cBN晶体的Raman光谱测量

 用R1000激光共聚焦Raman光谱仪研究了高温高压合成棒中的立方氮化硼（cBN）晶体、原材料六方氮化硼（hBN）和催化剂。Raman光谱测量结果表明：伴随cBN晶体生长的散射峰,出现了两条全新的Raman散射峰（约1.088 cm^-1和约1.368 cm^-1）。该散射峰所对应的物质可能是在高温高压条件下hBN向cBN转变时生成的不完全产物——BN的一种新相。这一结果将有助于进一步讨论cBN的生长机理。     

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.     

Large single crystal diamond grown in FeNiMnCo-S-C system under high pressure and high temperature conditions

Large diamonds have successfully been synthesized from FeNiMnCo-S-C system at temperatures of 1255-1393 ℃and pressures of 5.3-5.5 GPa.Because of the presence of sulfur additive,the morphology and color of the large diamond crystals change obviously.The content and shape of inclusions change with increasing sulfur additive.It is found that the pressure and temperature conditions required for the synthesis decrease to some extent with the increase of S additive,which results in left down of the V-shape region.The Raman spectra show that the introduction of additive sulfur reduces the quality of the large diamond crystals.The x-ray photoelectron spectroscopy(XPS) spectra show the presence of S in the diamonds.Furthermore,the electrical properties of the large diamond crystals are tested by a four-point probe and the Hall effect method.When sulfur in the cell of diamond is up to 4.0 wt.%,the resistance of the diamond is 9.628×10~5 Ω·cm.It is shown that the large single crystal samples are n type semiconductors.This work is helpful for the further research and application of sulfur-doped semiconductor large 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.     

Synergistic influences of titanium,boron, and oxygen on large-size single-crystal diamond growth at high pressure and high temperature

The synergistic influences of boron, oxygen, and titanium on growing large single-crystal diamonds are studied using different concentrations of B₂O₃ in a solvent-carbon system under 5.5 GPa-5.7 GPa and 1300 ℃-1500 ℃. It is found that the boron atoms are difficult to enter into the crystal when boron and oxygen impurities are doped using B₂O₃ without the addition of Ti atoms. However, high boron content is achieved in the doped diamonds that were synthesized with the addition of Ti. Additionally, boron-oxygen complexes are found on the surface of the crystal, and oxygen-related impurities appear in the crystal interior when Ti atoms are added into the FeNi-C system. The results show that the introduction of Ti atoms into the synthesis cavity can effectively control the number of boron atoms and the number of oxygen atoms in the crystal. This has important scientific significance not only for understanding the synergistic influence of boron, oxygen, and titanium atoms on the growth of diamond in the earth, but also for preparing the high-concentration boron or oxygen containing semiconductor diamond technologies.     

国产六面顶压机多晶种法合成宝石级金刚石单晶

对国产六面顶压机平台下使用多晶种法合成宝石级金刚石单晶进行了系统的研究. 通过合理调整温度梯度法的合成腔体组装, 采用多晶种法, 探索多晶种法金刚石合成的压力和温度区间, 在单个合成腔体内放置3–5颗金刚石晶种, 成功合成出多颗(3–5)优质Ib型宝石级金刚石单晶. 多颗晶种的引入, 单次实验合成的多个金刚石晶体晶形及品质一致; 同时, 晶体的整体生长速度也有明显的增大. 多晶种法金刚石单晶合成的研究, 可以有效地利用腔体空间、提高单次金刚石单晶合成的效率, 解决压机大型化下高温高压资源利用率低的问题; 同时, 为宝石级金刚石单晶商业化生产提供重要的依据. 关键词： 金刚石 国产六面顶 多晶种 温度梯度法     

MgO在Mg-hBN体系中对合成cBN晶体的影响

 以金属镁粉为触媒，以六角氮化硼为原料，其中加入适量比例的氧化镁，在国产六面顶压机上，在约5.0 GPa压力、1 500～1 800 K温度条件下，合成出了颜色均匀、晶形完整的黄色立方氮化硼单晶体。实验结果表明，在Mg-hBN体系中，氧化镁对合成cBN晶体的颜色及合成温度有很大的影响。     

高压熔渗生长法制备金刚石聚晶中碳的转化机制研究

在6 GPa和1500 ℃的压力和温度范围内, 利用高压熔渗生长法制备了纯金刚石聚晶, 深入研究了高温高压下金刚石聚晶生长过程中碳的转化机制. 利用光学显微镜、X-射线衍射、场发射扫描电子显微镜检测, 发现在熔渗过程中金刚石层出现了石墨化现象, 在烧结过程中金刚石颗粒表面形貌发生了变化. 根据实验现象分析, 在制备过程中存在三种碳的转化机制: 1)金属熔渗阶段金刚石颗粒表面石墨化产生石墨; 2)产生的石墨在烧结阶段很快转变为填充空隙的金刚石碳; 3)金刚石直接溶解在金属溶液中, 以金刚石形式在颗粒间析出, 填充空隙. 本文研究碳的转化机制为在高温高压金属溶剂法合成金刚石的条件下(6 GPa和1500 ℃的压力和温度范围内)工业批量化制备无添加剂、无空隙的纯金刚石聚晶提供了重要的理论指导.     

籽晶{100}面形状对高温高压合成金刚石大单晶的影响

选用不同形状的{100}金刚石籽晶面,以NiMnCo合金为触媒,利用温度梯度法在压力为5.5 GPa、温度为1260～1300℃的条件下,合成Ib型金刚石大单晶。通过光学显微镜和电子显微镜对晶体的形貌进行表征。研究发现,将合成籽晶的{100}晶面切割成不同形状,只会令晶体的长宽比发生改变,晶体并不会因籽晶形状的改变而偏离{100}晶体的正常形貌。晶体的合成质量受到籽晶长宽比的影响:在籽晶长宽比较小的情况下,晶体的合成质量能够得到保证;但当籽晶长宽比过大时,合成晶体的下表面出现较多缺陷。关于籽晶形状对晶体生长情况影响的研究,揭示了籽晶形状与合成晶体形貌之间的关系,有利于更深入理解晶体的生长过程和外延生长机理,对于今后合成不同形貌的金刚石具有借鉴意义。同时此项研究有助于扩大籽晶的选取范围,降低籽晶的选择难度,提升工业级金刚石的利用率,为合成金刚石大单晶的籽晶选取提供了技术支持。     

Growth of gem-grade nitrogen-doped diamond crystals heavily doped with the addition of Ba（N3）2

Additive Ba(N 3) 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(N 3) 2 display the tensile stress.