Si(111) 衬底上3C-SiC的超低压低温外延生长

研究了发展一种Si衬底上低温外延生长3C－SiC的方法。采用LPCVD生长系统，以SiH4和C2H4为气源，在超低压（30Pa) ,低温（900℃）的条件下，在Si(111衬底上外延生长出高质量的3C－SiC薄膜材料。采用俄歇能谱（AES），X射线衍射（XRD）和原子力显微镜（AFM）等分析手段研究了SiC薄膜的外延层组分，晶体结构及其表面形貌。AES结果表明薄膜中的Si/C的原子比例符合SiC的理想化学计量比，XRD结果显示了3C－SiC外延薄膜的良好晶体结构，AFM揭示了3C－SiC薄膜的良好的表面形貌。     

原料对碳化硅单晶生长的影响

研究了具有立方结构的碳化硅(β-SiC)粉料在单晶生长过程中的物相变化及对生长晶体均匀性、缺陷等的影响。实验发现,在晶体生长过程中原料的晶型转变和Si、C挥发不一致造成晶体沿生长方向存在一个Si/C摩尔比的最大值。晶体中的针孔等缺陷的形成与原料中的杂质和气相组分偏离Si/C=1摩尔比有关,并通过电子探针得到证实。     

硅碳比对Si(111)表面SSMBE异质外延SiC薄膜的影响

利用固源分子束外延(SSMBE)生长技术, 在不同的硅碳蒸发速率比(Si/C)条件下, 在Si(111)衬底上生长SiC单晶薄膜. 利用反射式高能电子衍射(RHEED)、X射线衍射(XRD)、原子力显微镜(AFM)和傅立叶变换红外光谱(FTIR)等实验技术, 对生长的样品形貌和结构进行了研究. 结果表明, 在Si/C比(1.1:1.0)下生长的薄膜样品, XRDω扫描得到半高宽为2.1°; RHEED结果表明薄膜具有微弱的衍射环, 有孪晶斑点. 在Si/C比(2.3:1.0)下生长的薄膜, XRDω扫描得到的半高宽为1.5°, RHEED显示具有Si的斑点和SiC的孪晶斑点. AFM显示在这两个Si/C比下生长的样品表面都有孔洞或者凹坑, 表面比较粗糙. 从红外光谱得出 薄膜存在着比较大的应力. 但在Si/C比(1.5:1.0)下生长的薄膜样品, XRDω 扫描得到的半高宽仅为1.1°; RHEED显示出清晰的SiC的衍射条纹, 并可看到SiC的3×3表面重构, 无孪晶斑点; AFM图像表明, 没有明显的空洞, 表面比较平整. FTIR谱的位置显示, 在此Si/C比下生长的薄膜内应力比较小. 因此可以认为, 存在着一个优化的Si/C比(1.5:1.0), 在这个Si/C比下, 生长的薄膜质量较好.     

Si(001)衬底上方形3 C-SiC岛的LPCVD生长

Si衬底上SiC的异质外延生长深受关注,为了了解Si衬底上的成核及长大过程,采用PLCVD方法在Si(001)衬底上生长出了方形3C-SiC岛,利用Nomarski光学显微镜和扫描电子显微镜（SEM）观察了SiC岛的形状,尺寸,密度和界面形貌,结果表明,3C－SiC岛生长所需的Si原子来自反应气源,衬底上的Si原子不发生迁移或外扩散,气相中C原子浓度决定了SiC岛的生长过程。     

几种无限供应的金属/硅体系离子束混合相变

研究了五种无限供应的 Bilayer 膜金属/硅体系中(Ni/Si,Cu/Si,Nb/Si,Mo/Si,Ti/Si),因离子束注入引起的界面原子交混及相变过程。界面温度和注入离子剂量显著影响薄膜相变,在生成各种金属 Si 化物及固溶体时,反应温度和生长激活能大大降低,相变动力学过程与热退火反应不尽相同,诱导离子和基体取向对成相生长也有影响。讨论了相应微观机理。     

VLS同质外延6H-SiC薄膜生长的研究

碳化硅(SiC)是第三代宽禁带半导体材料,在高温、高频、高功率、光电子及抗辐射等方面具有巨大的应用潜力.以CH4、SiH4为反应气体,H2为载气,采用化学气相沉积法,利用气-液-固(VLS)生长机理,同质外延6H-SiC薄膜.结果表明,VLS机制能在外延薄膜的表面有效地封闭微管,但是由于n(C)/n(Si)较大,薄膜表面存在大量的台阶.为了进一步改善薄膜表面形貌,采用"两步法"工艺外延SiC薄膜,在封闭微管的同时提高了表面平整度,得到了质量较好的6H-SiC外延薄膜.     

正交实验方法研究PECVD碳化硅薄膜的防水汽扩散性质

利用正交实验设计，研究了碳化硅薄膜的防水汽扩散性质。通过测试水汽在碳化硅薄膜中的扩散速率，初步确定了四种沉积参数影响碳化硅薄膜防水汽扩散能力的规律。实验发现，射频频率的变化对碳化硅薄膜的防水汽扩散能力的影响最大，气体流量比次之，而功率和气体压力的变化影响较小。     

分子束外延生长GaAs中δ掺杂研究

利用二次离子质谱（SIMS）和电化学剖面C－V方法研究了生长温度对GaAs中理想Siδ掺杂结构的偏离和掺杂原子电激活效率的影响。实验发现，外延生长Siδ掺杂GaAs时，随着生长温度的升高，Si掺杂分布SIMS峰非对称展宽，表面分凝作用加强，但不影响Si原子的扩散。另外，Si施主电激活效率随着生长温度的提高而增大。     

PECVD法低温沉积SiGx薄膜的防水汽扩散性能研究

外界水汽和离子的扩散对集成电路和传感器等器件的性能及使用寿命有很大影响，利用无机钝化材料阻挡水汽和离子的扩散是常用的提高器件寿命和稳定性和方法。本文采用ＰＥＣＶＤ方法在较低的衬底温度条件下沉积碳化硅薄膜，利用各种方法研究了碳化硅薄膜的防潮性能。实验证明，碳化硅薄膜是一种良好的水汽扩散阻挡材料，其防潮能力达到甚至超过了集成电路生产中常用的氮化硅薄膜。并且，低温碳化硅薄膜具有非常好的化学稳定性和抗刻蚀     

热丝CVD大面积金刚石薄膜的生长动力学研究

在传统工业型热丝化学气相沉积（HFCVD）反应腔内，相关工艺参数取模拟计算优化值的条件下，采用XRD，SEM及Raman光谱等分析手段研究了单晶Si（100）上较大面积金刚石薄膜的动力学生长行为，讨论了晶格取向的变化规律。结果表明：优化工艺参数条件下，在模拟计算的衬底温度和气体温度分布均匀的区域内，沉积的金刚石薄膜虽存在一定的内应力，但整体薄膜连续、均匀，几何晶形良好，质量较高，生长速率达1．8μm／h。薄膜生长过程中晶形显露面受衬底温度和活性生长基团浓度的影响较大。     

A comprehensive study of SiC growth processes in a VPE reactor

We performed an experimental study of the effect of the gas phase composition on the growth mechanism of 3C-SiC on Si(100) by atmospheric-pressure vapour phase epitaxy at 1350°C. Silane and propane diluted in hydrogen were used as precursors for the growth. We demonstrate the existence of an equilibrium partial pressure of carbon above the growing surface, which ensures a mirror-like morphology. For too low a carbon partial pressure (C/Si ratio in the gas phase lower than 2.7 with a growth rate of 3 μm h⁻¹), the layer morphology and crystalline quality quickly degrade. For too high a carbon partial pressure (C/Si ratio higher than 5 with the same growth rate), SiC clusters form on the growing layers. We propose a mechanism of formation for these clusters taking into account the interactions between the C and Si species in the hot boundary layer.     

Numerical study of SiC CVD in a vertical cold-wall reactor

The conventional heat and mass transport model is extended to describe silicon cluster formation in the gas phase and is employed for a numerical analysis of SiC chemical vapor deposition in a commercial vertical rotating disc reactor. The model is verified by comparing the computed growth rate with available experimental data. The growth rate is studied as a function of precursor flow rates varied in a wide range of values. It is found that the growth rate is limited by the gas mixture depletion in silicon atoms due to homogeneous nucleation. The secondary phase formation on the growing surface is analyzed. The SiC growth window depending on the precursor flow rates is calculated, and a significant influence of the homogeneous nucleation on the window width is shown. The model results predict that the Si/C ratio on the wafer can considerably differ from that at the reactor inlet.     

Kinetics of SiHCl3 chemical vapor deposition and fluid dynamic simulations

Though most of the current silicon photovoltaic technology relies on trichlorosilane (SiHCl3) as a precursor gas to deposit Si, only a few studies have been devoted to the investigation of its gas phase and surface kinetics. In the present work we propose a new kinetic mechanism apt to describe the gas phase and surface chemistry active during the deposition of Si from SiHCl3. Kinetic constants of key reactions were either taken from the literature or determined through ab initio calculations. The capability of the mechanism to reproduce experimental data was tested through the implementation of the kinetic scheme in a fluid dynamic model and in the simulation of both deposition and etching of Si in horizontal reactors. The results of the simulations show that the reactivity of HCl is of key importance in order to control the Si deposition rate. When HCl reaches a critical concentration in the gas phase it starts etching the Si surface, so that the net deposition rate is the net sum of the adsorption rate of the gas phase precursors and the etching rate due to HCl. In these conditions the possibility to further deposit Si is directly related to the rate of consumption of HCl through its reaction with SiHCl3 to give SiCl4. The proposed reaction mechanism was implemented in a 3D fluid dynamic model of a simple Siemens reactor. The simulation results indicate that the proposed interpretation of the growth process applies also to this class of reactors, which operate in what can be defined as a mixed kinetic-transport controlled regime.     

Stress and crystallization of plasma enhanced chemical vapour deposition nanocrystalline silicon films

Nanocrystalline Si films were prepared with a RF-PECVD system using different SiH4/H2 ratios, plasma powers, substrate temperatures and annealing conditions. The film's intrinsic stress was characterized in relation to the crystallization fraction. Results show that an increasing H2 gas ratio, plasma power or substrate temperature can shift the growth mechanism across a transition point, past which nanocrystalline Si is dominant in the film structure. The film's intrinsic stress normally peaks during this transition region. Different mechanisms of stress formation and relaxation during film growth were discussed, including ion bombardment effects, hydrogen induced bond-reconstruction and nanocomposite effects (nanocrystals embedded in an amorphous Si matrix). A three-parameter schematic plot has been proposed which is based on the results obtained. The film structure and stress are presented in relation to SiH4 gas ratio, plasma power and temperature.     

The shape control of ZnO based nanostructures

Tetrapod-shape ZnO nanostructures are formed on Si substrates by vapor phase transportation method. The effects of two important growth parameters, growth temperature and VI/II ratio, are investigated. The growth temperature is varied in the range from 600 degrees C to 900 degrees C to control the vapor pressure of group II-element and the formation process of nanostructures. VI/II ratio was changed by adjusting the flux of carrier gas which affects indirectly the supplying rate of group VI-element. From the scanning electron microscopy (SEM), systematic variation of shape including cluster, rod, wire and tetrapod was observed. ZnO tetrapods, formed at 800 degrees C under the carrier gas flux of 0.5 cc/mm2 min, show considerably uniform shape with 100 nm thick and 1-1.5 microm long legs. Also stoichiometric composition (O/Zn - 1) was observed without any second phase structures. While, the decrease of growth temperature and the increase of carrier gas flux, results in the irregular shaped nanostructures with non-stoichiometric composition. The excellent luminescence properties, strong excitonic UV emission at 3.25 eV without deep level emission, indicate that the high crystalline quality tetrapod structures can be formed at the optimized growth conditions.     

Crystallization of Au-Si/glass thin film: a real-time synchrotron X-ray scattering study

The crystallization of amorphous, Si-rich, Au28Si72/glass thin film was studied in real-time synchrotron X-ray scattering experiments. The amorphous film crystallizes first into Au and Si phases at a low temperature of 206 degrees C. At annealing temperatures above eutectic temperature (T(E) = 360 degrees C), the Au phase melts while the Si phase rapidly grows further. The crystallized Au28Si72 thin film has nanowire-type grains with 1000-nm-length and 10-nm-diameter. We confirm that the Au liquid phase contributes to the low-temperature crystallization of the Si solid phase for Si-nanowire growth.     

掺Si对MOCVD生长的GaN单晶膜的黄带发射及生长速率的影响

对ＭＯＣＶＤ生长ＧａＮ：Ｓｉ薄膜进行了研究,研究表明随ＳｉＨ４／ＴＭＧａ流量比增大,ＧａＮ：Ｓｉ单晶膜的电子浓度增大,迁移率下降,Ｘ射线双晶衍射峰半高宽增加,同时这发射强度得到了大大的提高,并报导了随ＳｉＨ４／ＴＭＧａ流量比增大,ＧａＮ：Ｓｉ的生长速率降低的现象,研究结果还表明,预反应对ＧａＮ：Ｓｉ单晶膜黄带发射影响很大,预反应的减小可以使黄带受到抑制。     

The Gorsky effect in the synthesis of silicon-carbide films from silicon by topochemical substitution of atoms

The mechanisms of evaporation of silicon from the surface of silicon carbide (SiC) grown by atomic substitution are studied. It is assumed that the emergence of elastic deformations at the stage of cooling of the sample with a SiC film is one of the causes of Si evaporation. It is demonstrated theoretically that elastic stresses induce the mechanochemical Gorsky effect in the SiC layer. This effect initiates redistribution of Si and C atoms in the SiC layer, which results in violation of the stoichiometry of films and asymmetry of their composition over the SiC-layer thickness. A method for growing epitaxial SiC films with a homogeneous composition and a low density of silicon vacancies from a gas mixture of carbon monoxide and trichlorosilane is proposed.     

Surface Crystallization of Liquid Au–Si and Its Impact on Catalysis

In situ transmission electron microscopy reveals that an atomically thin crystalline phase at the surface of liquid Au–Si is stable over an unexpectedly wide range of conditions. By measuring the surface structure as a function of liquid temperature and composition, a simple thermodynamic model is developed to explain the stability of the ordered phase. The presence of surface ordering plays a key role in the pathway by which the Au–Si eutectic solidifies and also dramatically affects the catalytic properties of the liquid, explaining the anomalously slow growth kinetics of Si nanowires at low temperature. A strategy to control the presence of the surface phase is discussed, using it as a tool in designing strategies for nanostructure growth.     

Yb2O3 掺杂氮化硅复合材料的高温动态疲劳行为

研究了N2 气氛加压烧结制备的6 wt %Yb₂O₃ 和2 wt %Al₂O₃ 掺杂氮化硅复合材料在高温下的动态疲劳行为。用维氏压痕法在试样上获得规范的预制裂纹。分别在1000 ℃、1200 ℃、1300 ℃、1400 ℃下, 以1 、0. 5 、0. 1 、0. 01 mm/ min 的不同压头速率对试样进行四点弯曲试验。不同温度下疲劳应力2加载速率函数曲线的对比表明, 这种材料在1200 ℃时, 对亚临界裂纹生长具有最高的抵抗力(即具有最大的亚临界裂纹生长指数N) 。XRD、TEM 分析表面晶界相的晶化、裂纹愈合可以提高亚临界裂纹生长指数。EDS 分析表明, 1200 ℃下氮化硅陶瓷断裂面的氧化有助于晶界相的晶化, 但是在更高的温度下, 则会产生不利影响。