利用不同压力和温度下的金刚石大单晶合成实验绘制了沿(100)和(111)面生长金刚石大单晶的晶形在V形生长区域内的分布示意图,表明沿(111)面生长的金刚石大单晶V形区温度下限明显比以(100)面生长的高,而沿这两面生长金刚石大单晶的V形区温度上限差别并不明显.对不同生长面V形区温度上下限的差别进行了解释,据此实现了Ib型金刚石大单晶的限形生长.     

Characterization of a growth-front interface in a HPHT-grown diamond crystal by transmission electron microscopy

The growth-front interface of a diamond single crystal, which was grown from the Fe-Ni-C system under high pressure and high temperature (HPHT), has been directly observed by transmission electron microscopy (TEM) for the first time. The presence of a cellular interface suggests that the diamond is grown from solution and there exists a narrow supercooling zone in front of the solid–liquid interface. Diamond-growth parallel layers were also found, which indicates that the diamond grows from solution layer by layer. It provides direct evidence that the diamond is synthesized through graphite dissolution and transformation to subcritical diamond particles in a molten catalyst, diamond subcritical particle connection to form diamond clusters, diffusion of the diamond clusters to the growing diamond, and unification of the diamond clusters on the growing diamond crystal. Received: 17 July 2000 / Accepted: 27 October 2000 / Published online: 10 January 2001     

AlN晶体物理气相传输法生长坩埚的热场分析

采用物理气相传输法在钨制坩埚上制备AlN单晶.通过采用COMSOL软件中的固体传热和磁场模块,对AlN晶体生长的坩埚的热场进行仿真,同时针对不同的线圈直径以及不同的线圈位置对坩埚热场的影响进行模拟,提出了相应的处理方式.结果表明:当线圈直径增大,坩埚结晶区和升华区的温度在相同的加热时间下会增加,并且增加的温度存在峰值.当线圈的垂直位置发生变化的时候,结晶区和升华区的温度场也会发生变化,从上向下移动的过程中仍然存在温度的峰值,并且结晶区和升华区的温度关系会发生翻转,导致温度梯度阻碍晶体生长.在晶体生长过程中升华区和结晶区的温度关系依旧会发生翻转.但是通过线圈跟随籽晶表面生长层的变厚而同步移动,可以保持相对稳定的温度关系,维持晶体正常持续生长.     

GaN外延层中的缺陷研究

采用阴极射线致发光法观察金属有机物汽相外延法生长的具有不同表面形貌的GaN外延层中黄色发光带的强度分布.结果表明六角金字塔形表面形貌对发光强度分布的测量有很大影响.测量和比较表面镜面加工样品的黄色发光带强度分布、原子序数衬度和X射线波谱发现,黄色发光带的强度在含有O和C等杂质缺陷附近较强.高分辨透射电子显微镜观察表明,杂质缺陷区的晶格结构不同于GaN基质,以及位错和裂缝等由应力引起的缺陷.认为此类缺陷可能是生长过程中,杂质在结晶小丘合并处的V形凹角中的沉积所产生. 关键词：     

GaN外延衬底LiGaO2晶体的生长和缺陷

ＬｉＧａＯ２与ＧａＮ的晶格失配率只有０．２％，是一种很有潜力的蓝光衬底材料。通过多次实验，用提拉法生长了尺寸为１５×６０ｍｍ的高质量ＬｉＧａＯ２单晶。利用化学侵蚀、光学显微镜、透射电子显微镜对晶体中的缺陷进行了分析，研究了生长参数、原料化学配比对晶体质量的影响。ＬｉＧａＯ２晶体在〈１００〉方向生长速率最快，在〈００１〉方向上生长较慢。由于原料按非化学计量比挥发致使组份偏离，容易产生γ－Ｇａ２Ｏ３包裹物。包裹物和位错的形成具有一定的相互促进作用，往往形成平行于（００１）面的亚晶界。通过调整原料配比、生长工艺参数可克服上述问题。     

Atom force microscopy study on HTHP as-grown diamond single crystals

For understanding the mechanism of diamond growth at high temperature–high pressure (HTHP) from a metallic catalyst–graphite system, it is of great interest to perform atomic force microscopy (AFM) experiments, which provide a unique technique different from that of normal optical and electronic microscopy studies, to study the topography of HTHP as-grown diamond single crystals. In the present paper, we report first AFM results on diamond single crystals grown from a Fe-Ni-C system at HTHP to reveal the growth mechanism of diamond single crystals at HTHP. AFM images for as-grown diamond samples show dark etch pits on the (111) surface, indicating dislocations. Some fine particles about 100–300 nm in dimension were directly observed on the (100) diamond surface. These particles are believed to have been formed through transition of graphite to diamond under the effect of the catalyst and to have been transported to the growing diamond surface through a metallic thin film by diffusion. The roughness of the (100) diamond surface is found to be about several tens of nanometers through profile analysis. The diamond growth at HTHP, in a sense, could be considered as a process of unification of these fine diamond particles or of carbon-atom-cluster recombination on the growing diamond crystal surface. Successive growth interlayer steps on the (111) diamond surface were systemically examined. The heights of the growth interlayer steps were measured by sectional analysis. It was shown that the heights of the growth interlayer steps are quite different and range from about 10 to 25 nm. The source of the interlayer steps might be dislocations. The diamond-growth mechanism at HTHP could be indicated by the AFM topography of the fine diamond particles and the train-growth interlayer steps on the as-grown diamond surfaces. Received: 29 March 2001 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Heteroepitaxial growth of cubic boron nitride films on single-crystalline (001) diamond substrates

Heteroepitaxial cubic boron nitride (c-BN) films of significantly improved crystalline quality have successfully been deposited on (001) diamond single crystals using an ion beam assisted preparation method. The results of various characterization techniques prove that films containing 100% pure c-BN phase were nucleated directly on top of diamond without any intermediate hexagonal BN layer. Epitaxially grown, 500-nm-thick c-BN films are mechanically stable even under ambient conditions, though they still exhibit a compressive stress of 5 GPa. Their rocking angles of 0.2°, as observed by X-ray diffraction, point to a hitherto unprecedented quality of the films. Their surface smoothness, the magnitude of their Youngs modulus as well as their ultrahardness corroborate the outstanding quality of these epitaxially grown c-BN films on single-crystalline diamond. PACS 68.55.Jk; 81.15.Jj; 62.20.Qp; 81.05.Je     

Simulation of polycrystalline 3D film growth: An investigation of the evolution of grain size and texture in diamond films

An analytical method for simulating gas phase film growth has been developed and used to study the growth of diamond films during prolonged deposition, i.e. the film thickness is much larger than the lateral grain size. From a model system composed of 10⁴ grains, reliable results can be evaluated for the growth of diamond films by (111) and (001) deposition under different initial conditions and with varying growth parameters. It is demonstrated that the rate of structure evolution is sensitively influenced by the aspect ratio of diamond crystal. A near-linear proportionality between the average grain size and the thickness of films can be approximately yielded for a large film thickness which is about 10 times of the average distance of the nuclei. The proportionality constant varies for a statistical nucleation from 0.0056 to 0.43 by changing the aspect ratio. Furthermore, the orientational distribution is drastically narrowed down so that the probability of coalescence of grains with a slight orientational difference is considerably increased. Received: 28 September 2000 / Accepted: 19 February 2001 / Published online: 3 May 2001     

高温下金属薄膜生长初期的模拟研究

采用实际的生长模型和物理参量,用Monte Carlo方法对高温下金属薄膜的生长过程进行了模拟研究.综合考虑了原子沉积、扩散、成核、生长和扩散原子的再蒸发、原子沿岛周界扩散和岛的合并等众多过程后,模拟得到与实验结果相当一致的薄膜生长形貌及其相应的定量结果.通过动态统计薄膜生长过程中的岛数目及薄膜生长率,得到实验中不易直接获得的高温下薄膜生长的许多细节,如岛数目和薄膜生长率随表面温度、覆盖度变化的详细情况等 关键词： 薄膜 Monte Carlo模拟 成核 岛密度 薄膜生长率