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.     

Monte Carlo studies on the burnup measurement for the high temperature gas cooling reactor

Online fuel pebble burnup measurement in a future high temperature gas cooling reactor is proposed for implementation through a high purity germanimn （HPGe） gamma spectrometer. By using KORIGEN software and MCNP Monte Carlo simulations, the single pebble gamma radiations to be recorded in the detector are simulated under different, irradiation histories. A specially developed algorithm is applied to analyze the generated spectra to reconstruct the gamma activity of the ~arCs monitoring nuclide. It is demonstrated that by taking into account the intense interfering peaks, the 137Cs activity in the spent pebbles can be derived with a standard deviation of 3.0% （l（r）. The results support the feasibility of utilizing the HPGe spectrometry in the online determination of the pebble burimp in future modular pebble bed reactors.     

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.     

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.     

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.     

高温高压下草酸脱羧反应中的拉曼光谱研究

应用水热金刚石压腔结合拉曼光谱技术研究了高温高压下草酸溶液的热稳定,使用拉曼光谱对其脱羧反应及产物进行监测。结果表明低温升温过程中,草酸的拉曼谱图中各个特征振动峰没有发生变化,随着温度的继续升高,其特征振动峰逐渐变弱。达到一定温度后,羧基的拉曼特征峰消失,草酸发生脱羧反应:C2H2O4—2CO2+H2生成CO2和H2。高温高压下草酸发生热分解的温度压力之间呈线性关系,其线性回归方程为P(MPa)=12.839 T(K)-5 953.7,R2=0.99。草酸脱羧反应的摩尔体积变化与温度压力的关系为ΔV(cm-3.mol-1)=16.69-0.002P(MPa)+0.005 2T(K),R2=0.99。     

Growth and annealing study of hydrogen-doped single diamond crystals under high pressure and high temperature

A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.     

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.     

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.     

硼硫协同掺杂金刚石的高压合成与电学性能研究

FeNiMnCo-C体系中,在压力6.5 GPa、温度1280—1300℃的极端物理条件下,采用温度梯度法成功合成了硼(B)、硫(S)协同掺杂金刚石大单晶.通过傅里叶红外光谱测试对高温高压所制备金刚石中的杂质进行了表征.借助霍尔效应对典型金刚石样品的电输运性能进行了测试,测试结果表明:硼硫协同掺杂有利于提高p型金刚石的电导率,而且硼硫在合成体系中的添加比例可以决定金刚石的p, n特性.此外,第一性原理计算结果表明,合成体系中不同比例的硼硫协同掺杂对金刚石的p, n特性以及电导率有着直接的影响,计算结果与实验测试结果相吻合.     

Influence of annealing treatment on as-grown Ib-type diamond crystal at a high temperature and high pressure

In this paper,we report on the influence of annealing treatment on as-grown Ib-type diamond crystal under high pressure and high temperature in a china-type cubic anvil high-pressure apparatus.Experiments are carried out at a pressure of 7.0 GPa and temperatures ranging from 1700 C to 1900 C for 1 h.Annealing treatment of the diamond crystal shows that the aggregation rate constant of nitrogen atoms in the as-grown Ib-type diamond crystal strongly depends on diamond morphology and annealing temperature.The aggregation rate constant of nitrogen remarkably increases with the increase of annealing temperature and its value in octahedral diamond is much higher than that in cubic diamond annealed at the same temperature.The colour of octahedral diamond crystal is obviously reduced from yellow to nearly colorless after annealing treatment for 1 h at 1900 C,which is induced by nitrogen aggregation in a diamond lattice.The extent of nitrogen aggregation in an annealed diamond could approach approximately 98% indicated from the infrared absorption spectra.The micro-Raman spectrum reveals that the annealing treatment can improve the crystalline quality of Ib-type diamond characterized by a half width at full maximum at first order Raman peak,and therefore the annealed diamond crystals exhibit nearly the same properties as the natural IaA-type diamond stones of high quality in the Raman measurements.     

Hardness of materials at high temperature and high pressure

The intrinsic character of the correlation between hardness and thermodynamic properties of solids has been established. The proposed thermodynamic model of hardness allows one to easily estimate hardness and bulk moduli of known or even hypothetical solids from the data on Gibbs energy of atomization of the elements or on the enthalpy at the melting point. The correctness of this approach is illustrated by an example of the recently synthesized superhard diamond-like BC₅ and orthorhombic modification of boron, γ-B₂₈. The pressure and/or temperature dependences of hardness were calculated for a number of hard and superhard phases, i.e. diamond, cBN, B₆O, B₄C, SiC, Al₂O₃, β-B₂O₃ and β-rh boron. Excellent agreement between experimental and calculated values is observed for temperature dependences of Vickers and Knoop hardness. In addition, the model predicts that some materials can become harder than diamond at pressures in the megabar range.     

Synthesis of N-type semiconductor diamonds with sulfur,boron co-doping in FeNiMnCo-C system at high pressure and high temperature

A series of diamonds with boron and sulfur co-doping were synthesized in the Fe Ni Mn Co-C system by temperature gradient growth(TGG) under high pressure and high temperature(HPHT). Because of differences in additives, the resulting diamond crystals were colorless, blue-black, or yellow. Their morphologies were slab, tower, or minaret-like. Analysis of the x-ray photoelectron spectra(XPS) of these diamonds shows the presence of B, S, and N in samples from which N was not eliminated. But only the B dopant was assuredly incorporated in the samples from which N was eliminated. Resistivity and Hall mobility were 8.510 ?·cm and 760.870 cm~2/V·s, respectively, for a P-type diamond sample from which nitrogen was eliminated. Correspondingly, resistivity and Hall mobility were 4.211×10~5 ?·cm and 76.300 cm~2/V·s for an N-type diamond sample from which nitrogen was not eliminated. Large N-type diamonds of type Ib with B–S doping were acquired.     

The baddeleyite-type high pressure phase of Ca(OH)2

Abstract

A phase transition from Ca(OH)₂ I (portlandite) to Ca(OH)₂ II at high pressure and temperature has been confirmed, using in situ x-ray diffraction in a multianvil high pressure device (DIA). The structure was determined at 9.5 GPa and room temperature from data collected after heating the sample at 300°C at 7.2 GPa in a diamond anvil cell. Both the Le Bail fit and preliminary Rietveld refinement suggest that the new phase, which reverts to Ca(OH), I during pressure release, has a structure related to that of baddeleyite (ZrO₁); it is monoclinic (P2₁/c) with a= 4.887(2), b= 5.834(2), c = 5.587(2), β = 99.74(2)°. The coordination number of Ca increases from six to seven (5 + 2) across the transition. At 500°C, the phase boundary is bracketed at 5.7 ± 0.4 GPa by reversal experiments performed in the DIA.     

高温高压下方解石相转变的拉曼光谱原位实验研究

用热液金刚石压腔装置结合拉曼光谱技术研究了高温高压下方解石的相变过程及拉曼光谱特征。结果表明:常温条件下,体系压力增至1 666和2 127 MPa时,方解石的拉曼特征峰155cm-1消失,1 087cm-1峰分裂为1 083和1 090cm-1两个谱峰、282cm-1峰突然降至231cm-1,证明其转变为方解石-Ⅱ和方解石-Ⅲ。在起始压力为2 761MPa和低于171℃的升温过程中,方解石-Ⅲ的拉曼散射的各个特征振动峰没有变化。当温度达到171℃,方解石晶体完全变成不透明状,其对称伸缩振动峰1 087cm-1、面内弯曲振动峰713cm-1和晶格振动峰155和282cm-1均发生突变,说明方解石-Ⅲ相变生成一种碳酸钙新相。体系降至常温,该新相一直保持稳定不变,表明高温高压下方解石向碳酸钙新相的转变过程是不可逆的。方解石-Ⅲ与碳酸钙新相之间的相变线方程为P(MPa)=9.09.T(℃)+1 880。碳酸钙新相的对称伸缩振动峰(ν1 087)随压力、温度的变化率分别为dν/dP=5.1(cm-1.GPa-1),dν/dT=-0.055 3(cm-1.℃-1)。     

Effects of Mg on diamond growth and properties in Fe–C system under high pressure and high temperature condition

Diamond crystal crystallized in Fe–Mg–C system with Archimedes buoyancy as a driving force is established under high pressure and high temperature conditions. The experimental results indicate that the addition of the Mg element results in the nitrogen concentration increasing from 87 ppm to 271 ppm in the diamond structure. The occurrence of the {100}plane reveals that the surface character is remarkably changed due to the addition of Mg. Micro-Raman spectra indicate that the half width of full maximum is in a range of 3.01 cm~(-1)–3.26 cm~(-1), implying an extremely good quality of diamond specimens in crystallization.     

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.     

Study on High-Temperature Spectra of Asymptotic Asymmetric-Top Molecule O3

The line intensities of 001-000 transition of the asymptotic asymmetric-top Oa molecule at several temperatures are calculated by directly calculating the partition functions and regarding the rotationless transition dipole moment squared as a constant. The calculated values of the total internM partition sums （TIPS） are consistent with the data of HITRAN database with -0.61% at 296 K. The calculated line intensity data at 500 K and 3000 K are also in excellent agreement with the data in HITRAN database with less than 0.659% and 5.458% at 500 K and 3000 K, which provide a strong support for the calculations of partition function and fine intensity at high temperature. Then we extend the calculation to higher temperatures. The line intensities and simulated spectra of v3 band of the asymptotic asymmetric-top O3 molecule at 4000 and 5000 K are reported. The results are of significance for the studying of the molecular high-temperature spectrum including experimental measurements and theoretical calculations.     

Ruby fluorescence lifetime measurements for temperature determinations at high (p,T)

The lifetime of the ruby R₁ fluorescence line was measured as a function of pressure (up to about 20 GPa) and temperature (550 K) in an externally heated diamond anvil cell (DAC). At constant temperatures, the lifetime is increasing linearly with increasing pressure. The slope of the pressure dependence is constant up to a temperature of 450 K and it is decreasing at higher temperatures. At constant pressure, the lifetime is exponentially decreasing with increasing temperature. The (p, T)-dependence can be parametrized by the combination of a linear and an exponential function. This allows an accurate p, T-determination by the combination of fluorescence spectroscopy using Sm²⁺-doped strontium tetraborate and lifetime measurements of ruby, as the energy of the Sm²⁺ fluorescence is nearly temperature-independent.     

添加Fe(C5H5)2合成氢掺杂金刚石大单晶及其表征

在Ni₇₀Mn₂₅Co₅-C体系中添加含氢化合物Fe(C₅H₅)₂作为新型氢源, 利用温度梯度法, 在压力为5.5-6.0 GPa、温度为1280-1400 ℃的条件下, 成功合成出氢掺杂的宝石级金刚石大单晶. 通过傅里叶显微红外光谱发现, 随着Fe(C₅H₅)₂添加量的增加, 合成晶体中与氢相关的对应于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2850和2920 cm^-1逐渐增强, 而晶体中氮含量却逐渐减少. 通过合成晶体的拉曼光谱分析发现, 金刚石的拉曼峰伴随Fe(C₅H₅)₂的添加向高频偏移, 这表明氢的进入在金刚石内部产生了压应力. 观察扫描电子显微镜图像发现, 在低含量Fe(C₅H₅)₂添加时晶体表面平滑, 而高含量添加时晶体表面缺陷增多, 且呈现出气孔状. 使用新的添加剂Fe(C₅H₅)₂作为氢源, 合成出含氢宝石级金刚石单晶, 丰富了金刚石单晶中对氢的研究内容, 也可为理解天然金刚石的形成机理提供帮助.