Photoacoustic spectroscopy of diamond powders and polycrystalline films

Photoacoustic spectroscopy is used to study optical absorption in diamond powders and polycrystalline films. The photoacoustic spectra of diamond powders with crystallite sizes in the range from ∼100 μm to 4 nm and diamond films grown by chemical vapor deposition (CVD) had a number of general characteristic features corresponding to the fundamental absorption edge for light with photon energies exceeding the width of the diamond band gap (∼5.4 eV) and to absorption in the visible and infrared by crystal-structure defects and the presence of non-diamond carbon. For samples of thin (∼10 μm) diamond films on silicon, the photoacoustic spectra revealed peculiarities associated with absorption in the silicon substrate of light transmitted by the diamond film. The shape of the spectral dependence of the amplitude of the photoacoustic signal in the ultraviolet indicates considerable scattering of light specularly reflected from the randomly distributed faces of the diamond crystallites both in the polycrystalline films and in the powders. The dependence of the shape of the photoacoustic spectra on the light modulation frequency allows one to estimate the thermal conductivity of the diamond films, which turns out to be significantly lower than the thermal conductivity of single-crystal diamond. Fiz. Tverd. Tela (St. Petersburg) 39, 1787–1791 (October 1997)     

Conductivity of boron-doped polycrystalline diamond films: influence of specific boron defects

The resistivity of boron doped polycrystalline diamond films changes with boron content in a very complex way with many unclear factors. From the large number of parameters affecting boron doped polycrystalline diamond film’s conductivity we focused on the role of boron atoms inside diamond grains in terms of boron contribution to the continuum of diamond electronic states. Using a combination of theoretical and experimental techniques (plane-wave Density Functional Theory, Neutron Depth Profiling, resistivity and Hall effect measurements, Atomic Force Microscopy and Raman spectroscopy) we studied a wide range of B defect parameters — the boron concentration, location, structure, free hole concentration and mobility. The main goal and novelty of our work was to find the influence of B defects (structure, interactions, charge localisation and spins) in highly B-doped diamonds — close or above the metal-insulator transition – on the complex material charge transport mechanisms.     

Nitrogen-Doped Chemical Vapour Deposited Diamond： a New Material for Room-Temperature Solid State Maser

Electron spin resonance （ESR） in polycrystalline diamond films grown by dc arc-jet and microwave plasma chemical vapour deposition is studied. The films with nitrogen impurity concentration up to 8 × 10^18 cm^-3 are also characterized by Raman, cathodoluminescence and optical absorption spectra. The ESR signal from P1 centre with g-factor of 2.0024 （nitrogen impurity atom occupying C site in diamond lattice） is found to exhibit an inversion with increasing the microwave power in an H102 resonator. The spin inversion effect could be of interest for further consideration of N-doped diamonds as a medium for masers operated at room temperature.     

p-Type doping of diamond films with a novel organoboron source

p-Type polycrystalline diamond films were prepared by hot-filament CVD method using a liquid cyclic organic borinate ester as the doping source. The obtained films were identified as diamond films by means of SEM and Raman spectroscopy. The resistivity of the doped films can be adjusted by changing the temperature of the boron source.     

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.     

Influence of structural characteristics on the thermal conductivity of polycrystalline diamond films

By analyzing the signal formed by the photoacoustic effect as a function of the light modulation frequency, it is shown that this effect may be used to determine the thermal conductivity of diamond materials. The method is checked experimentally for two types of polycrystalline diamond films grown by chemical vapor deposition with the gaseous medium activated by a dc discharge and a microwave discharge. The data obtained on the thermal conductivity of the films are discussed with reference to the results of an investigation of the optical absorption, Raman light scattering, and cathodoluminescence of similar films. It is shown that the thermal conductivity of polycrystalline diamond films depends on the structural characteristics, which are determined by the deposition conditions. Fiz. Tverd. Tela (St. Petersburg) 40, 1221–1225 (July 1998)     

热灯丝CVD金刚石膜硼掺杂效应研究

利用Ｒａｍａｎ谱和Ｘ射线衍射微分析研究了金刚石膜硼掺杂效应．研究发现，在硼浓度较低时，金刚石膜中非晶碳（Ｓｐ²键合）含量减少，而随着硼浓度增加，金刚石膜的Ｒａｍａｎ特征峰（Ｓｐ^３）向低频方向漂移，并且展宽和出现不对称．这是由于硼掺杂引起晶格变化及Ｆａｎｏ互作用所致 关键词：     

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     

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     

微喇曼和红外光谱法研究化学气相沉积金刚石多晶膜结晶质量特性

研究了化学气相沉积多晶膜的宏观性能（颜色和透光性）与微观性能（结晶质量、相纯度和氢杂质含量）之间的关系,喇曼谱与金刚石膜中氢杂质含量（红外光谱测得）的关联性.给出了根据颜色和透明度来区分样本膜质量的实验依据,颜色较深的膜的结晶质量差、相纯度低、氢杂质含量高,1 332 cm－1金刚石特征喇曼峰强度低,半峰宽大.由于多晶膜生长不均匀性、多晶以及粗糙度的影响,生长面的微喇曼光谱随采样点变化会产生较大的偏差,而光滑生长界面的喇曼光谱随采样点的变化偏差较小,因此生长界面的喇曼光谱更能反映化学气相沉积法制备金刚石膜的整体质量.     

Effect of pressure on the Raman spectra of synthetic diamonds with boron impurity

The raman scattering technique is used for studying diamonds with a 0.04–0.1 at % boron impurity under a pressure up to 3 GPa in a chamber with sapphire anvils. The Raman frequency increases linearly with pressure for all samples with pressure coefficients of 2.947 cm^?1/GPa for pure diamond and 3.01 cm^?1/GPa for boron-doped samples. The Raman linewidths remain unchanged for pure diamond and for diamond with a boron concentration of about 0.04 at % and decrease linearly upon an increase in pressure for samples with a boron concentration of about 0.1 at %. The Raman spectra with a line profile corresponding to the Fano resonance do not change qualitatively up to a pressure of 3 GPa. In diamond samples with a boron impurity exceeding 0.1 at %, the boron concentration in the surface layer can be substantially higher than at the center of the sample.     

Determination of thermal conductivity of CVD diamond films via photoacoustic measurements

A novel method of determination of polycrystalline diamond films’ thermoconductive properties using the photoacoustic effect is proposed. By this method, we studied the diamond films grown on silicon substrates using chemical vapor deposition technique. A value of thermal conductivity obtained for the films was less than half that for diamond single crystal. The decrease of thermal conductivity, as well as characteristic features of optical properties of the films, is explained by the presence of a large amount of intercrystallite boundaries and other structure defects and admixures detected using Raman and photoluminescent spectroscopies. Received: 22 October 1998 / Accepted: 27 January 1999 / Published online: 28 April 1999     

金刚石膜微结构的慢正电子束测量研究

用慢正电子束辅助以拉曼光谱方法对一批较高质量的PECVD金刚石膜的微结构进行测量研究．拉曼光谱实验结果显示,这批金刚石膜中金刚石相含量比较高,正电子湮没实验进一步从微观结构上指出各个金刚石膜之间存在很大差异,并且从缺陷角度发现各样品中缺陷尺寸和缺陷浓度不一样,造成膜质量不同．S-E曲线变化趋势反映出各样品金刚石晶体结构存在明显不同．这表明正电子湮没技术是测量金刚石膜微结构的有力手段．     

金刚石薄膜在多晶铜和磷脱氧铜基片上的生长

分别采用99.99%的多晶铜片和99.95%的磷脱氧铜片作为沉积金刚石薄膜的基片，通过热丝化学汽相沉积法在两种基片上都获得了大面积、自支撑的多晶金刚石膜.使用高分辨率光学显微镜、扫描电子显微镜、Raman光谱和X射线衍射比较分析了两种铜基片上的金刚石膜.脱氧铜上的金刚石膜质量并不亚于多晶铜上的金刚石膜，而且它的成核密度、生长速率以及应力都高于多晶铜上金刚石膜的同类参数.特别采用了退火工艺和优化的生长条件来获得大面积的连续金刚石膜. 关键词：     

Novel technique for hetero-epitaxial diamond film growth on cubic boron nitride from iron carbide at high temperature and high pressure

Cubic boron nitride (c-BN) crystals about 0.1–0.3 mmin dimension were treated with iron carbide powders (high purity 99%) with size of 80–100 mesh at a high temperature of 1620 K and a high pressure of 5.2 GPa. It was found that hetero-epitaxial diamond films have been grown on the c-BN from iron carbide. The formation of dia-mond films on the cubic boron nitride can be confirmed by laser Raman spectra, face scan of elements and reflective high-energy electron diffraction. It was suggested that diamond films could be epitaxially formed on the c-BN through decomposition of iron carbide. This approach provides a possible and very effective way to realize hetero-epitaxial growth of homogeneous and large-area diamond films on c-BN, which is different from the conventional technique using a chemical vapor deposition method. Received: 20 December 2000 / Accepted: 9 January 2001 / Published online: 28 February 2001     

The effect of boron ion implantation and annealing on the microstructure and electrical characteristics of the diamond films

Diamond films were doped by boron ion-implantation with the energy of 120 keV. The implantation dose ranged from 10¹⁴ to 10¹⁷ cm⁻². After the implantation, the diamond films were annealed at different temperatures (600–750°C) for different times (2–15 min). Scanning Electronic Microscope, Raman and Secondary Ion Mass-spectrum were used to investigate the effect of boron ion implantation and annealing on the microstructure of the diamond films. The electrical resistivities of the diamond films were also measured. It was found that the best dose of boron ion-implantation into the diamond film was around 10¹⁶ cm⁻². The appropriate annealing temperature and time was 700°C and 2–5 min, respectively. After implantation, the resistivities were reduced to 0.1 Ω cm (almost nine orders lower than the unimplanted diamond films). These results show that boron ion implantation can be an effective way to fabricate P-type diamond films.     

热丝CVD生长金刚石薄膜喇曼散射研究

本文报道热丝化学气相沉积法（ＨＦＣＶＤ）生长金钢石薄膜的喇曼散射结果。选取多种峰型，对金钢石薄膜喇曼谱（１１０－１８００ｃｍ－１）采用最小二乘法进行非线性拟合，得到最佳拟合模型，其计算得到的拟合曲线怀实验谱图符合得较好。该模型揭示，石墨Ｄ峰（１３５５ｃｍ－１）是金刚石薄膜喇曼谱中不可缺少的一个组份，并且结合石墨Ｄ峰和金刚石喇曼的空间相关线型，可以解释金刚石喇曼区特殊峰形的物理机制，拟合参量的进一步     

不同织构CVD金刚石膜的Hall效应特性

采用热丝化学气相沉积法在p型硅衬底上制备了不同织构的多晶金刚石膜,使用XRD表征了CVD金刚石膜的结构特征, 研究了退火后不同织构金刚石膜的电流特性, 使用Hall效应检测仪研究了金刚石膜的霍尔效应特性及随温度变化的规律, 结果表明所制备的金刚石膜是p型材料, 载流子浓度随着温度的降低而增加, 迁移率随着温度的降低而减小. 室温下[100]织构金刚石薄膜的载流子浓度和迁移率分别为4.3×10⁴ cm^-3和76.5 cm²/V·s.     

负偏压热灯丝CVD金刚石膜核化和早期生长的研究

利用扫描电子显微镜、Raman谱和X射线光电子能谱，研究了Si衬底上热灯丝CVD金刚石膜的核化和早期生长.在-300V和100mA条件下预处理15min，镜面抛光的Si(100)表面上金刚石核密度超过了10⁹cm^-2，但是核的分布极不均匀且可分为三个区域：A区，边缘处以锥体为主；B区，位于边和中心之间过渡区是纳米金刚石；C区，中心处有SiC层.无偏压下生长4h后，A区形成许多大而弧立的金刚石颗粒，B区成为织构金刚石膜，而C区变为含有大量缺陷的连续金刚石膜.衬底负 关键词：     

Study of microwave plasma-assisted chemical vapor deposition of poly-and single-crystalline diamond films

We study conditions for microwave plasma-assisted chemical vapor deposition of high-quality single-crystal diamond films in a CVD reactor. These conditions are studied using the results of homoepitaxial growth of polycrystalline diamond films on diamond substrates and on the basis of numerical simulation of the microwave discharge in a CVD reactor. A high-quality single-crystal diamond layer is synthesized on a synthetic, type Ib diamond substrate. The properties of the obtained monolayer are studied by means of Raman and X-ray diffraction spectroscopy as well as optical and atomic-force microscopy.