合成腔体尺寸对Ib型六面体金刚石单晶生长的影响

利用液压缸直径为550 mm的大缸径六面顶压机, 在5.6 GPa, 1200-1400 ℃的高压高温条件下, 分别采用单晶种法和多晶种法, 开展了Ib型六面体宝石级金刚石单晶的生长研究, 系统考察了合成腔体尺寸对Ib型六面体金刚石大单晶生长的影响. 首先, 阐述了合成腔体尺寸对合成设备油压传递效率的影响, 研究得到了设备油压与腔体内实际压力的关系曲线; 其次, 选择尺寸为Φ 14 mm的合成腔体, 分别采用单晶种法和多晶种法(5颗晶种), 进行Ib型六面体金刚石大单晶的生长实验, 研究阐述了Φ 14 mm合成腔体的晶体生长实验规律; 再次, 为了解决液压缸直径与合成腔体尺寸不匹配的问题, 将合成腔体尺寸扩大到26 mm, 并开展了多晶种法六面体金刚石大单晶的生长研究, 最多单次生长出14 颗优质3 mm级Ib型六面体金刚石单晶, 研究得到了Φ 26 mm合成腔体生长3 mm级Ib型六面体金刚石单晶的实验规律, 并就两种腔体合成金刚石单晶的总体生长速度与生长时间的关系进行了讨论; 最后, 借助于拉曼光谱, 将合成的优质六面体金刚石单晶与天然金刚石单晶进行对比测试, 对所合成晶体的结构及品质进行了表征.     

降温工艺对宝石级金刚石单晶品质的影响

在国产六面顶压机上,采用温度梯度法,在5.6 GPa,1200—1400?C的高压高温条件下,裂晶问题频繁出现的合成周期内,围绕裂晶现象开展了Ib型宝石级金刚石单晶的生长研究,系统考察了降温工艺对宝石级金刚石单晶品质的影响.针对宝石级金刚石单晶常见的裂纹缺陷,借助于扫描电子显微镜,分别对优质金刚石单晶和存在裂纹金刚石单晶的表面形貌进行了表征;利用微区傅里叶转换红外光谱测试手段,对上述两类晶体的N杂质含量分别进行了测试,依据测试结果,对裂晶出现的原因进行了分析;分别采用传统断电降温和缓慢降温工艺,考察了晶体生长结束后的降温工艺对宝石级金刚石单晶品质的影响.结果表明,缓慢降温工艺在很大程度上可以有效抑制裂晶问题出现.另外,从宝石级金刚石单晶品质和单晶受到的外应力两个方面着手,分别对裂晶出现的机理和采用缓慢降温工艺有效解决裂晶问题的机理进行了讨论.     

高氮含量宝石级金刚石单晶的高温高压合成

氮是金刚石（包括天然金刚石和人工合成金刚石）中最普遍的杂质,长期以来广受研究者的关注. 人工合成出类似天然金刚石的具有较高氮含量的金刚石晶体是极富挑战性的研究课题. 本工作通过在合金溶剂和石墨碳源中添加含氮物质,利用温度梯度法在国产六面顶高压设备上合成出了系列大尺寸、高氮含量的宝石级金刚石单晶. 借助显微红外光谱,对合成的金刚石晶体中的氮含量进行了测定. 研究发现随着含氮物质添加量的提高晶体中氮含量基本呈线性增加. 最终合成出了氮含量高达1707 ppm的毫米级高氮含量金刚石单晶,以及最大尺寸达3.5 mm,氮含量达1520 ppm的绿色高氮宝石级金刚石单晶.     

籽晶尺寸对宝石级金刚石单晶生长的影响

本文在国产六面顶压机上,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用边长0.8, 1.5和2.2 mm三种尺寸的籽晶,系统开展了Ib型宝石级金刚石单晶的生长研究.文中系统考察了籽晶尺寸对宝石级金刚石单晶生长的影响.首先,考察了籽晶尺寸变化对宝石级金刚石单晶裂晶问题带来的影响.研究得到了籽晶尺寸变大,裂晶出现概率增加的晶体生长规律.其次,在25 h的生长时间内,考察了上述三种尺寸籽晶生长金刚石单晶时,生长时间与单晶极限生长速度的关系.得到了选用大尺寸籽晶,可以提高优质单晶合成效率、降低合成成本的研究结论.借助扫描电子显微镜和光学显微镜,对三种尺寸籽晶生长金刚石单晶的表面形貌进行了标定.最后,傅里叶微区红外测试,对三种尺寸籽晶生长宝石级金刚石单晶的N杂质含量进行了表征.研究得到了选用大尺寸籽晶实现快速生长金刚石的同时,晶体的N杂质含量会随之升高的晶体生长规律.     

复合型多晶金刚石末级压砧的制备并标定六面顶压机6-8型压腔压力至35GPa

通过分析二级6-8型大腔体静高压装置八面体压腔的受力状况, 研制了一种使用成本低、尺寸大且易于加工的多晶金刚石-硬质合金复合二级(末级)顶锤(压砧). 采用原位电阻测量观测Zr在高压下相变(α-ω, 7.96 GPa; ω-β, 34.5 GPa)的方法, 标定了由多晶金刚石-硬质合金复合末级压砧构建的5.5/1.5(传压介质边长/二级顶锤锤面边长, 单位: mm)组装的腔体压力. 实验表明, 自行研制的多晶金刚石-硬质合金复合末级压砧可使基于国产六面顶压机构架的二级加压系统的压力产生上限从约20 GPa提高到35 GPa以上, 拓展了国内大腔体静高压技术的压力产生范围. 应用这一技术, 我们期望经过末级压砧材料与压腔设计的进一步优化, 在基于国产六面顶压机的二级6-8 型大腔体静高压装置压腔中产生超过50 GPa的高压. 关键词： 二级6-8型大腔体静高压装置 多晶金刚石-硬质合金复合末级压砧 压力标定     

基于有限元法分析宝石级金刚石的合成腔体温度场

以有限元法为理论分析手段模拟分析了温度梯度法合成宝石级金刚石大单晶的腔体温度场,实现了对宝石级金刚石的合成腔体内各位置温度同时测量.模拟结果表明:在宝石级金刚石合成过程中,其温度分布呈不均匀分布.腔体内高温区分布在样品(碳源+触媒)边缘,低温区分布在籽晶附近.样品腔内热量的传递方式和样品腔内的碳源输运方式相同,均由碳源的两侧向籽晶附近传输.籽晶附近轴向温度梯度大于径向温度梯度,导致单位时间内其轴向生长尺寸大于径向生长尺寸.宝石级金刚石腔体温度场分析的理论模型的成功构建,为新型宝石级金刚石腔体的研制提供了良好的设计基础,对促进优质宝石级金刚石的生长技术具有指导意义.     

基于国产铰链式六面顶压机的大腔体静高压技术研究进展

大腔体压机技术因具有静水压性好、样品尺寸大、样品腔内压力与温度分布均匀,且可与同步辐射X射线、中子衍射、超声测量等技术结合对样品进行原位测量等优点,越来越受到高压领域科研工作者的青睐。国内大腔体压机技术多基于国产铰链式六面顶压机构架,国产六面顶压机常规一级压腔所能产生的压力极限较低,约为6GPa,在一定程度上制约了国内高压科学及相关学科的发展。近几年,基于国产六面顶压机,设计了两种一级压腔增压系统,集成了6-8型二级压腔加压装置。目前,在提供厘米量级样品的前提下,设计的两种一级压腔所能达到的最高压力约为10GPa;若采用硬质合金二级顶锤,设计的6-8型二级压腔所能达到的最高压力约为20GPa。最近,自行设计并制备了可产生高于50GPa压力的多晶金刚石二级顶锤,采用此种顶锤将基于国产六面顶压机构建的二级加压系统的压力标定至35GPa,拓展了国内大腔体静高压技术的压力产生范围。     

高温高压法人造金刚石合成中工艺曲线的确定

以SPD6×2000型六面顶压机为合成设备,在高温高压条件下确定了合成金刚石的最低成核压力.采用合理的二次升压工艺方法,在暂停油压86MPa,生长油压94MPa,合成功率3500W的条件下成功地减少了劣晶的生成,合成出了晶型完整、表面平整的优质金刚石单晶.结果表明在最低成核压力点下对石墨进行再结晶的处理对合成高品级金刚石是完全必要的.     

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.     

应用于高压科学研究的国产铰链式六面顶压机技术发展历程

国产铰链式六面顶压机是我国独立发展起来的大腔体高压装置,经过50多年的不断发展,在工业高压合成和高压科学研究领域取得了丰硕成果,在国际上占据一席之地。本文仅以四川大学高压科学与技术实验室在国产铰链式六面顶压机应用于高压科学研究的技术研发为镜,展示国产铰链式六面顶压机大腔体高压装置在应用于高压科学研究领域的发展历程和技术特点,以利于该装置在今后的研发过程中继续保持和发挥其独特性能,为我国工业高压合成和高压科学研究发挥更大的作用。     

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.     

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.     

FeMn粉末触媒对合成金刚石的影响

 利用FeMn粉末触媒在国产六面顶压机上进行了合成金刚石单晶的实验,研究了高温高压条件下（5.7 GPa、1 550 ℃）,石墨-FeMn粉末触媒体系中金刚石单晶的生长特性。通过光学成像显微镜观测表明：合成出的金刚石单晶呈浅黄色,晶形完整,且都是八面体,晶体里含有白色物质,粒度集中在0.3~0.5 mm;通过扫描电镜观测了晶体的表面形貌,表面有熔坑;通过穆斯堡尔谱,发现粉末触媒里主要是FeMn合金和独立状态的Fe,金刚石内部主要是Fe和Fe₃C;利用X射线荧光光谱,检测出样品里有Fe和Mn元素。     

Effect of Carbon Source with Different Graphitization Degrees on the Synthesis of Diamond

Using three kinds of graphites with different graphitization degrees as carbon source and Fe-Ni alloy powder as catalyst, the synthesis of diamond crystals is performed in a cubic anvil high-pressure and high-temperature apparatus （SPD-6 × 1200）. Diamond crystals with perfect hexoctahedron shape are successfully synthesized at pressure from 5.0 to 5.5GPa and at temperature from 1570 to 1770K. The synthetic conditions, nucleation, morphology, inclusion and granularity of diamond crystals are studied. The temperature and pressure increase with the increase of the graphitization degree of graphite. The quantity of nucleation and granularity ofdiamonds decreases with the increase of graphitization degree of graphite under the same synthesis conditions. Moreover, according to the results of the M6ssbauer spectrum, the composition of inclusions is mainly Fe3 C and Fe-Ni alloy phases in diamond crystals synthesized with three kinds of graphites.     

用表面生长CVD金刚石的石墨合成高压金刚石

 用热灯丝CVD方法在多晶石墨衬底表面制备CVD金刚石颗粒，并用这种石墨在高温高压条件下采用六面顶压机合成出高压金刚石。初步实验结果表明：采用其表面生长CVD金刚石颗粒的石墨合成高压金刚石，可以提高金刚石的转化率和降低合成压力。     

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.     

FEM study on a double-beveled anvil and its application to synthetic diamonds

A new double-beveled anvil for the synthesis of high-quality diamonds has been described, which is used in a China-type large-volume, cubic-anvil, high-pressure apparatus (LV-CHPA, SPD-6X2000). Our results indicate that the pressure generation of a double-beveled anvil is more efficient than that of a single-beveled anvil. To gain the same cell pressure (5.5 GPa), the oil pressure of LV-CHPA using double-beveled anvils decreased by about 10%, compared to using single-beveled anvils. Furthermore, a double-beveled anvil can pressurize a cubic cell of 36 mm³ up to about 6.0 GPa, and simultaneously can increase the temperature up to 1360°C for routine operation. This provides considerable advantages to the synthesis of high-quality diamonds under ultra-high-pressure conditions with the same hydraulic rams.     

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 Al and Ti/Cu on Synthesis of Type-IIa Diamond Crystals in Ni70Mn25Co5-C System at HPHT

High-quality type-Ⅱa gem diamond crystals are successfully synthesized in a NiToMn25Co5-C system by temperature gradient method （TGM） at about 5.5 GPa and 1560 K. Al and Ti/Cu are used as nitrogen getters respectively. While nitrogen getter Al or Ti/Cu is added into the synthesis system, some inclusions and caves tend to be introduced into the crystals. When Al is added into the solvent alloy, we would hardly gain high-quality type-Ⅱa diamond crystals with nitrogen concentration Nc 〈 1 ppm because of the reversible reaction of Al and N at high pressure and high temperature （HPHT）. Piowever, when Ti/Cu is added into the solvent alloy, high-quality type-Ⅱa diamond crystals with Nc 〈 1 ppm can be grown by decreasing the growth rate of diamonds.