高温高压生长宝石级金刚石单晶的表面特征研究

本文利用高温高压温度梯度法,NiMnCo合金作为触媒,分别采用籽晶{100}和{111}作为生长面,合成了Ib型宝石级金刚石单晶,对其表面特征进行了分析和讨论.结果发现,宝石级金刚石单晶的表面特征不具有唯一性,多数情况下,晶体{111}面明显较{100}面平整,而且{100}面生长台阶的棱角不清晰,经常会出现经触媒融融过的痕迹,并且这种现象的出现跟籽晶生长面不同和合成温度条件高低无关;{111}面有时也会出现明显的生长台阶,棱角清晰,并且形状较为规则.宝石级金刚石晶体表面特征的不唯一性说明晶体表面特征对生长条件稳定性有更高的要求.     

优质立方六面体金刚石大单晶的生长研究

高温高压静压触媒法合成的金刚石单晶,往往呈现六八面体形貌,因为立方六面体单晶{100}面的生长区间相对较小.本研究利用高温高压温度梯度法,自制Fe-Ni合金触媒,通过对合成组装和工艺进行合理调整后,控制晶体在相对低温适合{100}面生长区域内生长,得到的晶体均呈现完整立方六面体形貌;同时为抑制包裹体和其他杂质的进入,人为的提高晶体的径向平铺生长速度,抑制其轴向生长速度.以在33 h内合成的优质立方六面体晶体为例,晶体最大方向尺寸达到7.3 mm,重1.2克拉,其径向生长速度达到0.22 mm/h,轴向生长速度仅为0.08 mm/h,增重速度为7.3 mg/h.     

Dependence of nitrogen vacancy color centers on nitrogen concentration in synthetic diamond

Crystallization of diamond with different nitrogen concentrations was carried out with a FeNiCo-C system at pressure of 6.5 GPa. As the nitrogen concentration in diamond increased, the color of the synthesized diamond crystals changed from colorless to yellow and finally to atrovirens (a dark green). All the Raman peaks for the obtained crystals were located at about 1330 cm^-1 and contained only the sp³ hybrid diamond phase. Based on Fourier transform infrared results, the nitrogen concentration of the colorless diamond was < 1 ppm and absorption peaks corresponding to nitrogen impurities were not detected. However, the C-center nitrogen concentration of the atrovirens diamond reached 1030 ppm and the value of A-center nitrogen was approximately 180 ppm with a characteristic absorption peak at 1282 cm^-1. Furthermore, neither the NV⁰ nor the NV^- optical color center existed in diamond crystal with nitrogen impurities of less than 1 ppm by photoluminescence measurement. However, Ni-related centers located at 695 nm and 793.6 nm were observed in colorless diamond. The NE8 color center at 793.6 nm has more potential for application than the common NV centers. NV⁰ and NV^- optical color centers coexist in diamond without any additives in the synthesis system. Importantly, only the NV^- color center was noticed in diamond with a higher nitrogen concentration, which maximized optimization of the NV^-/NV⁰ ratio in the diamond structure. This study has provided a new way to prepare diamond containing only NV^- optical color centers.     

金刚石大单晶中金属包裹体形态变化的研究

采用高温高压法对含有金属包裹体的金刚石大单晶进行了处理,发现在5.4 GPa的条件下,金属包裹体形态变化的温度区间与金刚石大单晶合成的温度区间具有一致性,约在1500 ～ 1650 K.在1525 ～1625 K这一温度范围内,金属包裹体随着温度的升高,其形态都有向球体变化的趋势,随着处理时间的延长,包裹体形态最终会趋于稳定.不同的温度条件下,包裹体的稳定形态也不同,但包裹体高温下的稳定形态具有一定的不可逆性,同时包裹体的稳定形态也与处理前晶体中包裹体的原始形态有关.红外光谱分析发现,处理前后金刚石中以孤氮为主的氮杂质存在形式未发生改变.     

人工合成金刚石表面三角锥缺陷的存在机理研究

天然金刚石主要生长面为{111},在其表面经常会存在大量凹陷的金字塔状或者底面平整的三角锥蚀坑缺陷,这种缺陷很少出现在人工合成金刚石单晶的表面.本研究在高温高压5.4 GPa、1550 K的条件下,以FeNi合金作为触媒,FeS为添加剂,利用温度梯度法(TGM)直接合成金刚石单晶的{111}表面同样发现有大量凹陷的金字塔状或者底面平整的三角锥蚀坑缺陷.而在体系中加入微量单质B时,高温高压直接合成金刚石单晶的{111}表面不仅存在大量金字塔状的三角锥蚀坑,还出现了天然金刚石表面不曾发现的大量规则的三角凸起平台和凸起的金字塔状或者顶面平整的三角锥缺陷.由此推断,尽管天然金刚石{111}表面经常出现的三角锥缺陷可能是在自然环境中后期腐蚀出现的,而在FeNi-C-FeS体系高温高压直接合成的金刚石单晶{111}表面出现的三角锥缺陷却是在晶体生长过程中直接形成的,FeS在这种表面缺陷的形成过程中起着不可或缺的作用.     

在FeNi-C-FeS-B体系内宝石级金刚石单晶的高温高压合成研究

本研究利用高温高压温度梯度法,在5.4 GPa、1550 K生长条件下,考察了FeNi-C体系中单掺FeS以及FeS-B共掺杂对单晶生长宝石级金刚石品质的影响.结果表明:在单掺FeS体系中,随着FeS的增加,晶体的质量以及透明度逐渐下降,(100)晶面存在的倒方形蚀坑面积逐渐增大,同时晶体的颜色也由黄色转变成灰黑色;在共掺杂体系中,当添加剂FeS含量一定时,随着协同添加剂B的增加,晶体品质呈现出先优化后劣化的变化趋势,晶面上蚀坑的分布逐渐由(100)晶面向(111)转移,晶体颜色也由灰黑色逐渐变浅到黄色、再到B单独发生作用时导致的蓝黑色.XRD光谱分析发现,在FeNi-C-FeS-B体系中出现了某种或者某些不明物质.     

Finite Element Analysis of Convection in Growth Cell for Diamond Growth Using Ni-Based Solvent

Thermal-electricaJ-fluid coupled finite element analyses are performed in the model of the growth cell in a high-pressure and high-temperature （HPHT） cubic apparatus in which the large diamond crystal can be grown by using Ni-based solvent with temperature gradient method （TGM）. The convection in the Ni-based solvent with different thicknesses at 1700-1800 K is simulated by finite element method （FEM）. The experiments of diamond crystal growth are also carried out by using Ni-based solvent at 5.7GPa and 1700-1800K in a China-type cubic high pressure apparatus （CHPA）. The simulation results show that the Rayleigh number in the solvent is enhanced obviously with the increasing solvent thickness. Good quality diamond single crystal cannot be grown if the Rayleigh number in the solvent is too high.