Hetero-Epitaxial Diamond Single Crystal Growth on Surface of cBN Single Crystals at High Pressure and High Temperature

We report a new diamond synthesis process in which cubic boron nitride single crystals are used as seeds, FesoNi20 alloy powder is used as catalyst/solvent and natural flake-like graphite is used as the carbon source. The samples are investigated using laser Raman spectra and x-ray diffraction （XRD）. Morphology of the sample is observed by a scanning electron microscope （SEM）. Based on the measurement results, we conclude that diamond single crystals have grown on the cBN crystal seeds under the conditions of high temperature 1230℃ and high pressure 4.8 GPa. This work provides an original method for synthesis of high quality hereto-semiconductor with cBN and diamond single crystals, and paves the way for future development.     

Effects of Al and Ti/Cu on Synthesis of Type-IIa Diamond Crystals in Ni70Mn25Co5-C System at HPHT

High-quality type-Ⅱa gem diamond crystals are successfully synthesized in a NiToMn25Co5-C system by temperature gradient method （TGM） at about 5.5 GPa and 1560 K. Al and Ti/Cu are used as nitrogen getters respectively. While nitrogen getter Al or Ti/Cu is added into the synthesis system, some inclusions and caves tend to be introduced into the crystals. When Al is added into the solvent alloy, we would hardly gain high-quality type-Ⅱa diamond crystals with nitrogen concentration Nc 〈 1 ppm because of the reversible reaction of Al and N at high pressure and high temperature （HPHT）. Piowever, when Ti/Cu is added into the solvent alloy, high-quality type-Ⅱa diamond crystals with Nc 〈 1 ppm can be grown by decreasing the growth rate of diamonds.     

Novel technique for hetero-epitaxial diamond film growth on cubic boron nitride from iron carbide at high temperature and high pressure

Cubic boron nitride (c-BN) crystals about 0.1–0.3 mmin dimension were treated with iron carbide powders (high purity 99%) with size of 80–100 mesh at a high temperature of 1620 K and a high pressure of 5.2 GPa. It was found that hetero-epitaxial diamond films have been grown on the c-BN from iron carbide. The formation of dia-mond films on the cubic boron nitride can be confirmed by laser Raman spectra, face scan of elements and reflective high-energy electron diffraction. It was suggested that diamond films could be epitaxially formed on the c-BN through decomposition of iron carbide. This approach provides a possible and very effective way to realize hetero-epitaxial growth of homogeneous and large-area diamond films on c-BN, which is different from the conventional technique using a chemical vapor deposition method. Received: 20 December 2000 / Accepted: 9 January 2001 / Published online: 28 February 2001     

HPHT Synthesis of Different Shape Coarse-Grain Diamond Single Crystals

Synthesis of coarse-grain diamond crystals is studied in a China-type SPD6× 1670T cubic high-pressure apparatus with high exact control system. To synthesize high quality coarse-grain diamond crystals, advanced indirect heat assembly, powder catalyst technology and optimized synthesis craft are used. At last, three kinds of coarse- grain diamond （about 0.85 mm） single crystals with hexahedron, hex-octahedron and octahedron are synthesized successfully under HPHT （about 5.4 GPa, 1300-1450℃）. The growth characters of different shape crystals are discussed. The results and techniques might be useful for the production of coarse-grain diamonds.     

Effects of catalyst height on diamond crystal morphology under high pressure and high temperature

The effect of the catalyst height on the morphology of diamond crystal is investigated by means of temperature gradient growth(TGG) under high pressure and high temperature(HPHT) conditions with using a Ni-based catalyst in this article. The experimental results show that the morphology of diamond changes from an octahedral shape to a cuboctahedral shape as the catalyst height rises. Moreover, the finite element method(FEM) is used to simulate the temperature field of the melted catalyst/solvent. The results show that the temperature at the location of the seed diamond continues to decrease with the increase of catalyst height, which is conducive to changing the morphology of diamond. This work provides a new way to change the diamond crystal morphology.     

Dependence of Limited Growth Rate of High-Quality Gem Diamond on Growth Conditions

The growth rate of diamond has been investigated for a long time and researchers have been attempting to enhance the growth rate of high-quality gem diamond infinitely. However, it has been found according to previous research results that the quality of diamond is debased with the increase of growth rate. Thus, under specific conditions, the growth rate of high-quality diamond cannot exceed a limited value that is called the limited growth rate of diamond. We synthesize a series of type Ib gem diamonds by temperature gradient method under high pressure and high temperature （HPHT） using the as-grown {100} face. The dependence of limited growth rate on growth conditions is studied. The results show that the limited growth rate increases when synthetic temperature decreases, also when growth time is prolonged.     

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     

Effect of Carbon Source with Different Graphitization Degrees on the Synthesis of Diamond

Using three kinds of graphites with different graphitization degrees as carbon source and Fe-Ni alloy powder as catalyst, the synthesis of diamond crystals is performed in a cubic anvil high-pressure and high-temperature apparatus （SPD-6 × 1200）. Diamond crystals with perfect hexoctahedron shape are successfully synthesized at pressure from 5.0 to 5.5GPa and at temperature from 1570 to 1770K. The synthetic conditions, nucleation, morphology, inclusion and granularity of diamond crystals are studied. The temperature and pressure increase with the increase of the graphitization degree of graphite. The quantity of nucleation and granularity ofdiamonds decreases with the increase of graphitization degree of graphite under the same synthesis conditions. Moreover, according to the results of the M6ssbauer spectrum, the composition of inclusions is mainly Fe3 C and Fe-Ni alloy phases in diamond crystals synthesized with three kinds of graphites.     

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     

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.     

Formation and crystal structure of metallic inclusions in a HPHT as-grown diamond single crystal

One of the most important characteristics associated with crystal growth technology is the entrapment of inclusions by the growing crystal. Diamond single crystals prepared under high temperature-high pressure (HPHT) usually contain metallic inclusions. In the present paper, metallic inclusions in a diamond grown from a Fe-Ni-C system using the HPHT method have been, for the first time, systematically examined by transmission electron microscopy (TEM). Energy dispersive X-ray spectrometry (EDS) , combined with selected area electron diffraction (SAD) patterns, has been used to identify the chemical composition and crystal structure of the metallic inclusions. The metallic inclusions were found to be composed mainly of cubic γ-(FeNi), face-centered cubic (FeNi)₂₃C₆, ortho-rhombic Fe₃C and hexagonal Ni₃C, which may have been formed through the entrapment of molten catalyst by the growth front or through reaction of the trapped melt with contaminants in the diamond. Received: 19 June 2000 / Accepted: 21 June 2000 / Published online: 16 August 2000     

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.     

基于有限元法分析宝石级金刚石的合成腔体温度场

以有限元法为理论分析手段模拟分析了温度梯度法合成宝石级金刚石大单晶的腔体温度场,实现了对宝石级金刚石的合成腔体内各位置温度同时测量.模拟结果表明:在宝石级金刚石合成过程中,其温度分布呈不均匀分布.腔体内高温区分布在样品(碳源+触媒)边缘,低温区分布在籽晶附近.样品腔内热量的传递方式和样品腔内的碳源输运方式相同,均由碳源的两侧向籽晶附近传输.籽晶附近轴向温度梯度大于径向温度梯度,导致单位时间内其轴向生长尺寸大于径向生长尺寸.宝石级金刚石腔体温度场分析的理论模型的成功构建,为新型宝石级金刚石腔体的研制提供了良好的设计基础,对促进优质宝石级金刚石的生长技术具有指导意义.     

FEM simulations and experimental studies of the temperature field in a large diamond crystal growth cell

We investigate the temperature field variation in the growth region of a diamond crystal in a sealed cell during the whole process of crystal growth by using the temperature gradient method (TGM) at high pressure and high temperature (HPHT). We employ both the finite element method (FEM) and in situ experiments. Simulation results show that the temperature in the center area of the growth cell continues to decrease during the process of large diamond crystal growth. These results are in good agreement with our experimental data, which demonstrates that the finite element model can successfully predict the temperature field variations in the growth cell. The FEM simulation will be useful to grow larger high-quality diamond crystal by using the TGM. Furthermore, this method will be helpful in designing better cells and improving the growth process of gem-quality diamond crystal.     

用表面生长CVD金刚石的石墨合成高压金刚石

 用热灯丝CVD方法在多晶石墨衬底表面制备CVD金刚石颗粒，并用这种石墨在高温高压条件下采用六面顶压机合成出高压金刚石。初步实验结果表明：采用其表面生长CVD金刚石颗粒的石墨合成高压金刚石，可以提高金刚石的转化率和降低合成压力。     

Surface Structure of Large Synthetic Diamonds by High Temperature and High Pressure

With NiMnCo and FeCoNi alloys as solvent metals, large single-crystal diamonds of about 3mm across are grown by temperature gradient method （TGM） under high temperature and high pressure （HPHT）. Although both {100} and {111} surfaces are developed by a layer growth mechanism, some different characteristic patterns are seen clearly on the different surfaces, no matter whether NiMnCo or FeCoNi alloys are taken as the solvent metals. For {100} surface, it seems to have been melted or etched greatly, no dendritic patterns to be found, and only a large number of growth hillocks are dispersed net-likely; while for {111} surface, it often seems to be more smooth-faced, no etched or melted traces are present even when a lot of depressed trigonal growth layers. This distinct difference between {111} and {100} surfaces is considered to be related to the difference of surface-atom distribution of different surfaces, and {111} surfaces should be more difficult to be etched and more steady than {100} surfaces.     

Influence of annealing treatment on as-grown Ib-type diamond crystal at a high temperature and high pressure

In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 C to 1900 C for 1 h.Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature.The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature.The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 C,which is induced by nitrogen aggregation in a diamond lattice.The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra.The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak,and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.     

Nucleation studies and characterization of potassium thiocyanate added KDP crystals grown by seed rotation technique

The effect of the addition of potassium thiocyanate on potassium dihydrogen phosphate (KDP) crystals, grown from aqueous solution by the temperature lowering method using a microcontroller based seed rotation technique has been studied. As part of nucleation studies, metastable zone width, induction period and crystal growth rate of additive added KDP are determined and analyzed with the pure system. Dielectric measurements were carried out on pure and doped crystals at various temperatures ranging from 313 to 423 K and compared. The crystalline perfection of the grown crystal was studied by the high resolution X-ray diffraction analysis. The crystal grown from additive added solution was subjected to structural, optical transmission, second harmonic generation and hardness studies and the effect of additive on pure system is investigated.     

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     

高长径比柱状金刚石的高温高压合成与机理研究

为了拓展金刚石的种类和解决金刚石工具使用过程中因把持力不足造成的使用寿命降低等, 在中国式六面顶压机上, 通过对FeNi触媒成分和工艺的优化, 成功合成出高质量长径比大于2.5, 平均粒度在0.8—1.0 mm的柱状金刚石晶体. 该晶体独特的形貌, 将极大改善金刚石工具的在使用过程中出现的"脱粒"现象. 另外, 实验中发现, 柱状金刚石晶体的生长速度也远大于传统晶体的生长速度. 采用扫描电镜(SEM)和能谱(EDS)等手段对柱状金刚石晶体及晶体周围触媒成分进行了表征; 结果表明, 柱状金刚石晶体在生长过程中存在{100}和{111}晶面拉长, 以及包覆在晶体周围的触媒成分偏析. 在此基础上, 阐明了柱状晶体生长机理.