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.     

高温高压下氮氢协同掺杂对{100}晶面生长宝石级金刚石的影响

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.     

高温高压下金刚石大单晶研究进展

金刚石具有一系列优于其他材料的极限特性,应用领域十分广泛.金刚石大单晶更能充分发挥其功能特性,从而成为国内外研究的热点.为此,本文在介绍金刚石大单晶高温高压合成原理及工艺技术的基础上,重点综述了四种类型的金刚石大单晶以及掺杂金刚石大单晶的研究现状和研究重点. Ⅰa型金刚石大单晶可由Ⅰb型金刚石通过高温高压退火处理得到,其中氮的转变机制及效率研究十分重要;对Ⅰb型金刚石大单晶的表面分析表征、晶体缺陷控制、再结晶石墨析出、多晶种法批量化生产方面进行了综述;对Ⅱa型金刚石大单晶中除氮剂和触媒的选择、微晶石墨析出与抑制方面的研究进行了介绍;研究了Ⅱb型金刚石中硼元素的扇区存在及其对合成金刚石生长特性的影响;掺杂金刚石大单晶主要从B, N, S, P等不同掺杂元素的不同掺杂源或与硼等协同掺杂的研究状况进行了介绍.并提出金刚石大单晶需要在Ⅰb及Ⅱa型的批量化、Ⅱb型的超导特性、掺杂n型半导体方面加强研究.     

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。     

类天然金刚石的高温高压合成研究

本文利用高温高压(HPHT)法分别合成出普通Ib型、高氮型和高氮含氢型金刚石单晶,然后对金刚石单晶进行高温高压退火处理成功制备出IaA型,IaAB型类天然金刚石大单晶. 详细研究了氮在不同退火温度下的聚集行为,及氢存在情况下C心氮的转化情况. 研究发现高氮型金刚石中氮的聚集行为直接受退火温度的影响,随着退火温度的上升,氮的聚集态转化率升高. 1850 ℃时氮的聚集态转化率达到100%,晶体颜色几乎为无色,红外吸收谱与天然IaA型钻石基本无差别. 氢的存在有利于氮原子从C心聚集到A心和B心. 退火高氮含氢晶体得到可与天然金刚石相媲美的IaAB型类天然金刚石. 此外,我们在较低压力2.5 GPa下对Ib型金刚石退火成功制备出IaA型金刚石.     

B2O3添加宝石级金刚石单晶的生长特性

利用温度梯度法, 在5.3-5.7 GPa压力、1200-1600 ℃的温度条件下, 将B₂O₃粉添加到FeNiMnCo+C合成体系内, 进行B₂O₃添加宝石级金刚石单晶的合成. 研究得到了FeNiMnCo触媒生长B₂O₃添加宝石级金刚石单晶的相图分布规律. 结果表明B₂O₃添加会使晶体生长的“V”形区上移和低温六面体单晶生长区间变宽. 通过晶体生长实验, 研究合成了不同形貌的B₂O₃添加宝石级金刚石单晶. 研究同时证实, B₂O₃的过量添加会对宝石级金刚石单晶生长带来不利影响. 当B₂O₃的添加量高于约3 wt‰、生长时间超过20 h时, 很难实现优质B₂O₃添加宝石级金刚石单晶的生长. 但B₂O₃的适量添加(不超过1 wt‰), 有助于提高低温板状六面体宝石级金刚石单晶的成品率. 通过对晶体生长速度的研究发现, B₂O₃的添加使得优质晶体的生长速度明显降低, 随着晶体生长时间的延长, B₂O₃添加剂对晶体生长的抑制作用会越发明显. 扫描电镜测试结果表明, 合成体系内B₂O₃添加剂的引入, 导致晶体表面的平整度明显下降.     

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     

温度梯度法宝石级金刚石的合成及表征

利用温度梯度法,在5．0—5．7GPa,1250---1600℃条件下,研究了FeNiMnCo触媒合成宝石级金刚石的温度和压力区间,给出了P-T相图．基于有限元法的温度场模拟及碳素浓度梯度拟合结果表明,I型温度场只适合生长大尺寸优质板状及小尺寸塔状金刚石单晶;II型温度场可以合成出大尺寸优质板状或塔状金刚石单晶．该结论被Ib型及掺硼宝石级金刚石晶体生长实验所证实．提出碳素浓度梯度是决定晶体生长速度及合成晶体品质的关键因素．研究得到了只有触媒中温度场分布与晶体尺寸、形貌相匹配时,才能合成出优质宝石级金刚石单晶的晶体生长规律．揭示了{110},和{113}高指数晶面在Ib型金刚石“V”形区内的分布规律．通过傅里叶红外光谱检测发现,FeNiMnCo触媒合成金刚石的氮含量较低,较低的氮含量是由铁会降低金刚石氮含量所致．氮含量低有利于金刚石的光谱透过性．     

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.     

高温高压金刚石单晶生长界面的研究

 利用扫描电镜及Auger电子谱技术研究了高温高压下金刚石单晶生长界面的特性，观察到了金刚石单晶表面及金属膜表面的沟槽结构及金刚石-金属、金属-石墨两个主界面间的过渡层结构及界面间C原子电子组态的变化。     

Synthesis and characterization of a single diamond crystal with a high nitrogen concentration

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 P₃N₅additive 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 P₃N₅additive 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.     

Synthesis and characterization of a single diamond crystal with a high nitrogen concentration

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.     

Effects of additive NaN_3 on the HPHT synthesis of large single crystal diamond grown by TGM

In this paper,large single crystal diamond with perfect shape and high nitrogen concentration approximately 1671-1742 ppm was successfully synthesized by temperature gradient method (TGM) under high pressure and high temperature (HPHT).The HPHT synthesis conditions were about 5.5 GPa and 1500-1550 K.Sodium azide (NaN3) with different amount was added as the source of nitrogen into the synthesis system of high pure graphite and kovar alloy.The effects of additive NaN3 on crystal growth habit were investigated in detail.The crystal morphology,nitrogen concentration and existing form in synthetic diamond were characterized by means of scanning electron microscope (SEM) and infrared (IR) absorption spectra,respectively.The results show that with an increase of the content of NaN3 added in the synthesis system,the region of synthesis temperature for high-quality diamond becomes narrow,and crystal growth rate is restricted,whereas the nitrogen concentration in synthetic diamond increases.Nitrogen exists in diamond mainly in dispersed form (C-centers) and partially aggregated form (A-centers).The defects occur more frequently on crystal surface when excessive NaN3 is added in the synthesis system.     

Formation and crystal structure of metallic inclusions in a HPHT as-grown diamond single crystal

One of the most important characteristics associated with crystal growth technology is the entrapment of inclusions by the growing crystal. Diamond single crystals prepared under high temperature-high pressure (HPHT) usually contain metallic inclusions. In the present paper, metallic inclusions in a diamond grown from a Fe-Ni-C system using the HPHT method have been, for the first time, systematically examined by transmission electron microscopy (TEM). Energy dispersive X-ray spectrometry (EDS) , combined with selected area electron diffraction (SAD) patterns, has been used to identify the chemical composition and crystal structure of the metallic inclusions. The metallic inclusions were found to be composed mainly of cubic γ-(FeNi), face-centered cubic (FeNi)₂₃C₆, ortho-rhombic Fe₃C and hexagonal Ni₃C, which may have been formed through the entrapment of molten catalyst by the growth front or through reaction of the trapped melt with contaminants in the diamond. Received: 19 June 2000 / Accepted: 21 June 2000 / Published online: 16 August 2000     

硼氢协同掺杂Ib型金刚石大单晶的高温高压合成与电学性能研究

在压力6.0 GPa和温度1600 K条件下, 利用温度梯度法研究了(111)晶面硼氢协同掺杂Ib型金刚石的合成. 傅里叶红外光谱测试表明: 氢以sp³杂化的形式存在于所合成的金刚石中, 其对应的红外特征吸收峰位分别位于2850 cm^-1和2920 cm^-1处. 此外, 霍尔效应测试结果表明: 所合成的硼氢协同掺杂金刚石具有p型半导体材料特性. 相对于硼掺杂金刚石而言, 由于氢的引入导致硼氢协同掺杂金刚石电导率显著提高. 为了揭示硼氢协同掺杂金刚石电导率提高的原因, 对不同体系进行了第一性原理理论计算, 计算结果表明其与实验结果符合. 该研究对金刚石在半导体领域的应用有重要的现实意义.     

掺氮金刚石的光学吸收与氮杂质含量的分析研究

研究了金刚石光学特性与氮杂质及其含量的关系,从传统的金刚石氮含量标定方法出发,修正了金刚石氮含量的计算方法,并且用添加叠氮化钠的原料在六面顶压机上进行了高氮含量金刚石的制备研究.随着体系中叠氮化钠的添加,金刚石红外吸收谱在800—1400 cm^-1范围的吸收强度相对于基线不断升高,这表明金刚石中存在的氮含量在随着叠氮化钠添加而升高,金刚石在单声子区域吸收强度大大增强.用含叠氮化钠的原料制备的金刚石呈现绿色、墨绿色甚至黑色,颜色的深浅依赖于叠氮化钠添加的多少.傅里叶红外光谱测试结果表明 关键词： 金刚石 光学材料 杂质 红外     

高长径比柱状金刚石的高温高压合成与机理研究

为了拓展金刚石的种类和解决金刚石工具使用过程中因把持力不足造成的使用寿命降低等, 在中国式六面顶压机上, 通过对FeNi触媒成分和工艺的优化, 成功合成出高质量长径比大于2.5, 平均粒度在0.8—1.0 mm的柱状金刚石晶体. 该晶体独特的形貌, 将极大改善金刚石工具的在使用过程中出现的"脱粒"现象. 另外, 实验中发现, 柱状金刚石晶体的生长速度也远大于传统晶体的生长速度. 采用扫描电镜(SEM)和能谱(EDS)等手段对柱状金刚石晶体及晶体周围触媒成分进行了表征; 结果表明, 柱状金刚石晶体在生长过程中存在{100}和{111}晶面拉长, 以及包覆在晶体周围的触媒成分偏析. 在此基础上, 阐明了柱状晶体生长机理.     

Evolution of nitrogen structure in N-doped diamond crystal after high pressure and high temperature annealing treatment

In this paper, we have reported an investigation on the evolution of nitrogen structures in diamond crystals which contain nitrogen donor atoms in the range of 1500 ppm-1600 ppm following an annealing treatment at a high pressure of about 6.5 GPa and high temperatures of 1920 K-2120 K. The annealing treatment was found to completely transform nitrogen atoms originally arranged in a single substitutional form （C-center）, into a pair form （A-center）, indicated from infrared （IR） spectra. The photoluminescence （PL） spectra revealed that a small fraction of nitrogen atoms remained in C-center form, while some nitrogen atoms in A-center form were further transformed into N3 and H3 center structures. In addition, PL spectra have revealed the existence of two newly observed nitrogen-related structures with zero phonon lines at 611 nm and 711 nm. All these findings above are very helpful in understanding the formation mechanism of natural diamond stones of the Ia-type, which contains nitrogen atoms in an aggregated form.     

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.     

Shape-controlled synthesis of diamond crystal by epitaxial growth under high pressure and high temperature conditions

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.