Study on growth of coarse grains of diamond with high quality under HPHT

The growth of coarse grains of diamond was observed with graphite as carbon source and Fe₈₀Ni₂₀ alloy powder as catalyst at HPHT in a China-type SPD 6×1670T cubic high-pressure apparatus with highly exact control system. To synthesize coarse grains of diamond crystal with high quality, advanced indirect heat assembly, powder catalyst technology and catalyst with optimal granularity were used. Especially the nucleation of diamond and the growth rate were strictly controlled by the optimized synthesis craft. At last, diamond crystals (about 0.85 mm) in the perfect hex-octahedron shape were successfully synthesized at ~5.4 GPa and ~1360℃ in 60 min. The characteristic of crystal growth with powder catalyst technology under HPHT was discussed. The results and techniques might be useful for production of coarse grains of diamond.     

Microstructures of metallic film and diamond growth from Fe-Ni-C system

The microstructures of metallic film surrounding diamond have been systemically studied using the transmission electron microscopy (TEM) and the atom force microscopy (AFM). The film can be divided into three layers (inner layer near diamond, external layer near graphite and middle layer). The graphite cannot be directly transformed into diamond in the film at HTHP; there exists a parallel relationship between (−111) of γ-(Fe,Ni) and (110) of Fe₃C in the inner layer; the sawtooth-like step morphology found by AFM on the film is similar to that of corresponding diamond surface. A new model for diamond growth at HPHT is proposed from the parallel relationship and sawtooth-like step morphology. It is believed that Fe₃C may be a transitional phase in the course of diamond growth, γ-(Fe,Ni) in the inner layer can absorb carbon atom groups with lamella structure from Fe₃C, and then the carbon groups stack on growing diamond.     

Growth and characterization of large, high quality cubic diamond crystals

High quality cubic diamond crystals were grown using the temperature gradient method at high pressure and high temperature(HPHT),in a new FeNi alloy as solvent.The crystals were grown at relatively low temperatures suitable for the growth of {100} faces.An increase in the radial growth rate,and inhibition of the axial growth caused the growth of large,high quality cubic diamond single crystals at high growth rates.For example,over 33 h,the radial growth rate was 0.22 mm/h,while the axial growth rate was only 0.08 mm/h;the growth rate by weight was also increased to 7.3 mg/h.The yellow color of our crystal samples was more uniform than samples from Sumitomo Corporation of Japan and Element Six Corp.The Raman FWHW of the 1332 cm 1 peak in our diamond sample was smaller than the Element Six Corp.sample,but larger than that of the Sumitomo Corp.sample.The nitrogen content of our diamond samples was 240 ppm,which was much higher than the Sumitomo and Element Six samples because of the higher growth rate of our diamond samples.     

Selective interfacial bonding and thermal conductivity of diamond/Cu-alloy composites prepared by HPHT technique

Cu-based and Cu-alloy-based diamond composites were made by high-pressure-high-temperature (HPHT) sintering with the aim of maximizing the thermal conductivity of the composites. Improvements in interfacial bonding strength and thermo-physical properties of the composites were achieved using an atomized copper alloy with minor additions of Co, Cr, B, and Ti. The thermal conductivity (TC) obtained exhibited as high as 688 W·m-1·K-1, but also as low as 325 W·m-1·K-1. A large variation in TC can be rationalized by the discrepancy of diamond-matrix interfacial bonding. It was found from fractography that preferential bonding between diamond and the Cu-alloy matrix occurred only on the diamond {100} faces. EDS analysis and Raman spectra suggested that selective interfacial bonding may be attributed to amorphous carbon increasing the wettability between diamond and the Cu-alloy matrix. Amorphous carbon was found to significantly affect the TC of the composite by interface modification.     

Analysis of the carbon source for diamond crystal growth

The lattice constants of diamond and graphite at high pressure and high temperature （HPHT） were calculated on the basis of linear expansion coefficient and elastic constant. According to the empirical electron theory of solids and molecules （EET）, the valence electron structures （VESs） of diamond, graphite crystal and their common planes were calculated. The relationship between diamond and graphite structure was analyzed based on the boundary condition of the improved Thomas-Fermi-Dirac theory by Cheng （TFDC）. It was found that the electron densities of common planes in graphite were not continuous with those of planes in diamond at the first order of approximation. The results show that during the course of diamond single crystal growth at HPHT with metal catalyst, the carbon sources forming diamond structure do not come from the graphite structure directly. The diamond growth mechanism was discussed from the viewpoint of valence electron structure.     

Effects of Ti additive on HPHT diamond synthesis in Fe-Ni-C system

Diamond crystals with low nitrogen concentration were synthesized from the Fe-Ni-C system with Ti additive at high pressure and high temperature （HPHT） in a china-type cubic high pressure apparatus （CHPA）. The synthesis pressure range was 4.8-5.2 GPa, and the temperature range was 1420-1600 K. The lowest synthesis pressure for diamond fell first and then rose with the increase of Ti additive. The color, shape, surface morphology and nitrogen impurity concentration of the synthesized diamond crystals were characterized using optical microscopy （OM）, scanning electron microscopy （SEM） and micro Fourier transform infrared （FTIR） spectrometry. The results show that the Ti additive has significant effects on color, growth rate, crystal shape, surface morphology and nitrogen impurity con- centration of the synthesized diamond crystals. The color of diamond crystals synthesized without Ti additive is yellow, while that with Ti additive becomes light and nearly colorless. The growth rate without Ti additive is higher than that with Ti additive. The crystal shapes of as-grown diamond crystals vary with the increase of Ti additive. The {111} crystal faces become dominant and some {311} crystal faces appear with the increase of Ti additive. The concentration of nitrogen impurity in diamond crystals without Ti additive is higher than that with Ti additive.     

电镀晶种法合成金刚石单晶实验研究

目的寻求一种合成金刚石大单晶的有效方法。方法采用在金刚石单晶上面电镀一层金属镍膜作为触媒,镀有镍膜的金刚石晶种被规则地放在石墨片上预先刻好的洞中,每两个洞之间保持相等的间距,然后与其他石墨片交替组装在高温高压下进行实验合成。结果实验结果表明,在合成压力、温度和时间分别~5.8 GPa、~1 460℃和14 min的条件下,合成后的单晶尺寸约是原晶种的3倍。与传统的合成工艺相比较,合成后的金刚石单晶具有较好的形貌与质量。结论采用电镀晶种法合成对高品级金刚石大单晶的合成具有一定参考意义。     

Structure properties for the superconductor MgCNi<Subscript>3</Subscript> under high pressure with synchrotron radiation

In situ high pressure energy dispersive X-ray diffraction measurements on cubic-perovskite superconductor MgCNi₃ under pressure up to 22 GPa have been performed by using diamond anvil cell with synchrotron radiation. We have investigated its crystal structure and compressibility. The results show that the structure of MgCNi₃ is stable under pressure up to 22 GPa. According to Birch-Murnaghan state equation, when we assume B ₀′ = 4, we get B₀ = 267.8 ± 7.2 GPa.     

Mechanism of diamond-to-graphite transformation at diamond-stable conditions

The diamond-to-graphite transformation at diamond-stable conditions is studied by temperature gradient method （TGM） under high pressure and high temperature （HPHT）, although it is unreasonable from the view of thermodynamic considerations. It is found that, at diamond-stable conditions, for example, at 5.5 GPa and 1550 K, with fine diamond grits as carbon source and NiMnCo alloy as metal solvent assisted, not only large diamond crystals, but metastable regrown graphite crystals would be grown by layer growth mechanism, and the abundance of carbon source in the higher temperature region is indispensable for the presence of metastable regrown graphite crystals. From this transformation, it is concluded that, with metal solvent assisted, although the mechanism of crystal growth could be understood by the macro-mechanism of solubility difference between diamond and graphite in metal solvents, from the point of micro-mechanism, the minimum growth units for diamond or graphite crystals should be at atomic level and unrelated to the kinds of carbon source （diamond or graphite）, which could be accumulated free-selectively on the graphite with Sp2Tr or diamond crystals with sp3 bond structure.     

Effect of sintering parameters on the microstructure and thermal conductivity of diamond/Cu composites prepared by high pressure and high temperature infiltration

Pure Cu composites reinforced with diamond particles were fabricated by a high pressure and high temperature (HPHT) infiltration technique. Their microstructural evolution and thermal conductivity were presented as a function of sintering parameters (temperature, pressure, and time). The improvement in interfacial bonding strength and the maximum thermal conductivity of 750 W/(m·K) were achieved at the optimal sintering parameters of 1200℃, 6 GPa and 10 min. It is found that the thermal conductivity of the composites depends strongly on sintering pressure. When the sintering pressure is above 6 GPa, the diamond skeleton is detected, which greatly contributes to the excellent thermal conductivity.     

Effect of additive boron on type-Ib gem diamond single crystals synthesized under HPHT

The boron-doped type-Ib gem diamond crystals were synthesized successfully by adding amorphous boron into a system of graphite and Kovar catalyst under high pressure and high temperature (HPHT).The effect of additive boron on type-Ib gem diamond was extensively studied including the growth characteristic,morphology and nitrogen concentration.The synthesized boron-doped type-Ib gem diamond crystals were characterized by optical microscope (OM),scanning electron microscope (SEM) and infrared spectrometer (IR)...     

Study on the HPHT synthetic diamond crystal from Fe-C（H） system and its significance

Investigations of crystal habit, micro-topographic imaging, micro-composition and micro-structural analysis of HPHT synthetic diamonds from the Fe-C（H） system indicate that most of them have an octahedral habit. The crystals grow mainly layer-to-layer from center to periphery. HPHT synthetic diamond is smaller in size than natural diamond because it only goes through nucleation and growth in the early stage. In the middle and late stages, due to the coalescence of diamond grains related to differences of surface energy, the growth of HPHT synthetic diamond is limited. The active energy （E） of transforming single nitrogen into a nitrogen-pair is lowered and the time of transforming single nitrogen into a nitrOgen-pair is shortened because of the existence of hydrogen. Therefore, aggregate nitrogen （A-centers） may exist in synthetic diamond from HPHT and explosive detonation processes. It needs further discussion on a worldwide view that the time of natural diamond formation extracted from nitrogen aggregation is some hundred million years. Consideration of the way in which surface energy influences the growth of diamond can help to understand some of the remaining issues （e.g. growth mechanism, etc.） in the HPHT synthetic process and effectively explain the formation of natural diamond in terms of HPHT thermodynamic theory. Especially, it is important to pay more attention to the influence of hydrogen on surface energy in that hydrogen may be a ＂bridge＂ for explaining the formation of HPHT synthetic and natural diamond.     

Synthesis of high quality type-Ib diamond crystals in carats grade

High quality type-Ib tower-shape gem-diamond crystals in carats grade were synthesized in cubic anvil high pressure apparatus (SPD-6×1200) at 5.4 GPa and 1250-1450°C. The relationship between the growth time and the weight of growth diamond has been gained. The faces of {110} and {113} were found in the synthetic diamond crystals frequently. We found that the relative growth rate of {113} face was descending with the increase of growth temperature, and that of {110} face had no obvious change with the incre...     

Effects of boron on the microstructure and thermal properties of Cu/diamond composites prepared by pressure infiltration

Diamond reinforced copper (Cu/diamond) composites were prepared by pressure infiltration for their application in thermal management where both high thermal conductivity and low coefficient of thermal expansion (CTE) are important. They were characterized by the microstructure and thermal properties as a function of boron content, which is used for matrix-alloying to increase the interfacial bonding between the diamond and copper. The obtained composites show high thermal conductivity (>660 W/(m·K)) and low CET (<7.4×10-6 K-1) due to the formation of the B₁₃C₂ layer at the diamond-copper interface, which greatly strengthens the interfacial bonding. Thermal property measurements indicate that in the Cu-B/diamond composites, the thermal conductivity and the CTE show a different variation trend as a function of boron content, which is attributed to the thickness and distribution of the interfacial carbide layer. The CTE behavior of the present composites can be well described by Kerner’s model, especially for the composites with 0.5wt% B.     

Effects of carbon diffusing field in alloy solvent on the growth of tower-shape diamond single crystal

High-quality type-Ib tower-shape diamond single crystals were synthesized in cubic anvil high pressure apparatus (SPD-6×1200) at 5.4 GPa and 1250-1450°C. The (100) face of seed crystal was used as the growth face, and FeNiMnCo alloy was used as the solvent/catalyst. Two kinds of carbon diffusing fields (type-B and type-G) were simulated by finite element method (FEM). Using the two kinds of carbon diffusing fields, many diamond single crystals were synthesized. The effects of carbon diffusing fields on the ...     

Fe-Si-C体系合成金刚石的生长特性

研究高温高压下掺Si合成金刚石, 并与Fe-C体系合成的金刚石进行比较. 实验结果表明, 体系中掺入Si, 合成的晶体颜色比Fe-C体系合成的晶体颜色浅, 在相同的合成时间内, Fe-Si-C体系合成金刚石的粒度比Fe-C体系合成金刚石的粒度小; 通过X射线衍射(XRD)可见, 该体系产生FeSi和Fe₃C两种新物质.      

Dependence of nitrogen concentration in type Ib diamonds on synthesis temperature

Type Ib diamonds were grown by the temperature gradient method (TGM) at 5.5 GPa and 1500－1560 K in a china-type cubic anvil high pressure apparatus using Ni₇₀Mn₂₅Co₅ alloy as solvent/catalyst. The concentration of nitrogen (C_N) in type Ib diamonds synthesized at different synthesis temperatures was measured by a Fourier transform infrared (FTIR) spectrometer. The dependence of C_N in diamond on synthesis temperature was studied. For the type Ib diamonds synthesized using Ni₇₀Mn₂₅Co₅ as catalyst, its C_N decreases along with the increase of synthesis temperature.     

Ultrasonic measurements of single-crystal gold under hydrostatic pressures up to 8 GPa in a Kawai-type multi-anvil apparatus

Ultrasonic measurements were conducted on single-crystal gold at ambient condition and hydrostatic pressures up to 8 GPa at room temperature in a Kawai-type multi-anvil apparatus. The P-wave velocities measured at high pressures were in good agreement with Daniels and Smith’s ultrasonic study. The three independent elastic constants of gold at ambient condition were determined to be C11=192.7 GPa, C12=162.9 GPa, and C44=42.4 GPa. On the basis of an analysis of previous elastic data and the present ultrasonic data, the pressure derivatives of three elastic constants were estimated to be C1 ′1= 7.12,C 1′2 = 6.24,and C4′4 = 1.82. The calculated values of isothermal bulk modulus (KT0) and its pressure derivatives ( KT ′0) are KT0 = 166.44 GPa and KT ′0= 6.56. This indicates that Anderson et al.’s model of equation of state of gold might underestimates pressure about 1 GPa at pressure around 23 GPa and ambient temperature. Our results explained the discrepancies among the models of equation of state of gold proposed previously.     

Polishing technology of surface for diamond film using the method of laser ablation

Conclusion Good unity in thickness and a smooth surface of diamond film are obtained by using the methods of laser ablation and machine grind to the surface of diamond film. Compared with the machine polishing method, the polishing rate increased by over 10 times. After laser ablation and machine polishing, the thickness change and the roughness of a diamond film with 400 μm thickness and 1 cm² area are 10–15 μm and 0.05 μm, and this film is basically suitable to using in electronics.     

球形金刚石的生长机理研究

用热丝化学气相沉积设备研究了钢渗铬层、P-Si（100）基片和三氧化二铝基底表面形成的球形金刚石．研究结果表明：在不适合球形金刚石形成的工艺爷件下,在P-Si（100）基片和三氧化二铝表面沉积的晶形很好的金刚石膜中也存在球形金刚石团块（称为异常长大金刚石团块）;首次使用金刚石“异常晶核”解释了异常长大金刚石团块的形成．球形金刚石膜由异常长大金刚石团块组成．异常长大金刚石团块的形成不但与沉积工艺参数有关,而且与CVD金刚石生长特性有关．