硼掺杂对直流热阴极CVD金刚石薄膜生长特性的影响

采用直流热阴极CVD法以B(OCH3)3为掺杂剂制备了硼掺杂金刚石薄膜,利用等离子体发射光谱、SEM、Raman和XRD研究了硼掺杂对金刚石薄膜生长特性的影响,通过与未掺杂金刚石薄膜的对比发现:在直流热阴极CVD系统中,低浓度硼掺杂条件下能够长时间维持稳定的辉光放电. 掺硼后辉光等离子体活性基团(Hα、Hβ、C2、CH)的种类没有改变,但C2基团的浓度升高,而CH基团的浓度下降,薄膜的生长速率提高到0.65mg·cm-2·h-1. 硼掺杂金刚石薄膜为多晶薄膜,晶体生长良好,取向以(111)晶面为主,质量较未掺杂薄膜有所提高. 硼原子以取代或填隙的方式掺杂进入金刚石晶格,没有破坏金刚石晶体结构.     

(111)晶面同质外延生长单晶金刚石的研究

利用微波等离子体化学气相沉积(MPCVD)法,在天然金刚石衬底的(111)晶面上同质外延生长单晶金刚石,研究了沉积温度、CH_4浓度以及小角度偏离(111)晶面的衬底对金刚石生长的影响。采用SEM和Raman对外延生长的金刚石进行表征,结果表明:高沉积温度、高CH_4浓度条件下,金刚石呈现出无序的多晶生长现象,随着沉积温度的降低,形貌和质量明显提高,在低沉积温度条件下金刚石表现出一致的单晶生长,但是表面形貌较为粗糙。进一步降低CH_4浓度可外延生长质量高、表面平整的单晶金刚石,速率达4.7μm/h.使用倾斜抛光方法将部分衬底面偏离(111)晶面约6°,对比实验发现,微小偏离(111)晶面的斜面衬底在高沉积温度、高CH_4浓度条件下也能生长出质量较好的单晶金刚石,生长速率明显提高,达到了9μm/h。     

{100}织构化学气相沉积金刚石薄膜的取向生长过程

为了研究化学气相沉积（CVD）金刚石薄膜生长过程中{100}织构的形成机理,采用x射线衍射、电子背散射衍射和扫描电镜研究了CVD自支撑金刚石薄膜的宏观织构、微区晶界分布和表面形貌。结果表明：金刚石薄膜以{111}面或{100}面为生长前沿面都能够形成{100}织构,但形成的表面形貌不同;通过吸附CH3-和CH3-在{1...     

基于第一性原理方法研究基团在CVD金刚石薄膜(001)表面上的生长

采用基于密度泛函理论的第一性原理方法研究CVD金刚石薄膜(001)表面的生长机理。计算清洁金刚石表面和氢(H)终止金刚石表面的构型。考察H原子和活性基团(C,CH,CH2和CH3)在清洁重构金刚石表面及在单层H终止金刚石表面上的吸附演变。结果表明:清洁金刚石表面发生了对称二聚体重构,H原子终止金刚石表面稳定了金刚石结构;基团在金刚石(001)表面吸附演变过程中,H原子起到激活石墨和萃取表面H原子产生活性位的作用;CH2基团比CH3基团能够更好地提高CVD金刚石薄膜的生长率,是薄膜生长过程中最有效基团;CH基团阻碍了薄膜的生长。     

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。     

高气压下温度对金刚石膜择优取向的影响

采用自主改进的圆柱谐振腔式MPCVD装置,以H2-CH4为气源、反应腔压强30kPa、微波功率6kW、CH4浓度2%,在不同的沉积温度下进行了多晶金刚石膜的制备研究。采用扫描电镜、X-射线衍射技术对所制备样品的表面形貌、物相及晶面取向进行了分析。结果表明,在高气压条件下,沉积温度由800℃升高至900℃时,金刚石膜的表面形貌由(111)晶面择优取向逐渐转向(100)晶面择优取向;沉积温度由900℃升高至1050℃时,金刚石的表面形貌由(100)晶面择优取向逐渐转向(111)晶面择优取向。     

以Al2O3为过渡层脉冲激光法制备PZT铁电薄膜

为实现PZT铁电薄膜与半导体衬底的直接集成引入Al2O3为过渡层，首先用真空电子束蒸发法在Si(100)，多昌金刚石（111）衬底上生长约20nm厚的Al2O3过渡层，接着在上述衬底上采用脉冲激光淀积（PLD）法淀积PZT薄膜，衬底温度为350-550℃。X光电子能谱（XPS）测试表明，在高真空下，电子束蒸发Al2O3固态源能获得化学配比接近蒸发源的Al2O3薄膜。X射线衍射（XRD）测试说明，不论衬底是硅还是多晶金刚石，当衬底温度为550℃时，PZT在Al2O3过渡层上呈现（222）取向的焦绿石相结构，当衬底是金刚石时，通过如下工艺：（1）较低温度（350℃）淀积；（2）空气氛围650℃快速退火5min，可以在Al2O3过渡层上获得高度（101）取向的钙钛矿结构的铁电相PZT薄膜，最后AFM测试显示，在硅衬底上，PZT薄膜的表面均方根粗糙度为9.78nm；而在多晶金刚石衬底上，PZT薄膜的表面均方根粗糙度为17.2nm。     

(111)SrTiO_3衬底处理调制ZnO薄膜的面内外延关系研究

采用脉冲激光法在未处理和水浸泡的(111)SrTiO_3(STO)衬底上都生长得到了c轴取向的纤锌矿结构ZnO薄膜。ZnO薄膜与STO衬底之间的外延关系使用X射线进行研究。发现在未处理和水浸泡的(111)SrTiO_3衬底的面内排列分别是[1120]_(ZnO)//[110]_(STO)和[1100]_(ZnO)//[110]_(STO),它们之间相互旋转30o。ZnO薄膜相对于STO衬底的面内取向强烈依赖于衬底处理。可能是未处理和水浸泡STO衬底终止面的差别导致了外延关系的改变。相比来说,[1100]_(ZnO)//[110]_(STO)比[1120]_(ZnO)//[110]_(STO)能量更低,这是由于SrO_3比Ti终止STO衬底具有更高的成键密度和较低的界面能。     

不同等离子体体系中纳米金刚石薄膜制备的研究

利用微波等离子体化学气相沉积（MPCVD）法分别在CH4／H2／Ar体系、CH4／H2／O2体系和C2H5OH／H2体系中进行纳米金刚石（NCD）薄膜的制备研究。采用原子力显微镜（AFM）和激光拉曼光谱（Raman）等方法对不同体系中制备得到的NCD薄膜的表面形貌及其质量进行了检测。结果表明：在CH4／H2体系中添加O2对于促进高平整度NCD薄膜的效果明显优于添加At;C2H5OH／H2体系更有利于制备颗粒更细、金刚石相含量更高的NCD薄膜。利用等离子体CVD技术的相关理论对上述结论进行了理论分析。     

压力对热丝化学气相沉积的CH_4/H_2/Ar气氛中的纳米金刚石薄膜生长的影响(英文)

在热丝化学气相沉积体系中,系统研究了气压对CH4/H2/Ar气氛中纳米金刚石薄膜生长的影响.研究发现,体系气压对纳米金刚石的生长有很大的影响.在40torr的气压下,在CH4/H2/Ar气氛中的Ar气含量需高达90%才能保证纳米金刚石薄膜的生长,但降低气压至5torr时,50%的Ar气含量即可保证纳米金刚石薄膜的生长.压力对薄膜生长表面的气体浓度的影响是这个转变的主要原因.在同样的Ar含量下,在5torr下的C2活性基团的浓度高于40 torr的浓度,因而低的Ar含量会保证纳米金刚石薄膜的生长.     

无支撑优质金刚石膜研制中的相关问题探讨

无支撑优质金刚石膜在微波真空器件和光学器件中的广泛应用,有赖于制备成本的下降和工艺的完善。结合微波等离子体化学气相沉积(MPCVD)金刚石膜的工艺研究结果,本文就沉积速率、晶面取向以及内应力的相关问题进行了初步探讨。对于给定的设备,沉积速率与多种因素有关,包括膜的质量、膜厚均匀性和有效沉积面积、以及形核的密度。在通常情况下,金刚石膜呈(111)择优取向,而样品位置下移5mm后,观察到(100)取向。对内应力的初步研究表明,CH4/H2比例较低(1.5)时,金刚石膜的内应力趋向于压应力,而(100)取向的出现则有助于使内应力降到最低。     

甲烷浓度对CVD金刚石薄膜晶体学生长过程的影响

采用X射线衍射技术、电子背散射衍射技术和扫描电镜分别观察了不同甲烷浓度条件下沉积的CVD自支撑金刚石薄膜的宏观织构、微区晶界分布和表面形貌.研究了金刚石晶体{100}面和{111}面生长的晶体学过程.研究表明,{100}面通过吸附活性基团CH^2- 2,而{111}面通过交替吸附活性基团CH^-3和CH^-3后脱氢堆积碳原子.低甲烷浓度时,{111}面表面能低于{100}面,使{111}面生长略快于{100}面.甲烷浓度升高,动力学作用增强使{100}面生长明显快于{111}面,使金刚石薄膜产生{100}纤维织构;同时显露的{100}面平行于薄膜表面,竞争生长使位于晶体侧面的{111}面由于相互覆盖而减小,形成了不同于单晶体自由生长的薄膜表面形貌组织.     

The growth and transformation of Pd2Si on (111), (110) and (100) Si

Thin Pd films on (111), (110), (100) and amorphous Si substrates form [001] fiber textured Pd₂Si in the temperature range 100°–700°C. The degree of texture is a function of substrate orientation, increasing in the order amorphous Si, (100) Si, (110) Si and (111) Si. Only on the (111) Si substrate is the Pd₂Si film epitaxially oriented. Temperature-dependent growth on this orientation can be characterized by [001] textured growth, epitaxial azimuth orientation at the Si interface and progressive layer by layer formation of the mosaic crystal to the thin film surface.During Pd deposition, rapid non-diffusion-controlled growth of epitaxial Pd₂Si on (111) Si occurs at substrate temperatures of 100° and 200°C. An unidentified palladium silicide of low crystallographic symmetry forms during Pd deposition onto a 50°C substrate. The diffusion-controlled growth of Pd₂Si on (111) Si follows a t^0.5 dependence. The velocity constant is

$\text{k = 7 × 10}{}^{\mathrm{?2}}\text{exp}\text{?}\text{29200±800}\text{RT}\text{cm}{}^2\text{/}\text{sec}$

Palladium deposited on 100°C (111) Ge substrates reacts during deposition to form epitaxially oriented Pd₂Ge. However, growth of this phase at higher temperatures results in a randomly oriented film. The transformation of Pd₂Ge to PdGe is kinetically controlled. After a 15 min anneal at 560°±10°C in N₂ only PdGe is detectable on (111) Ge.The high temperature stability of thin film Pd₂Si is controlled by time- temperature kinetics. For a given annealing cycle, the nucleation and growth rates of the PdSi phase are inversely related to the crystalline perfection of Pd₂Si. Decreasing transformation rates follow the order (100), (110), (111) Si. formation of thin film Pd₂Si occurs by the formation of PdSi and subsequent growth of Si within the PdSi phase. After a 30 min N₂ anneal, initial transformation occurs at 735°C on (100) Si, 760°C on (110) Si and 840°C on (111) Si. Extended high temperature annealing produces a two-phase structure of highly twinned and misoriented Si and small PdSi grains that penetrate as much as 3 μm into the Si.     

低偏压下化学气相沉积金刚石薄膜的生长形貌研究

在微波等离子体化学气相沉积装置中，研究了偏压电压、甲烷浓度及沉积气压对金刚石晶形显露的影响。实验结果表明，生长时施加低的衬底偏压对金刚石的晶形显露有较大的影响，正的偏压有利于(111)面显露，负偏压有利于(100)面显露。在低偏压条件下生长时，低的沉积气压和甲烷浓度有利于(111)面显露；而高的气压和甲烷浓度有利于(100)面显露。过高的甲烷浓度将恶化金刚石质量，出现菜花状组织，无明显的晶面显露。     

Atomistic simulation of chemical vapor deposition of (111)-oriented diamond film using a kinetic Monte Carlo method

Chemical vapor deposition (CVD) of (111)-oriented diamond film is modeled using a kinetic Monte Carlo atomic scale method. The method is parameterized by the rates of the accompanying surface chemical reactions and permits one of these reactions to take place at each simulation step. The effect of local surface structure and morphology on the rates of surface reaction is examined. Film growth at two different chemical compositions of the feed gas and two substrate temperatures is studied in order to determine the effect of these process parameters on (a) the quality of the deposed film and (b) the rate of deposition. The quality of the film is judged by concentration of the point defects (vacancies and H atoms embedded in the film) and by surface roughness. The results obtained show that the parameters that increase the deposition rate, primarily the substrate temperature and the concentration of CH4 in the feed gas, also increase the defect content and surface roughness.     

两段成长法改善微波电浆辅助化学气相沉积多晶金刚石之品质

以化学气相沉积法成长多晶金刚石薄膜时,薄膜的品质会受到成长时间、成长压力、反应气体比例、偏压与否及成核的机制等因素影响.研究采用微波电浆辅助化学气相沉积(MPECVD)法,以甲烷(CH4)和氢气(H2)作为反应气体原料,在P型(111)硅基板沉积多晶金刚石薄膜.典型沉积多晶金刚石薄膜的制程可分为四个阶段:抛蚀表面阶段、渗碳阶段、偏压增强成核(BEN)阶段及成长阶段.研究将成长阶段划分为两个阶段,第一阶段压力较低(成长Ⅰ阶段),第二阶段压力较高(成长Ⅱ阶段).结果表明:第一阶段可大大改善金刚石薄膜的品质,所获多晶金刚石薄膜的晶粒具有明确的颗粒边界、较低的碳化物或缺陷,电导率急剧降低,显现出本徵金刚石半绝缘的性质.可以认为金刚石薄膜品质的改善完全为低压成长所致.实验发现在成长Ⅰ阶段或成长Ⅱ阶段施加偏压时,只会降低多晶金刚石薄膜的品质.     

Nucleation and Oriented Textured Growth of Diamond Films on Si(100) via Electron Emission in Ho.t Filament Chemical Vapor Deposition

1. IntroductionIn recent years, there has been increasing illterest in the heteroepitaxial growth of diamond films'by chemicisl vapor deposition(CVD) owing to theirpromising applications for the electronic devices. Epitaxial diamond films have been successfully grown onc-BN and monocrystal diamond substrated~4]. However, it is a more imperative task to deposit heteroepitarial diamond films on St which was anticipated tobe as a low cost substrate to achieve synthesis of singlecrystalline diam…     

Low-temperature growth of nanostructured diamond films

Nanostructured diamond films are grown on a titanium alloy substrate using a two-step deposition process. The first step is performed at elevated temperature (820 degrees C) for 30 min using a H2/CH4/N2 gas mixture to grow a thin (approximately 600 nm) nanostructured diamond layer and to improve film adhesion. The remainder of the deposition involves growth at low temperature (< 600 degrees C) in a H2/CH4/O2 gas mixture. The continuation of the smooth nanostructured diamond film growth during low-temperature deposition is confirmed by in situ laser reflectance interferometry, atomic force microscopy, micro-Raman spectroscopy, and surface profilometry. Similar experiments performed without the initial nanostructured diamond layer resulted in poorly adhered films with a more crystalline appearance and a higher surface roughness. This low-temperature deposition of nanostructured diamond films on metals offers advantages in cases where high residual thermal stress leads to delamination at high temperatures.     

Low Resistance Polycrystalline Diamond Thin Films Deposited by Hot Filament Chemical Vapour Deposition

Polycrystalline diamond thin films with outgrowing diamond (OGD) grains were deposited onto silicon wafers using a hydrocarbon gas (CH4) highly diluted with H2 at low pressure in a hot filament chemical vapour deposition (HFCVD) reactor with a range of gas flow rates. X-ray diffraction (XRD) and SEM showed polycrystalline diamond structure with a random orientation. Polycrystalline diamond films with various textures were grown and (111) facets were dominant with sharp grain boundaries. Outgrowth was observed in flowerish character at high gas flow rates. Isolated single crystals with little openings appeared at various stages at low gas flow rates. Thus, changing gas flow rates had a beneficial influence on the grain size, growth rate and electrical resistivity. CVD diamond films gave an excellent performance for medium film thickness with relatively low electrical resistivity and making them potentially useful in many industrial applications.