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.     

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.     

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.     

锌添加对大尺寸金刚石生长的影响

利用温度梯度法,在6.2—6.4 GPa,1270—1400℃条件下,通过在NiMnCo-C体系中添加不同比例的锌粉成功合成出3 mm左右的大尺寸金刚石单晶.研究了锌添加对金刚石颜色、形貌、内部氮杂质以及晶体结晶度的影响.结果表明:随着锌添加量逐渐增加,晶体的颜色逐渐变浅,晶体的透光性增强;当锌添加比例达到3 wt.%时,晶体表面出现大量不规则的凹坑;晶体内氮杂质主要以C心形式存在,随着锌添加量的增多晶体内氮含量逐渐降低,基于锌的除氮能力总结出两种可能的除氮机制;拉曼光谱测试结果表明,在锌添加量小于3.0 wt.%的研究范围内,锌的添加有利于提高晶体的结晶度.本研究不仅有助于天然金刚石形成机制的探究,而且对丰富金刚石的种类以及扩展人工合成金刚石的应用领域都有着重要意义.     

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.     

Lateral IBIC characterization of single crystal synthetic diamond detectors

In order to evaluate the charge collection efficiency (CCE) profile of single‐crystal diamond devices based on a p‐type/intrinsic/metal configuration, a lateral Ion Beam Induced Charge (IBIC) analysis was performed over their cleaved cross sections using a 2 MeV proton microbeam. CCE profiles in the depth direction were extracted from the cross‐sectional maps at variable bias voltage. IBIC spectra relevant to the depletion region extending beneath the frontal Schottky electrode show a 100% CCE, with a spectral resolution of about 1.5%. The dependence of the width of the high efficiency region from applied bias voltage allows the constant residual doping concentration of the active region to be evaluated. The region where the electric field is absent shows an exponentially decreasing CCE profile, from which it is possible to estimate the diffusion length of the minority carriers by means of a drift–diffusion model. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of catalyst height on diamond crystal morphology under high pressure and high temperature

The effect of the catalyst height on the morphology of diamond crystal is investigated by means of temperature gradient growth(TGG) under high pressure and high temperature(HPHT) conditions with using a Ni-based catalyst in this article. The experimental results show that the morphology of diamond changes from an octahedral shape to a cuboctahedral shape as the catalyst height rises. Moreover, the finite element method(FEM) is used to simulate the temperature field of the melted catalyst/solvent. The results show that the temperature at the location of the seed diamond continues to decrease with the increase of catalyst height, which is conducive to changing the morphology of diamond. This work provides a new way to change the diamond crystal morphology.     

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.     

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     

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.     

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.     

具有广阔应用前景的纳米金刚石膜

纳米金刚石膜的制备、表征和应用研究已经成为CVD金刚石膜研究领域的一个新的热点．文章重点介绍了Gruen等人在贫氢和无氢环境中制备纳米金刚石膜的开创性工作,并和在富氢气氛中制备的纳米金刚石膜进行了对比评述．对纳米金刚石膜的表征技术和应用前景进行了讨论．     

氮对金刚石缺陷发光的影响

利用低温显微荧光光谱研究了IIa型、Ib型、Ia型金刚石的缺陷发光性质. 研究发现, 随着氮含量增加, 间隙原子及空位逐渐被氮原子所束缚, 从而使得GR1中心、533.5 nm及580 nm中心等本征缺陷发光减弱, 而氮-空位复合缺陷(NV中心)及523.7 nm中心等氮相关缺陷发光增强. 高温退火后, 间隙原子与空位可以自由移动, IIa型金刚石中出现了NV⁰中心, Ib型金刚石中只剩下了NV中心, Ia型金刚石中氮原子之间发生团聚, 出现了H3中心及N3中心. 另外, 氮作为施主原子, 有利于负电荷缺陷的形成, 如3H 中心、NV^- 中心.     

Synthesis and characterizations of boron and nitrogen co-doped high pressure and high temperature large single-crystal diamonds with increased mobility

We synthesized and investigated the boron-doped and boron/nitrogen co-doped large single-crystal diamonds grown under high pressure and high temperature (HPHT) conditions (5.9 GPa and 1290℃). The optical and electrical properties and surface characterization of the synthetic diamonds were observed and studied. Incorporation of nitrogen significantly changed the growth trace on surface of boron-containing diamonds. X-ray photoelectron spectroscopy (XPS) measurements showed good evident that nitrogen atoms successfully incorporate into the boron-rich diamond lattice and bond with carbon atoms. Raman spectra showed differences on the as-grown surfaces and interior between boron-doped and boron/nitrogen co-doped diamonds. Fourier transform infrared spectroscopy (FTIR) measurements indicated that the nitrogen incorporation significantly decreases the boron acceptor concentration in diamonds. Hall measurements at room temperature showed that the carriers concentration of the co-doped diamonds decreases, and the mobility increases obviously. The highest hole mobility of sample BNDD-1 reached 980 cm²·V^-1·s^-1, possible reasons were discussed in the paper.     

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.     

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.     

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.     

氮氢共掺杂金刚石中氢的典型红外特征峰的表征

所有天然Ia型金刚石红外光谱中都存在3107 cm-1特征峰,而在金属触媒直接合成的金刚石红外光谱中没有检测出3107 cm-1特征峰.本文在6.3 GPa,1500?C条件下,通过Fe70Ni30触媒中添加P3N5直接合成出具有3107 cm-1特征峰的氮氢共掺杂的金刚石.红外光谱分析表明,合成的金刚石中氢有两种存在形式:一种对应着乙烯基团C=CH2中C—H键的伸缩振动(3107 cm-1)和弯曲振动(1450 cm-1)的吸收峰,另一种对应着sp3杂化C—H键的对称伸缩振动(2850 cm-1)和反对称伸缩振动(2920 cm-1)的吸收峰.通过分析发现,3107 cm-1吸收峰与金刚石中聚集态的氮原子有关,当金刚石中没有聚集态的氮元素时,即使氮含量高也不会出现3107 cm-1峰;并且2850和2920 cm-1附近的吸收峰比3107 cm-1附近的吸收峰更为普遍存在.这说明sp3杂化C—H键比乙烯基团的C—H键更广泛存在于金刚石中,从两者的峰值看,天然金刚石中的氢杂质主要以乙烯基团C=CH2存在.3107 cm-1吸收峰与聚集态的氮原子的这种存在关系为天然金刚石形成机制的研究提供了一种新思路,同时较低的合成条件也可能为氢与其他元素共掺杂合成具有n型半导体特性的金刚石提供一个较理想的合成环境.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

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.