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.     

B-C Bond in Diamond Single Crystal Synthesized with h-BN Additive at High Pressure and High Temperature

The synthesis of diamond single crystal in the Fe_(64)-Ni_(36)-C system with h-BN additive is investigated at pressure6.5 GPa and temperature range of 1300~140℃.The color of the obtained diamond crystals translates from yellow to dark green with increasing the h-BN addition.Fourier-transform infrared(FTIR) results indicate that sp~2 hybridization B-N-B and B-N structures generate when the additive content reaches a certain value in the system.The two peaks are located at 745 and 1425 cm~(-1),respectively Furthermore,the FTIR characteristic peak resulting from nitrogen pairs is noticed and it tends to vanish when the h-BN addition reaches 1.1 wt%.Furthermore,Raman peak of the synthesized diamond shifts down to a lower wavenumber with increasing the h-BN addition content in the synthesis system.     

High thermal stability of diamond-cBN-B_4C-Si composites

Improving the thermal stability of diamond and other superhard materials has great significance in various applications. Here, we report the synthesis and characterization of bulk diamond–cBN–B_4C–Si composites sintered at high pressure and high temperature(HPHT, 5.2 GPa, 1620–1680 K for 3–5 min). The results show that the diamond, cBN, B_4C,B_xSiC, SiO_2 and amorphous carbon or a little surplus Si are present in the sintered samples. The onset oxidation temperature of 1673 K in the as-synthesized sample is much higher than that of diamond, cBN, and B_4C. The high thermal stability is ascribed to the covalent bonds of B–C, C–N, and the solid-solution of B_xSiC formed during the sintering process. The results obtained in this work may be useful in preparing superhard materials with high thermal stability.     

Synthesis and Characteristics of Type Ib Diamond Doped with NiS as an Additive

Large diamond single crystals doped with NiS are synthesized under high pressure and high temperature. It is found that the effects on the surface and shape of the synthesized diamond crystals are gradually enhanced by increasing the NiS additive amount. It is noted that the synthesis temperature is necessarily raised to 1280℃ to realize the diamond growth when the additive amount reaches 3.5% in the synthesis system. The results of Fourier transform infrared spectroscopy(FTIR) demonstrate that S is incorporated into the diamond lattice and exists in the form of C–S bond. Based on the FTIR results, it is found that N concentration in diamond is significantly increased, which are ascribed to the NiS additive. The analysis of x-ray photoelectron spectroscopy shows that S is present in states of C–S, S–O and C–S–O bonds. The relative concentration of S compared to C continuously increases in the synthesized diamonds as the amount of additive NiS increases. Additionally,the electrical properties can be used to characterize the obtained diamond crystals and the results show that diamonds doped with NiS crystals behave as n-type semiconductors.     

Effects of Fe additive on diamond crystallization from carbonyl nickel powders-C system under HPHT condition

In this paper, diamond crystallization from carbonyl nickel powders-C and carbonyl nickel powders + Fe–C systems are investigated in detail at a pressure of 6.0 GPa and temperatures ranging from 1410°C–to 1435°C by temperature gradient growth. The effects of Fe additive on the crystal morphology are discussed in the diamond crystallization process.Furthermore, Fourier infrared measurement results indicate that the spectrum of the diamond obtained from Ni + Fe–C system after annealing treatment is nearly consistent with that of natural diamond crystal. We believe that this study is of benefit to a further understanding of the growth mechanism of natural diamond.     

A New Dopant of NaN3 for High-Concentration-Nitrogen Diamond Synthesized by HPHT

Nitrogen is successfully doped in diamond by adding sodium azide （NaN3 ） as the source of nitrogen to the graphite and iron powders. The diamond crystals with high nitrogen concentration, 1000-2200ppm, which contain the same concentrations of nitrogen with natural diamond, have been synthesized by using the system of iron-carbon- additive NAN3. The nitrogen concentrations in diamond increase with the increasing content of NAN3. When the content of NaN3 is increased to 0.7-1.3 wt. %, the nitrogen concentration in the diamond almost remains in a nitrogen concentration range from 1250ppm to 2200ppm, which is the highest value and several times higher than that in the diamond synthesized by a conventional method without additive NaN3 under high pressure and high temperature （HPHT） conditions.     

Influences of grain size and microstructure on optical properties of microcrystalline diamond films

Microcrystalline diamond(MCD) films with different grain sizes ranging from 160 nm to 2200 nm are prepared by using a hot filament chemical vapor deposition(HFCVD) system, and the influences of grain size and structural features on optical properties are investigated. The results show that the film with grain size in a range of 160 nm–310 nm exhibits a higher refractive index in a range of(2.77–2.92). With grain size increasing to 620±300 nm, the refractive index shows a value between 2.39 and 2.47, approaching to that of natural diamond(2.37–2.55), and a lower extinction coefficient value between 0.08 and 0.77. When the grain size increases to 2200 nm, the value of refractive index increases to a value between 2.66 and 2.81, and the extinction coefficient increases to a value in a range of 0.22–1.28. Visible Raman spectroscopy measurements show that all samples have distinct diamond peaks located in a range of 1331 cm~(-1)–1333 cm~(-1),the content of diamond phase increases gradually as grain size increases, and the amount of trans-polyacetylene(TPA)content decreases. Meanwhile, the sp~2 carbon clusters content and its full-width-at-half-maximum(FWHM) value are significantly reduced in MCD film with a grain size of 620 nm, which is beneficial to the improvement of the optical properties of the films.     

Ceramic synthesis of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 under high pressure and high temperature

In this paper, the preparation of 0.08BiGaO_3–0.90BaTiO_3–0.02LiNbO_3 is investigated at pressure 3.8 GPa and temperature 1100–1200?C. Experimental results indicate that not only is the sintered rate more effective, but also the sintered temperature is lower under high pressure and high temperature than those of under normal pressure. It is thought that the adscititious pressure plays the key role in this process, which is discussed in detail. The composition and the structure of the as-prepared samples are recorded by XRD patterns. The result shows that the phases of Ba TiO_3, BaBiO_(2.77), and Ba_2Bi_4Ti_5O_(18) with piezoelectric ceramic performance generate in the sintered samples. Furthermore, the surface morphology characteristics of the typical samples are also investigated using a scanning electron microscope. It indicates that the grain size and surface structure of the samples are closely related to the sintering temperature and sintering time. It is hoped that this study can provide a new train of thought for the preparation of lead-free piezoelectric ceramics with excellent performance.     

Effect of FeS doping on large diamond synthesis in FeNi-C system

The large single-crystal diamond with FeS doping along the(111) face is synthesized from the FeNi–C system by the temperature gradient method(TGM) under high-pressure and high-temperature(HPHT). The effects of different FeS additive content on the shape, color, and quality of diamond are investigated. It is found that the(111) face of diamond is dominated and the(100) face of diamond disappears gradually with the increase of the FeS content. At the same time, the color of the diamond crystal changes from light yellow to gray-green and even gray-yellow. The stripes and pits corrosion on the diamond surface are observed to turn worse. The effects of FeS doping on the shape and surface morphology of diamond crystal are explained by the number of hang bonds in different surfaces of diamond. It can be shown from the test results of the Fourier transform infrared(FTIR) spectrum that there exists an S element in the obtained diamond. The N element content values in different additive amounts of diamond are calculated. The XPS spectrum results demonstrate that our obtained diamond contains S elements that exist in S–C and S–C–O forms in a diamond lattice. This work contributes to the further understanding and research of FeS-doped large single-crystal diamond characterization.     

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.     

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.     

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.     

Dependence of nitrogen vacancy color centers on nitrogen concentration in synthetic diamond

Crystallization of diamond with different nitrogen concentrations was carried out with a FeNiCo-C system at pressure of 6.5 GPa. As the nitrogen concentration in diamond increased, the color of the synthesized diamond crystals changed from colorless to yellow and finally to atrovirens (a dark green). All the Raman peaks for the obtained crystals were located at about 1330 cm^-1 and contained only the sp³ hybrid diamond phase. Based on Fourier transform infrared results, the nitrogen concentration of the colorless diamond was < 1 ppm and absorption peaks corresponding to nitrogen impurities were not detected. However, the C-center nitrogen concentration of the atrovirens diamond reached 1030 ppm and the value of A-center nitrogen was approximately 180 ppm with a characteristic absorption peak at 1282 cm^-1. Furthermore, neither the NV⁰ nor the NV^- optical color center existed in diamond crystal with nitrogen impurities of less than 1 ppm by photoluminescence measurement. However, Ni-related centers located at 695 nm and 793.6 nm were observed in colorless diamond. The NE8 color center at 793.6 nm has more potential for application than the common NV centers. NV⁰ and NV^- optical color centers coexist in diamond without any additives in the synthesis system. Importantly, only the NV^- color center was noticed in diamond with a higher nitrogen concentration, which maximized optimization of the NV^-/NV⁰ ratio in the diamond structure. This study has provided a new way to prepare diamond containing only NV^- optical color centers.     

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.     

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.     

高温高压处理对褐色CVD钻石谱学特征的影响

目前CVD法合成单晶钻石是超硬材料科学和宝石学关注的热点之一,该方法合成的单晶钻石常带有褐色调。通常采用高温高压法（HPHT）提高褐色CVD钻石的色级和透明度,在前期HPHT处理褐色CVD钻石实验基础上,选出颜色改善明显的三颗样品,对其处理前后谱学特征进行对比。采用紫外-可见吸收光谱、红外光谱、光致发光光谱、三维荧光光谱、激光拉曼光谱以及X射线摇摆曲线进行分析。结果表明,褐色和深褐色样品褪色温度较高,处理后样品紫外-可见吸收光谱吸收系数明显减小,透明度明显提高。样品中红外与近红外光谱显示,在1 332 cm-1处的吸收峰与N+中心有关,该中心是褐色CVD钻石常见特征。在3 124 cm-1处吸收峰与NVH0缺陷中心有关,该峰在CVD钻石和HPHT处理钻石中常见。另外在2 700~3 200 cm-1范围变化的一组吸收峰,与C-H键伸缩振动有关。高温对CVD钻石含H基团影响较大,在5~6 GPa压力下处理温度在1 500~1 700 ℃范围,会在近红外波段4 673,6 352,7 354,7 540,7 804和8 535 cm-1出现一组吸收峰,可指示样品经过较高温度处理。目前针对CVD钻石以及经过HPHT处理的CVD钻石近红外波段的论述较少,该研究可以为鉴定CVD钻石及HPHT处理CVD钻石提供依据。综合光致发光光谱和三维荧光光谱分析,处理后样品NV-缺陷比例减小,SiV-中心缺陷比例增加。在5~6 GPa压力下,仅当处理温度高于1 500 ℃时,样品三维荧光光谱在λ_ex/λ_em=500 nm/575 nm处荧光峰增强,在λ_ex/λ_em=490 nm/550 nm处荧光峰消失,从某种意义上该峰位变化可指示样品经过较高温度处理。物相分析结果显示,HPHT处理后CVD钻石在1 332 cm-1处拉曼位移半高宽和XRD摇摆曲线半高宽均减小,表现出了较好的一致性,说明经HPHT处理的褐色CVD钻石结晶质量变优。     

Different effect of NiMnCo or FeNiCo on the growth of type-Ⅱa large diamonds with Ti/Cu as nitrogen getter

In order to synthesize high-quality type-Ⅱa large diamond, the selection of catalyst is very important, in addition to the nitrogen getter. In this paper, type-IIa large diamonds are grown under high pressure and high temperature(HPHT) by using the temperature gradient method(TGM), with adopting Ti/Cu as the nitrogen getter in Ni_(70)Mn_(25)Co_5(abbreviated as NiMnCo) or Fe_(55)Ni_(29)Co_(16)(abbreviated FeNiCo) catalyst. The values of nitrogen concentration(N_c) in both synthesized high-quality diamonds are less than 1 ppm, when Ti/Cu(1.6 wt%) is added in the FeNiCo or Ti/Cu(1.8 wt%) is added in the NiMnCo. The difference in solubility of nitrogen between both catalysts at HPHT is the basic reason for the different effect of Ti/Cu on eliminating nitrogen. The nitrogen-removal efficiency of Ti/Cu in the NiMnCo catalyst is less than in the FeNiCo catalyst. Additionally, a high-quality type-Ⅱa large diamond size of 5.0 mm is obtained by reducing the growth rate and keeping the nitrogen concentration of the diamond to be less than 1 ppm, when Ti/Cu(1.6 wt%) is added in the FeNiCo catalyst.     

钾镁胁迫对橡胶幼苗叶片物质成分影响的FTIR表征

养分亏缺是作物产量和质量提升的重要限制因子。我国砖红壤植胶区钾、镁缺乏及其低的有效性长期制约天然橡胶的产、质量。以“热研7-33-97”橡胶幼苗为研究对象,利用傅里叶变换红外光谱（FTIR）对钾、镁胁迫下橡胶树叶片物质组成特征进行研究,分析不同钾、镁胁迫条件下叶片红外光谱图谱特征峰的变化及其差异,探讨钾、镁胁迫对叶片物质成分和结构的影响,以期为钾镁缺乏影响橡胶树生长与生理代谢的机理研究提供参考。结果表明：（1）缺钾条件下,1 554,1 519和1 075 cm-1处的吸收峰缺失,表明橡胶叶片中蛋白质酰胺Ⅱ带、酚类物质、碳水化合物的化学结构受到破坏,并且其他特征峰吸光度与正常处理相比均有不同程度的升高,表明缺钾造成蛋白质、碳水化合物等物质在叶片中大量积累,物质转运效率降低;（2）缺镁条件下,1 554 cm-1处吸收峰向高频方向位移了6 cm-1,说明缺镁造成蛋白质酰胺Ⅱ带的结构发生改变,同时,1 550~1 350 cm-1波数范围内吸收峰相对吸光度明显下降,说明缺镁降低了细胞壁多糖以及含油脂化合物的含量,且该波数范围内的三个吸收峰较其他吸收峰变化敏感,表明该波段可以较好地指示橡胶叶片镁营养状况;（3）钾镁同时缺乏条件下,各吸收峰的相对吸光度和强度明显减弱,1 554,1 519和1 075 cm-1处的吸收峰缺失,说明蛋白质酰胺Ⅱ带、酚类物质、碳水化合物的化学结构受到破坏,1 057 cm-1处吸收峰向高频方向位移了11 cm-1,表明橡胶叶片中果胶类多糖分子结构发生了变化。综上所述,缺钾造成橡胶叶片蛋白质、糖类物质的含量的大量积累,缺镁造成叶片细胞壁多糖和油脂化合物下降,而钾镁同时缺乏时蛋白质、脂类、糖类物质等物质含量均明显下降。研究表明,使用FTIR技术对养分缺乏下的橡胶叶片物质成分定性分析具有一定的可行性,同时可为橡胶钾、镁营养生理代谢的机制研究提供新的思路和方法。     

退火温度对硼掺杂纳米金刚石薄膜微结构和p型导电性能的影响

采用热丝化学气相沉积法制备硼掺杂纳米金刚石 (BDND) 薄膜, 并对薄膜进行真空退火处理, 系统研究退火温度对BDND薄膜微结构和电学性能的影响. Hall效应测试结果表明掺B浓度为5000 ppm (NHB) 的样品的电阻率较掺B浓度为500 ppm (NLB) 的样品的低, 载流子浓度高, Hall迁移率下降. 1000 ℃退火后, NLB和NHB 样品的迁移率分别为53.3和39.3 cm²·V^-1·s^-1, 薄膜的迁移率较未退火样品提高, 电阻率降低. 高分辨透射电镜、紫外和可见光拉曼光谱测试结果表明, NLB样品的金刚石相含量较NHB样品高, 高的硼掺杂浓度使薄膜中的金刚石晶粒产生较大的晶格畸变. 经1000 ℃退火后, NLB和NHB薄膜中纳米金刚石相含量较未退火时增大, 说明薄膜中部分非晶碳转变为金刚石相, 为晶界上B扩散到纳米金刚石晶粒中提供了机会, 使得纳米金刚石晶粒中B浓度提高, 增强纳米金刚石晶粒的导电能力, 提高薄膜电学性能. 1000 ℃退火能够恢复纳米金刚石晶粒的晶格完整性, 减小由掺杂引起的内应力, 从而提高薄膜的电学性能. 可见光Raman光谱测试结果表明, 1000℃退火后, Raman谱图中反式聚乙炔 (TPA) 的1140 cm^-1峰消失, 此时薄膜电学性能较好, 说明TPA减少有利于提高薄膜的电学性能. 退火后金刚石相含量的增大、金刚石晶粒的完整性提高及TPA含量的大量减少有利于提高薄膜的电学性能. 关键词： 硼掺杂纳米金刚石薄膜 退火 微结构 电学性能     

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.