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.
在压力为5.5—6.2 GPa,温度为1280—1450℃的条件下,利用温度梯度法详细考察了氮氢协同掺杂对{100}晶面生长宝石级金刚石的影响.实验结果表明伴随合成腔体内氮、氢浓度的升高,合成条件明显升高,金刚石生长V形区间上移;晶体的红外光谱中与氮相关的吸收峰急剧增强,氮含量可达2000 ppm,同时位于2850 cm 1和2920 cm 1对应于sp3杂化C—H键的对称伸缩振动和反对称伸缩振动的红外特征峰逐渐增强,表明晶体中既有高的氮含量,同时又含有氢.对晶体进行电镜扫描发现,氮氢协同掺杂对晶体形貌影响明显,出现拉长的{111}面,且晶体表面上有三角形生长纹理.拉曼测试表明,晶体的峰位向高频偏移、半峰宽变大,说明氮、氢杂质的进入对晶体内部产生了应力.本文成功地以{100}晶面为生长面合成出高氮含氢宝石级金刚石单晶,在探究氮氢共存环境下金刚石生长特性的同时,也可为理解天然金刚石的形成机理提供帮助.
In this paper,the diamond epitaxial growth mechanism has been studied in detail by employing several types of diamond as a seed in a catalyst-graphite system under high pressure and high temperature (HPHT) conditions.We find that the diamond nucleation,growth rate,crystal orientation,and morphology are significantly influenced by the original seeds.The smooth surfaces of seeds are beneficial for the fabrication of high-quality diamond.Our results reveal that the diamond morphology is mainly determined by the original shape of seeds in the early growth stage,but it has an adjustment process during the growth and leads to well symmetry.Additionally,we have also established the growth model for the twinned diamond grown on several seeds,and proposed the possible growth processes by tracking the particular shapes of seeds before and after treatment under HPHT conditions.These results suggest that the shape-controlled synthesis of diamond with well morphology can be realized by employing certain suitable diamond seeds.This work is expected to play an important role in the preparation of trustworthy diamond-based electronic and photonic devices.
In this paper,we explore diamond synthesis with a series of experiments using an Fe-Ni catalyst and a P3N5 additive in the temperature range of 1250-1550 ℃ and the pressure range of 5.0-6.3 GPa.We also investigate the influence of nitrogen on diamond crystallization.Our results show that the synthesis conditions(temperature and pressure) increase with the amount of P3N5 additive increasing.The nitrogen impurity can significantly influence the diamond morphology.The diamonds stably grow into strip and lamellar shapes in the nitrogen-rich environment.The Fourier-transform infrared spectrum shows that the nitrogen concentration increases rapidly with the content of P3N5 additive increasing.By spectrum analysis,we find that with the increase of the nitrogen concentration,the Ib-type nitrogen atoms can aggregate in the A-centre form.The highest A-centre nitrogen concentration is approximately 840 ppm.
A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.
