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.     

高温高压下掺硼宝石级金刚石单晶生长特性的研究

本文在5.1—5.6 GPa,1230—1600℃的压力、温度条件下,以FeNiMnCo作为触媒,进行单质硼添加宝石级金刚石单晶的生长研究.借助于有限元法,对触媒内的温度场进行模拟.研究得到了FeNiMnCo-C-B体系下,金刚石单晶生长的P-T相图.该体系下合成金刚石单晶的最低压力、温度条件分别为5.1 GPa,1230℃左右.研究发现,在单晶同一{111}扇区内部,硼元素呈内多外少的分布规律.有限元模拟结果给出,该分布规律是由在晶体生长过程中,{111}扇区的增长速度逐渐减小所致.{111}晶向的晶体生长实验结果表明,硼元素优先从{111}次扇区进入晶体.研究发现,这是该扇区增长速度相对较快,硼元素扩散逃离可用时间短导致的.另外,同磨料级掺硼金刚石单晶生长相比,对于温度梯度法生长掺硼宝石级金刚石单晶,由于晶体的增厚速度较慢,即使硼添加量相对较高,也可以实现表面无凹坑缺陷的优质金刚石单晶的生长.     

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.     

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.     

碳酸钙掺杂对Ⅰb型金刚石沿不同晶面生长行为的影响

作为天然金刚石生长环境的碳酸盐,研究其掺杂对人造金刚石晶体生长行为的影响具有重要的学术价值。本文运用高温高压下的温度梯度法,将碳酸钙(CaCO₃)按照不同比例掺杂到金刚石合成腔体内的碳源中,用以研究其掺杂对金刚石分别沿(100)或(111)晶面生长行为的影响。利用光学显微成像对掺杂合成金刚石晶体形貌的表征表明:随着碳酸钙掺量的增加,沿(100)面生长的金刚石晶形由塔状变为板状且出现了裂晶、连晶现象,晶体颜色先变浅再变黑,内部出现了包裹体;同样,沿(111)面生长的金刚石晶形由板状逐渐变为塔状且出现了裂晶、孪晶现象,晶体颜色逐渐变黑,内部包裹体增多。用激光拉曼光谱对掺杂金刚石晶体质量的表征表明:随着碳酸钙掺量的增加,沿(100)或(111)面生长的掺杂金刚石的拉曼峰位偏移量均增大,半峰全宽均变大。这说明碳酸钙掺杂使得金刚石晶格畸变增加、内应力变大。本文对碳酸钙掺杂影响沿两不同面生长金刚石的晶形、颜色、内部质量等行为的成因进行了分析,为本课题后续研究奠定了基础。     

立方氮化硼体积分数对颗粒增强铝基复合材料性能的影响

在高压条件下制备了具有高致密性的立方氮化硼(c-BN)颗粒增强铝基复合材料,研究了颗粒增强相c-BN的体积分数对铝基复合材料性能的影响.对c-BN颗粒增强铝基复合材料的致密性、组分、布氏硬度以及热导率等方面的影响进行了表征.研究结果表明:使用高压的方法可以有效降低基体与增强相反应生成的新相、提高材料的致密性和样品洁净度,样品的相对密度在96.3;～98.5;之间;随着c-BN体积分数的增加,复合材料的硬度逐渐增大,布氏硬度在32.4～78.2 HB之间;热导率在191.5～198.5 W/(m·K)之间,高体积分数c-BN铝基复合材料的热导率高于低体积分数的热导率.高压方法为复合材料的制备提供了新手段和思路.     

热电材料PbTe1-xSex的高压制备及电学性能研究

 利用高温高压技术,制备了热电材料PbTe和PbSe的固溶体合金PbTe_1-xSe_x,在室温下对其结构及电学性质进行了研究。X射线衍射（XRD）测试结果表明：PbTe_1-xSe_x具有NaCl结构;晶格常数随着Se含量（x）的增加而减小;PbTe_1-xSe_x的电阻率和Seebeck系数的绝对值随x的增大而减小;功率因子随x的增大先增大而后减小,当x=0.1时功率因子最高,达到21.7 μW/(cm·K²),比相同条件下制备的PbTe高20%。     

不同类型宝石级金刚石生长过程中石墨的不同析出形式

在压力5.3 GPa、温度1603 K的FeNiCo(wt; 55∶ 29∶ 16)触媒中沿{111}面合成Ⅰb型及Ⅱa型宝石级金刚石过程中金刚石周围分别伴随有片状及粉末状石墨析出.这两种不同形态的石墨均会对金刚石生长产生不利影响.对这两种石墨进行XRD和SEM测试分析表明:生长Ⅰb型和Ⅱa型金刚石时所析出的石墨分别为再结晶石墨和微晶石墨.本文分析了这两种石墨析出原因的异同点.     

HPHT Synthesis of Different Shape Coarse-Grain Diamond Single Crystals

Synthesis of coarse-grain diamond crystals is studied in a China-type SPD6× 1670T cubic high-pressure apparatus with high exact control system. To synthesize high quality coarse-grain diamond crystals, advanced indirect heat assembly, powder catalyst technology and optimized synthesis craft are used. At last, three kinds of coarse- grain diamond （about 0.85 mm） single crystals with hexahedron, hex-octahedron and octahedron are synthesized successfully under HPHT （about 5.4 GPa, 1300-1450℃）. The growth characters of different shape crystals are discussed. The results and techniques might be useful for the production of coarse-grain diamonds.     

Synthesis of large diamond crystals containing high-nitrogen concentration at high pressure and high temperature using Ni-based solvent by temperature gradient method

This paper reprots that with Ni-based catalyst/solvent and with a dopant of NaN 3,large green single crystal diamonds with perfect shape are successfully synthesized by temperature gradient method under high pressure and high temperature in a China-type cubic anvil high-pressure apparatus (SPD-6×1200),and the highest nitrogen concentration reaches approximately 1214-1257 ppm calculated by infrared absorption spectra.The synthesis conditions are about 5.5 GPa and 1240-1300 C.The growth behaviour of diamond with high-nitrogen concentration is investigated in detail.The results show that,with increasing the content of NaN 3 added in synthesis system,the width of synthesis temperature region for growth high-quality diamonds becomes narrower,and the morphology of diamond crystal is changed from cube-octahedral to octahedral at same temperature and pressure,the crystal growth rate is slowed down,nevertheless,the nitrogen concentration doped in synthetic diamond increases.