Significant suppression of residual nitrogen incorporation in diamond film with a novel susceptor geometry employed in MPCVD

This work proposed to change the structure of the sample susceptor of the microwave plasma chemical vapor deposition (MPCVD) reaction chamber, that is, to introduce a small hole in the center of the susceptor to study its suppression effect on the incorporation of residual nitrogen in the MPCVD diamond film. By using COMSOL multiphysics software simulation, the plasma characteristics and the concentration of chemical reactants in the cylindrical cavity of MPCVD system were studied, including electric field intensity, electron number density, electron temperature, the concentrations of atomic hydrogen, methyl, and nitrogenous substances, etc. After introducing a small hole in the center of the molybdenum support susceptor, we found that no significant changes were found in the center area of the plasma, but the electron state in the plasma changed greatly on the surface above the susceptor. The electron number density was reduced by about 40%, while the electron temperature was reduced by about 0.02 eV, and the concentration of atomic nitrogen was decreased by about an order of magnitude. Moreover, we found that if a specific lower microwave input power is used, and a susceptor structure without the small hole is introduced, the change results similar to those in the surface area of the susceptor will be obtained, but the spatial distribution of electromagnetic field and reactant concentration will be changed.     

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     

3mm回旋行波管微波等离子体化学气相沉积金刚石输出窗

为了解决目前3mm回旋行波管所使用的蓝宝石输出窗因功率容量不足而发生破裂的问题。从抗热震性和功率容量两个方面出发,对常用的几种窗片材料进行了对比。在国内首次以微波等离子体化学气相沉积金刚石为窗片材料,利用数值计算及ANSYS软件仿真设计了用于3mm回旋行波管的低反射,低吸收,宽带宽,高功率容量的输出窗。结果表明,所设计的输出窗适用于TE01模式输出,其S11参数小于-20dB的带宽为6GHz。同时,该输出窗具有良好的抗热震性,在自然对流散热条件下具有61kW的功率容量。     

掺杂CVD金刚石薄膜的应力分析

在不同实验条件下，用微波等离子体化学气相沉积(MPCVD)技术在Si基体上制备了S掺杂和B-S共掺杂CVD金刚石薄膜，利用X射线衍射仪和拉曼光谱仪研究掺杂对CVD金刚石薄膜的应力影响.研究结果发现，随着S掺杂浓度的增加，薄膜中sp²杂化碳含量和缺陷增多，CVD金刚石薄膜压应力增加；小尺寸的B原子与大尺寸的S原子共掺杂时，微量B的加入改变了CVD金刚石薄膜的应力状态，共掺杂形成B-S复合体进入金刚石晶体后降低金刚石晶体的晶格畸变程度，减少S原子在晶界上偏聚数量和晶体中非金刚石结构相含量，降低由于杂质、缺陷及sp²杂化碳含量产生的晶格畸变和薄膜压应力，提高晶格完整性. 关键词： 金刚石薄膜 掺杂 应力     

Impact of nitrogen doping on growth and hydrogen impurity incorporation of thick nanocrystalline diamond films

A much larger amount of bonded hydrogen was found in thick nanocrystalline diamond(NCD) films produced by only adding 0.24% N2 into 4% CH4 /H2 plasma,as compared to the high quality transparent microcrystalline diamond(MCD) films,grown using the same growth parameters except for nitrogen.These experimental results clearly evidence that defect formation and impurity incorporation(for example,N and H) impeding diamond grain growth is the main formation mechanism of NCD upon nitrogen doping and strongly support the model proposed in the literature that nitrogen competes with CH x(x=1,2,3) growth species for adsorption sites.     

Mo离子注入对金刚石涂层附着性能的影响

采用Mo离子注入工艺对YG6硬质合金基体表面进行处理,用微波等离子体CVD(MPCVD)法沉积金刚石涂层,研究了Mo离子注入工艺对金刚石涂层附着性能的影响.结果表明,Mo离子注入后,硬质合金基体表面的化学成分发生了明显变化;采用适当剂量的Mo离子注入基体,可使CVD金刚石涂层的附着性能显著提高. 关键词： 金刚石涂层 Mo离子注入 硬质合金基体 附着性能     

氢气浓度对MPCVD金刚石膜色度的影响

利用自行设计的直接耦合石英管微波等离子体化学气相沉积装置, 以氢气和甲烷为反应气体, 沉积出八个金刚石膜样品。研究了氢气浓度对所沉积金刚石膜色度的影响。结果表明, 饱和纯度和色纯度随着H2浓度的增大而升高; 当H2浓度达到94.137%时, 饱和纯度和色度纯度达到最大, 分别为8.5%和9.5%; 之后随着H2浓度的进一步升高饱和纯度和色纯度开始下降。     

MPCVD金刚石的Raman光谱分析

用微波等离子体化学气相淀积法（MPCVD）在Si基片上生长了金刚石薄膜，通过对其进行Raman光谱分析，一次表征了金刚石的结构，纯度及应力状况等材料性能，同时并研究了生长过程中微波功率与金刚石性质的关系。研究表明，微波等离子体化学气相溶积法生长的金刚石薄膜，除了金刚石成分的生长外，还会有部分非金刚石成分的生长，金刚石的纯度与微波功率的关系不明显，另外此种方法生长的金刚石薄膜主要表现为张应力。     

金刚石膜/多孔硅复合材料的性能表征

提出了一种新颖的多孔硅表面钝化技术,即采用微波等离子体辅助的化学气相沉积（MPCVD）方法在多孔硅上沉积金刚石薄膜。采用原子力显微镜（AFM）、扫描电子显微镜（SEM）、X射线衍射仪（XRD）、拉曼光 谱仪和荧光分光度计对多孔硅及金刚石膜的表面形貌、结构和发光特性进行了表征。结果表明采用微波等离子体化学气相沉积法可在多孔硅基片上形成均匀、致密、性能稳定且对可见光具有全透性的金刚石膜。金刚石膜与多孔硅的复合,大大稳定了多孔硅的发光波长和强度,同时增强了多孔硅的机械强度。     

单晶金刚石边缘表面倾斜角度对同质外延生长的影响

利用微波等离子体化学气相沉积法,对单晶金刚石(100)晶面边缘进行精细切割抛光处理,形成偏离(100)晶面不同角度的倾斜面,在CH_4/H_2反应气体中进行同质外延生长,研究单晶金刚石边缘不同角度倾斜面对边缘金刚石外延生长的影响.实验结果表明,边缘倾斜面角度对边缘的单晶外延生长质量有影响,随着单晶金刚石边缘倾斜面角度的增大,边缘多晶金刚石数量先减少后增多,在倾斜角3.8°时边缘呈现完整的单晶外延生长特性.分析认为,边缘不同角度的倾斜面会改变周围电场强度和等离子体密度,导致到达衬底表面的含碳前驱物发生改变,倾斜面台阶表面的含碳前驱物浓度低于能形成层状台阶生长的临界浓度是减弱单晶金刚石生长过程中边缘效应的主要原因.     

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.     

EPR study of nitrogen-doped mesoporous TiO2 powders

Mesoporous titanium dioxide powders were synthesized by the sol-gel route either directly or using the P123 templating agent and nitrogen doping from thiourea. X-ray diffraction studies show that doping and structuring give rise to rutile growth at a relatively low temperature of 400 °C compared to the transition point of pure TiO₂, which is close to 900 °C. Systematic EPR experiments were performed in order to monitor the involved paramagnetic centres with respect to calcination treatments and also to probe the nitrogen doping efficiency in the host media. Several paramagnetic species were found in these mesostructured samples mainly with oxygen radicals for calcinations at 400 °C, while nitrogen centres appear for calcination temperature as high as 500 °C. The effect of material microstructure on the effective incorporation of nitrogen in the TiO₂ lattice is also examined and compared in representative samples.     

Enhanced field emission characteristics of boron doped diamond films grown by microwave plasma assisted chemical vapor deposition

Boron doped diamond films were synthesized on silicon substrates by microwave plasma chemical vapor deposition (MPCVD) technique. The effect of B₂O₃ concentration varied from 1000 to 5000 ppm on the field emission characteristics was examined. The surface morphology and quality of films were characterized by scanning electron microscope (SEM) and Raman spectroscopy. The surface morphology obtained by SEM showed variation from facetted microcrystal covered with nanometric grains to cauliflower of nanocrystalline diamond (NCD) particles with increasing B₂O₃ concentration. The Raman spectra confirm the formation of NCD films. The field emission properties of NCD films were observed to improve upon increasing boron concentration. The values of the onset field and threshold field are observed to be as low as 0.36 and 0.08 V/μm, respectively. The field emission current stability investigated at the preset value of ∼1 μA is observed to be good, in each case. The enhanced field emission properties are attributed to the better electrical conductivity coupled with the nanometric features of the diamond films.     

Nonmetallic crystals with high thermal conductivity

Nonmetallic crystals transport heat primarily by phonons at room temperature and below. There are only a few nonmetallic crystals which can be classed as high thermal conductivity solids, in the sense of having a thermal conductivity of > 1 W/cmK at 300K. Thermal conductivity measurements on natural and synthetic diamond, cubic BN, BP and AIN confirm that all of them are high thermal conductivity solids. Studies have been made of the effect on the thermal conductivity of nitrogen impurities in diamond, and oxygen impurities in AIN. The nitrogen impurities scatter phonons mostly from the strain field, the oxygen impurities scatter phonons mostly from the mass defects caused by aluminum vacancies. Pure A1N as well as pure SiC, BeO, BP and BeS conduct heat almost as well as does copper at room temperature, while pure natural and synthetic diamonds conduct heat five times better than copper.All of the nonmetallic solids that are known to possess high thermal conductivity have either the diamond-like, boron carbide, or graphite crystal structure. There are twelve different diamond-like crystals, a few boron carbide-type crystals, and two graphite structure crystals that have high thermal conductivity. Analyses of the rock-salt, fluorite, quartz, corundum and other structures show no candidates for this class. The four rules for finding crystals with high thermal conductivity are that the crystal should have (1) low atomic mass, (2) strong bonding, (3) simple crystal structure, and (4) low anharmonicity. The prime example of such a solid is diamond, which has the highest known thermal conductivity at 300K.     

Laser Nitriding of Iron,Stainless Steel,and Plain Carbon Steel Investigated by Mössbauer Spectroscopy

Nitriding is a common method for improving the hardness, mechanical properties, wear and corrosion resistance of metals. Laser nitriding of metals is an efficient process, where the irradiation of surfaces in air or nitrogen atmospheres with short laser pulses leads to a fast take-up of nitrogen into the irradiated surfaces. This process has been extensively investigated for pure iron, but usually, no tools or functional parts are made of pure iron. Mainly steel or cast iron is used as a base material. Therefore, when looking for technical applicability, also the influence of alloying elements on the laser nitriding process is of great interest. Besides the pure iron various carbon steels and an austenitic stainless steel were studied in laser nitriding experiments in order to investigate the influence of the material itself. Here, the process is investigated via Conversion Electron and X-ray Mössbauer Spectroscopy (CEMS and CXMS), Resonant Nuclear Reaction Analysis (RNRA), and X-Ray Diffraction (XRD). It appears that carbon steels are even better suited for the laser nitriding process than pure iron, and the laser nitriding also works efficiently for the stainless steel which is normally difficult to be nitrided.     

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.     

Ground-state properties of boron-doped diamond

Boron-doped diamond undergoes an insulator-metal or even a superconducting transition at some critical value of the dopant concentration. We study the equilibrium lattice parameter and bulk modulus of boron-doped diamond experimentally and in the framework of the density functional method for different levels of boron doping. We theoretically consider the possibility for the boron atoms to occupy both substitutional and interstitial positions and investigate their influence on the electronic structure of the material. The data suggest that boron softens the lattice, but softening due to substitutions of carbon with boron is much weaker than due to incorporation of boron into interstitial positions. Theoretical results obtained for substitution of carbon are in very good agreement with our experiment. We present a concentration dependence of the lattice parameter in boron-doped diamond, which can be used for to identify the levels of boron doping in future experiments. The text was submitted by the authors in English.     

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.