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.

Synthesis and characterization of p-type boron-doped IIb diamond large single crystals

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K. The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively. The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique. The electrical properties including resistivities, Hall coefficients, Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method. The results show that large p-type boron-doped diamond single crystals with few nitrogen impurities have been synthesized. With the increase of quantity of additive boron, some high-index crystal faces such as {113} gradually disappear, and some stripes and triangle pits occur on the crystal surface. This work is helpful for the further research and application of boron-doped semiconductor diamond.

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba(N_3)_2

Additive Ba（N3）2 as a source of nitrogen is heavily doped into the graphite-Fe-based alloy system to grow nitrogendoped diamond crystals under a relatively high pressure （about 6.0 GPa） by employing the temperature gradient method. Gem-grade diamond crystal with a size of around 5 mm and a nitrogen concentration of about 1173 ppm is successfully synthesised for the first time under high pressure and high temperature in a China-type cubic anvil highpressure apparatus. The growth habit of diamond crystal under the environment with high degree of nitrogen doping is investigated. It is found that the morphologies of heavily nitrogen-doped diamond crystals are all of octahedral shape dominated by {111} facets. The effects of temperature and duration on nitrogen concentration and form are explored by infrared absorption spectra. The results indicate that nitrogen impurity is present in diamond predominantly in the dispersed form accompanied by aggregated form, and the aggregated nitrogen concentration in diamond increases with temperature and duration. In addition, it is indicated that nitrogen donors are more easily incorporated into growing crystals at higher temperature. Strains in nitrogen-doped diamond crystal are characterized by micro-Raman spectroscopy. Measurement results demonstrate that the undoped diamond crystals exhibit the compressive stress, whereas diamond crystals heavily doped with the addition of Ba（N3）2 display the tensile stress.

Growth characteristics of type IIa large single crystal diamond with Ti/Cu as nitrogen getter in FeNi–C system

High-quality type IIa large diamond crystals are synthesized with Ti/Cu as nitrogen getter doped in an FeNi–C system at temperature ranging from 1230℃to 1380℃and at pressure 5.3–5.9 GPa by temperature gradient method.Different ratios of Ti/Cu are added to the Fe Ni–C system to investigate the best ratio for high-quality type IIa diamond.Then,the different content of nitrogen getter Ti/Cu(Ti:Cu=4:3)is added to this synthesis system to explore the effect on diamond growth.The macro and micro morphologies of synthesized diamonds with Ti/Cu added,whose nitrogen concentration is determined by Fourier transform infrared(FTIR),are analyzed by optical microscopy(OM)and scanning electron microscopy(SEM),respectively.It is found that the inclusions in the obtained crystals are minimal when the Ti/Cu ratio is 4:3.Furthermore,the temperature interval for diamond growth becomes narrower when using Ti as the nitrogen getter.Moreover,the lower edge of the synthesis temperature of type IIa diamond is 25℃higher than that of type Ib diamond.With the increase of the content of Ti/Cu(Ti:Cu=4:3),the color of the synthesized crystals changes from yellow and light yellow to colorless.When the Ti/Cu content is 1.7 wt%,the nitrogen concentration of the crystal is less than 1 ppm.The SEM results show that the synthesized crystals are mainly composed by(111)and(100)surfaces,including(311)surface,when the nitrogen getter is added into the synthesis system.At the same time,there are triangular pits and dendritic growth stripes on the crystal surface.This work will contribute to the further research and development of high-quality type IIa diamond.

Effect of Seed Sizes on Growth of Large Synthetic Diamond Crystals

For the growth of large synthetic diamond crystals by temperature gradient method （TGM）, the grit sizes of seed crystals have great effects on the growth rate and quality of large grown crystals. Because of the limited area of seed surfaces, the maximum diffusion flux of carbon source, which could be absorbed by the seed, is related to the seed size. And with increasing the seed sizes, the growth rates also increase markedly. However, the seed sizes should be lower than a certain value, which determines the crystal quality directly. For example, with NiMnCo alloy as the metal solvent, when the seed size increases from 0.5 to 1.8 mm, the growth rate increases greatly from about 1.1 to 3.2 mg/h; when the size is beyond 2.0 mm, more and more metal inclusions would be incorporated into the grown crystals, and the crystal quality is destroyed heavily. Finite element analysis （FEA） shows that, due to the special assembly of growth cell, the diffusion of carbon source in the metal solvent is very inhomogeneous, which could be substantiated directly by the appearances and shapes of large grown crystals and the remains of carbon source. And this inhomogeneous diffusion of carbon source would be very harmful to the growth of large diamond crystals, especially when large-size seed crystals are used.

Morphology Change of Metastable Regrown Graphite with Boron Additive under HPHT

By temperature gradient method under high pressure and high temperature （HPHT）, with NiMnCo alloy as the solvent metal, at diamond-stable region of about 5.4 GPa and 1500 K, metastable regrown graphite crystals of different morphology were synthesized. With B as an additive incorporated into the NiMnCo-C system, metastable regrown graphite crystals of sphere-like shape were firstly obtained under HPHT. If the growth system does not contain B, sheet-like regrown graphite crystals, most with regular hexagonal morphology, are grown upwards and standing vertically in the metal solvent. When B additive of 1.0 wt pct was added into carbon source （graphite powder）, all metastable regrown graphite crystals took on the habit of regular sphere-like morphology, and were grown by a spiral layer growth mechanism.