Study of microwave plasma-assisted chemical vapor deposition of poly-and single-crystalline diamond films

We study conditions for microwave plasma-assisted chemical vapor deposition of high-quality single-crystal diamond films in a CVD reactor. These conditions are studied using the results of homoepitaxial growth of polycrystalline diamond films on diamond substrates and on the basis of numerical simulation of the microwave discharge in a CVD reactor. A high-quality single-crystal diamond layer is synthesized on a synthetic, type Ib diamond substrate. The properties of the obtained monolayer are studied by means of Raman and X-ray diffraction spectroscopy as well as optical and atomic-force microscopy.     

High quality CVD diamond: a Raman scattering and photoluminescence study

High quality synthetic diamonds were grown on single-crystal silicon by microwave plasma enhanced chemical vapour deposition (CVD). A careful optimisation of both the experimental setup and the growth parameters was necessary before that the achievement of the best results was made possible. The films were deposited using a CH₄-H₂ gas mixture at methane concentrations variable in the range 0.6-2.2%, while the substrate temperature was fixed at 750 ^°C. Raman spectroscopy and photoluminescence (PL) were utilised to monitor the quality of the deposited films and to study the spatial distribution of defects, respectively. Micro-Raman analysis shows that linewidths of the diamond peak lower than 2.4 cm^-1 can be easily measured at the growth surface, indicating that the crystalline quality of individual grains is comparable to that of the best natural diamonds. The excellent phase purity of the diamond microcrystals at the growth surface is witnessed by the complete absence of any non-diamond carbon feature and by a very weak luminescence background in the 1.6-2.4 eV spectral range. A worsening of the quality of the diamond particles is found moving from the growth surface towards the film-substrate interface. A photoluminescence feature at about 1.68 eV, commonly associated to Si impurities, is distinctly observed as the exciting laser beam is focused close to the interface. A progressive degradation of the global quality of the films is found with increasing methane concentration in the gas mixture, as witnessed by an increased PL background in the films grown at higher methane concentrations. Received 24 November 2000     

Real-time monitoring of diamond nucleation and growth using field-enhanced thermionic emission current

Diamond nucleation and growth in the combustion-flame method were monitored in real time using thermionic emission current from the deposited diamond films. It was observed that the emission current evolved over three periods, the incubation, the fast increase, and the saturation periods. Ball-shaped diamond particles, faceted diamond crystals, and diamond films with well-faceted crystals were formed in the three periods. The current from a diamond-seeded substrate started to increase immediately without an incubation period, confirming that the current is from the diamond. Therefore, the current could be used for real-time monitoring of the diamond nucleation and growth.     

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.     

锌添加对大尺寸金刚石生长的影响

利用温度梯度法,在6.2—6.4 GPa,1270—1400℃条件下,通过在NiMnCo-C体系中添加不同比例的锌粉成功合成出3 mm左右的大尺寸金刚石单晶.研究了锌添加对金刚石颜色、形貌、内部氮杂质以及晶体结晶度的影响.结果表明:随着锌添加量逐渐增加,晶体的颜色逐渐变浅,晶体的透光性增强;当锌添加比例达到3 wt.%时,晶体表面出现大量不规则的凹坑;晶体内氮杂质主要以C心形式存在,随着锌添加量的增多晶体内氮含量逐渐降低,基于锌的除氮能力总结出两种可能的除氮机制;拉曼光谱测试结果表明,在锌添加量小于3.0 wt.%的研究范围内,锌的添加有利于提高晶体的结晶度.本研究不仅有助于天然金刚石形成机制的探究,而且对丰富金刚石的种类以及扩展人工合成金刚石的应用领域都有着重要意义.     

Effects of carbon convection field on large diamond growth under high-pressure high-temperature conditions

Large diamond crystals were successfully synthesized by FeNi-C system using temperature gradient method under high-pressure high-temperature conditions. The assembly of the growth cell was improved and the growth process of diamond was investigated. Effects of the symmetry of carbon convection field around the growing diamond crystal were investigated systematically by adjusting the position of seed crystal in the melted catalyst/solvent. The results indicate that morphologies and metal inclusion distributions of the synthetic diamond crystals vary obviously in both symmetric and non-symmetric carbon convection fields with temperature. Moreover, finite element method was applied to analyze carbon convection mode of the melted catalyst/solvent around the diamond crystal. This work is helpful for understanding the growth mechanism of diamond.     

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.     

高温高压下金刚石单晶生长过程的声发射动态特征

采用声发射技术对高温高压下人造金刚石单晶的生长过程进行了动态检测。结合合成压块的断口形貌,对金刚石单晶生长过程对应的主要声发射参数进行了分析。结果表明,声发射信号的能量计数、振铃计数、幅度和上升时间等特征参数能客观反映金刚石单晶在高温高压下的动态生长规律,为研究金刚石单晶的生长机制提供了重要的实验依据。     

Ensembles of indium phosphide nanowires: physical properties and functional devices integrated on non-single crystal platforms

A new route to grow an ensemble of indium phosphide single-crystal semiconductor nanowires is described. Unlike conventional epitaxial growth of single-crystal semiconductor films, the proposed route for growing semiconductor nanowires does not require a single-crystal semiconductor substrate. In the proposed route, instead of using single-crystal semiconductor substrates that are characterized by their long-range atomic ordering, a template layer that possesses short-range atomic ordering prepared on a non-single-crystal substrate is employed. On the template layer, epitaxial information associated with its short-range atomic ordering is available within an area that is comparable to that of a nanowire root. Thus the template layer locally provides epitaxial information required for the growth of semiconductor nanowires. In the particular demonstration described in this paper, hydrogenated silicon was used as a template layer for epitaxial growth of indium phosphide nanowires. The indium phosphide nanowires grown on the hydrogenerated silicon template layer were found to be single crystal and optically active. Simple photoconductors and pin-diodes were fabricated and tested with the view towards various optoelectronic device applications where group III–V compound semiconductors are functionally integrated onto non-single-crystal platforms.     

Growth and structure of epitaxial diamond films grown on Si(111) single crystals

Experiments on growing single-crystal diamond films on silicon crystals with (111) surface orientation have been performed. Results attesting to the possibility of obtaining thin heteroepitaxial films are presented. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 5, 414–418 (10 March 1997)     

Effects of a carbon convection field on large diamond growth under high-pressure high-temperature conditions

Large diamond crystals were successfully synthesized by a FeNi-C system using the temperature gradient method under high-pressure high-temperature conditions. The assembly of the growth cell was improved and the growth process of diamond was investigated. Effects of the symmetry of the carbon convection field around the growing diamond crystal were investigated systematically by adjusting the position of the seed crystal in the melted catalyst/solvent. The results indicate that the morphologies and metal inclusion distributions of the synthetic diamond crystals vary obviously in both symmetric and non-symmetric carbon convection fields with temperature. Moreover, the finite element method was applied to analyze the carbon convection mode of the melted catalyst/solvent around the diamond crystal. This work is helpful for understanding the growth mechanism of diamond.     

A relation between a metallic film covering on diamond formed during growth and nanosized inclusions in HPHT as-grown diamond single crystals

One of the most important characteristics and basic phenomena during diamond growth from liquid metal catalyst solutions saturated with carbon at high temperature–high pressure (HPHT) is that there exists a thin metallic film covering on the growing diamond, through which carbon-atom clusters are delivered to the surface of the growing diamond by diffusion. A study of microstructures of such a metallic film and a relation between the thin metallic film and the inclusions trapped in HPHT as-grown diamond single crystals may be helpful to obtain high-purity diamond single crystals. It was found that both the metallic film and the HPHT as-grown diamond single crystals contain some nanostructured regions. Examination by transmission electron microscopy suggests that the microstructure of the thin metallic film is in accordance with nanosized particles contained in HPHT as-grown diamond single crystals. The nanosized particles with several to several tens of nanometers in dimension distribute homogeneously in the metallic film and in the diamond matrix. Generally, the size of the particles in the thin metallic film is relatively larger than that within the diamond matrix. Selected area electron diffraction patterns suggest that the nanosized particles in the metallic film and nanometer inclusions within the diamond are mainly composed of f.c.c. (FeNi)₂₃C₆, hexagonal graphite and cubic γ-(FeNi). The formation of the nanosized inclusions within the diamond single crystals is thought not only to relate to the growth process and rapid quenching from high temperature after diamond synthesis, but also to be associated with large amounts of defects in the diamond, because the free energy in these defect areas is very high. The critical size of carbide, γ-(FeNi)and graphite particles within the diamond matrix should decrease and not increase according to thermodynamic theory during quenching from HPHT to room temperature and ambient pressure. Received: 13 September 2001 / Accepted: 12 June 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-0531/295-5081; E-mail: yinlw@sdu.edu.cn     

Influence of MgO substrate treatment on the structure-sensitive properties of epitaxial films (by the example of iron films)

A new technology of growing thin single-crystal MgO films on the MgO crystal surface using the method of chemical transport reactions is developed. The quality of deposited sublayers is checked with the structure-sensitive properties of iron epitaxial films.     

金刚石单晶生长的声发射实时检测初探

采用声发射检测技术,对高温高压下人造金刚石单晶的生长过程进行了检测和分析。利用由PCI-8型声发射仪和LMD-800型铰链式六面顶压机组成的声发射检测系统,检测了金刚石单晶的生长过程。将金刚石单晶生长和不生长过程中检测到的声发射信号进行对比和频谱分析,结果表明:声发射信号与金刚石单晶生长过程存在对应关系;金刚石单晶生长对应的声发射信号是一种低频信号,可以利用声发射信号的变化规律研究金刚石单晶在高温高压条件下的原位反应机理。     

Anisotropy of the mean free paths of phonons in single-crystal films of germanium,silicon, and diamond at low temperatures

The physical aspects of the influence of the elastic energy anisotropy of crystals on the anisotropy of the mean free paths of phonons in single-crystal films of germanium, silicon, and diamond in the diffuse scattering of phonons at the boundaries of the samples have been considered. It has been shown that, for sufficiently wide films of germanium, silicon, and diamond with the {100} and {111} orientations and the lengths of less than or equal to their width, the phonon mean free paths are isotropic (independent of the direction of the temperature gradient in the plane of the film). The anisotropy of the phonon mean free paths depends primarily on the orientation of the film plane and is determined by the focusing and defocusing of phonon modes. For single-crystal films of germanium, silicon, and diamond with the {100} and {111} orientations and lengths much larger than their width, the phonon mean free paths are anisotropic.     

Deposition and characterization of diamond epitaxial thin films on silicon substrates

Heteroepitaxial diamond growth has been attempted on mirror-polished monocrystalline (001), (111), and (110) silicon substrates by microwave plasma CVD. The surface morphology and the crystallographic properties of the films were characterized by means of Scanning Electron Microscopy (SEM), Raman spectroscopy, X-ray diffraction, and X-ray and Raman pole-figure analysis. The results demonstrate epitaxial growth of diamond on both (001) and (111) oriented silicon substrates. Preliminary results give strong evidence for substrate-induced orientation of the diamond crystallites also on (110) oriented silicon substrate. The heteroepitaxy can be assigned to the oriented covalent bonding across the interface between diamond and silicon.     

Effects of additive NaN_3 on the HPHT synthesis of large single crystal diamond grown by TGM

In this paper,large single crystal diamond with perfect shape and high nitrogen concentration approximately 1671-1742 ppm was successfully synthesized by temperature gradient method (TGM) under high pressure and high temperature (HPHT).The HPHT synthesis conditions were about 5.5 GPa and 1500-1550 K.Sodium azide (NaN3) with different amount was added as the source of nitrogen into the synthesis system of high pure graphite and kovar alloy.The effects of additive NaN3 on crystal growth habit were investigated in detail.The crystal morphology,nitrogen concentration and existing form in synthetic diamond were characterized by means of scanning electron microscope (SEM) and infrared (IR) absorption spectra,respectively.The results show that with an increase of the content of NaN3 added in the synthesis system,the region of synthesis temperature for high-quality diamond becomes narrow,and crystal growth rate is restricted,whereas the nitrogen concentration in synthetic diamond increases.Nitrogen exists in diamond mainly in dispersed form (C-centers) and partially aggregated form (A-centers).The defects occur more frequently on crystal surface when excessive NaN3 is added in the synthesis system.     

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     

Domain epitaxial growth of ferroelectric films of barium strontium titanate on sapphire

A model of the epitaxial growth of crystalline multicomponent films on single-crystal substrates with a domain correspondence is presented using a solid solution of barium strontium titanate on sapphire substrates (r cut). The domain epitaxial growth suggests the matching of the lattice planes of the film and the substrate having similar structures by comparison of domain multiple of an integral number of the interplanar spacings. Variation of the component composition of the solid solution enables changes in the domain size in the range sufficient for epitaxial growth. This method can be used to project the epitaxial growth of films of various solid solutions on single-crystal substrates.     

Scanning tunneling microscopy studies of temperature-dependent etching of diamond (100) by atomic hydrogen

We present a technique for obtaining atomic resolution ultrahigh vacuum scanning tunneling microscopy images of diamond (100) films, and use this technique to study the temperature dependence of the etching of epitaxial diamond (100) films by atomic hydrogen. We find that etching by atomic hydrogen is highly temperature dependent, resulting in a rough and pitted surface at T approximately 200 and 500 degrees C, respectively. At T approximately 1000 degrees C etching results in a smooth surface and is highly anisotropic, occurring predominantly in the direction of dimer rows. This observation supports recent theoretical models that propose anisotropic etching as the mechanism for the growth of smooth diamond (100) films.