单晶金刚石在高端技术领域的应用

阐述单晶金刚石在高端技术领域的应用,包括微型超精金刚石切削工具如加工成形随意曲率超细槽的方形立铣刀,用于三维表面微凹坑和任意曲率面加工的超精纳微型球形立铣刀,以剃削和快速切削加工直线超细槽的切削工具,此外还有人造单晶金刚石制作的高压水力喷射切割装置的喷射喉管,以及单晶金刚石制作的微型光学元件,并述及大单晶CVD金刚石的潜在用途.     

关于人造含硼金刚石晶体结构及抗氧化性的研究

人造金刚石的抗氧化性是国际上评价其性能优劣的重要指标.文章以粉末铁基触媒中掺入不同含量的供硼剂为硼源,用静压法得到含硼量不同的人造金刚石.利用光学显微镜、X射线衍射仪和差热分析仪对含硼金刚石的晶形、晶体结构和抗氧化性能进行了研究,并与同样工艺条件下得到的普通金刚石进行对比,结果证明此种合成方法能够得到抗氧化性能优异的金刚石.     

Electrical properties of the high quality boron-doped synthetic single-crystal diamonds grown by the temperature gradient method

Temperature dependencies of the resistivity and the Hall coefficient in high-quality boron-doped synthetic single crystal diamonds grown by the high-pressure-high-temperature (HPHT) method with different boron contents have been investigated. The concentration of acceptors was varied in the range of 2 × 10¹⁵ to 3 × 10¹⁷ cm^–3 in (001) cut plates by a change of boron content in a growth mixture in a range from 0.0004 to 0.04 atomic percent. A special sample preparation has been used for precise measurements. Thin rectangular plates with uniform boron content and without linear and planar structure defects have been laser cut after X-ray topography and UV-luminescence mapping. The donor and acceptor concentrations in each sample have been calculated from the Hall effect data and capacitance–voltage characteristics. The concentrations correlate with the boron content in a growth mixture. Minimum donor to acceptor compensation ratio slightly below 1% was observed at 0.002 at.% boron content in a growth mixture, while it increased at an increase and decrease of boron amount. Samples grown at such boron concentration had maximum carrier mobility. It was 2200 cm² / (V × s) at T = 300 K and 7200 cm² / (V × s) at T = 180 K. The phonon scattering of holes dominates in the entire temperature range of 180–800 K, while the scattering by point defects such as neutral and ionized impurity atoms is insignificant. Due to a perfect crystal quality and lattice scattering mechanism bulk diamond crystals grown from the mixture containing 0.0005 to 0.002 at.% of boron may serve as reference semiconductor materials.     

含硼金属包覆膜的物相结构与含硼金刚石的生成

使用以FeB为硼源的含硼粉末冶金铁基触媒,在六面顶压机上高温高压合成含硼金刚石单晶.金相观察发现,金刚石金属包覆膜由粗大的板条状渗碳体和细密的莱氏体共晶组织构成.X射线衍射(XRD)发现,金属包覆膜的物相组成为(Fe,Ni)3C、(Fe,Ni)3(C,B)、石墨(Gr)以及γ-(Fe,Ni)(A).使用透射电镜(TEM)在包覆膜中发现了颗粒状的Fe3(C,B),条状的γ-(Fe,Ni) 和颗粒状的Fe23(C,B)6.电子探针分析(EPMA)结果表明,硼元素在包覆膜中存在浓度梯度,越接近含硼金刚石,硼元素的含量越高.分析认为,高温高压下硼是以铁-碳-硼化合物的形式通过金属包覆膜向金刚石晶体扩散的,Fe3(C,B)或(Fe,Ni)3(C,B)极有可能是含硼金刚石生长的直接碳源和硼源.     

Synthesis of boron-doped homoepitaxial single crystal diamond by microwave plasma chemical vapor deposition

The deposition of boron-doped homoepitaxial single crystal diamond is investigated using a microwave plasma-assisted chemical vapor deposition system. The objective is to deposit high-quality boron-doped single crystal diamond and establish the relationships between the deposition conditions and the diamond growth rate and quality. Experiments are performed using type Ib HPHT diamond seeds as substrates and growing diamond with varying amounts of diborane in a methane–hydrogen gas mixture. The deposition system utilized is a 2.45 GHz microwave plasma-assisted CVD system operating at 135–160 Torr. Experiments are performed with methane concentrations of 4–6% and diborane concentrations of 5–50 ppm in the feedgas. Diamond is deposited with growth rates of 2 to 11 µm/h in this study. The deposited diamond is measured to determine its electrical conductivity and optical absorption versus wavelength in the UV, visible and IR portions of the spectrum. Data is presented that relates the growth rate and diamond properties to the deposition conditions including substrate temperature and feedgas composition.     

Properties of boron-doped epitaxial diamond layers grown on (110) oriented single crystal substrates

Boron doped diamond layers have been grown on (110) single crystal diamond substrates with B/C ratios up to 20 ppm in the gas phase. The surface of the diamond layers observed by scanning electron microscopy consists of (100) and (113) micro-facets. Fourier Transform Photocurrent Spectroscopy indicates substitutional boron incorporation. Electrical properties were measured using Hall effect from 150 to 1000 K. Secondary ion mass spectrometry analyses are consistent with the high incorporation of boron determined by electrical measurements. A maximum mobility of 528 cm² V^− 1 s^− 1 was measured at room temperature for a charge carrier concentration of 1.1 10¹³ cm^− 3. Finally, properties of boron doped (110) diamond layers are compared with layers on (100) and (111) orientated substrates.     

Vibrational sum-frequency observation of synthetic diamonds

Sum-frequency generation (SFG) spectroscopy was applied to the study of plasma hydrogenated diamond C(100) surface of a synthetic diamond. Two vibrational resonance peaks with the intensities strongly dependent on the polarization combinations of the visible and infrared beams were observed at 2899 and 2924 cm⁻¹. From the results of SFG measurements for various polarization combinations, the 2899 and 2924 cm⁻¹ peaks were assigned, respectively, to the antisymmetric and symmetric CH stretching modes of HCCH group on H/C(100)-2×1 surface. In addition, a strong background signal with an oscillatory profile was observed.     

Deposition of thick boron-doped homoepitaxial single crystal diamond by microwave plasma chemical vapor deposition

The deposition of high quality single crystal boron-doped diamond is studied. The experimental conditions for the synthesis of 1–2 mm thick boron-doped diamond are investigated using a high power density microwave plasma-assisted chemical vapor deposition reactor. The boron-doped diamond is deposited at a rate of 8–11.5 μm/h using 1 ppm diborane in the feed gas as the boron source, and the capability to overgrow defects is demonstrated. The experimental study also investigates the deposition of diamond with both 10 ppm diborane and 2.5–500 ppm of nitrogen added to the feedgas. Synthesized material properties are measured including the electrical conductivity using a four-point probe and the substitutional boron content using infrared absorption.     

Low temperature time of flight mobility measurements on synthetic single crystal diamond

We study the temperature dependence of low charge injection drift mobility in single crystal (SC) diamond using an alpha particle source. We present time of flight (ToF) mobility measurements to investigate the charge carrier scattering mechanisms in SC synthetic diamond in the temperature range 200 K–300 K. We have used a gold contacted pad detector, with a “sandwich” contact structure, fabricated using a SC chemical vapour deposition (CVD) diamond synthesised by Element Six Ltd. ToF analysis of alpha particle induced current pulses shows a strong increase in hole mobility at reduced temperatures, consistent with acoustic phonon scattering processes dominating the charge carrier transport. On the other hand, electron mobility values appear to remain relatively constant with lower temperatures suggesting different mechanisms than optical or acoustic phonon scattering limiting the charge transport.     

The effect of CO2 on the high-rate homoepitaxial growth of CVD single crystal diamonds

In this paper, we report the effect of gaseous carbon dioxide (CO₂) introduced in the typical reaction atmosphere of CH₄/H₂/N₂ (60/500/1.8 in sccm) on the growth rate, morphology and optical properties of homoepitaxy single crystal diamonds (SCDs) by microwave plasma chemical vapor deposition. The additional carbonaceous sources supplied by CO₂ are favorable to increase the growth rate, and meanwhile, the oxygen related species generated would enhance the etching effect not only to eliminate the non-diamond phase of SCD but also to decrease the growth rate. The appropriate addition of CO₂ can increase the high growth rate, decrease the surface roughness, and reduce the concentration of N-incorporation. It is demonstrated that adding CO₂ strongly affects the contents of various reaction species in plasma, which would determine the growth features of CVD SCDs.     

Characterization of boron-doped diamonds using 11B high-resolution NMR at high magnetic fields

¹¹B static/magic-angle spinning (MAS) NMR experiments are applied to four different B-doped diamond samples prepared by either high-pressure and high-temperature (HPHT) or CVD methods with various starting materials. Application of MAS enhances the spectral resolution appreciably and differences of the four B-doped diamond samples are well reflected in the corresponding MAS spectra. From the comparison among the MAS spectra, and also their dependences on the magnetic-field and the pulse-flip angle, it is suggested that at least four kinds of boron including two kinds of impurities exist in B-doped diamond. We further examine ¹¹B spin-lattice relaxation times (T₁) for the four components and find that one of them is extremely short (ca. 500 ms) while others are in the range of several seconds. Relation between the component having the short T₁ and the super conducting transition temperature (T_c) value is suggested.     

The influence of recess depth and crystallographic orientation of seed sides on homoepitaxial growth of CVD single crystal diamonds

Microwave plasma chemical vapor deposition (MPCVD) has gained increasing attention as a feasible and effective way to produce large, high-quality, single-crystal diamonds. However, the growth of polycrystalline diamond on the periphery of the seed crystal and the cracking generated by the internal stress during the growing process lead to significant decline of the quality and integrity of the CVD diamond, thus increasing the difficulty of synthesizing large diamond layers. Although optimized growth parameters and refined substrate holders have been employed by some researchers to improve the periphery quality of CVD diamond layers, more research needs to be done in this area. In this study, we used a specially designed substrate holder with a circular recess, in which the seed crystal was placed. By designing substrate holders with different recess depths and a seed crystal with different side-surface crystallographic orientations, we aimed to determine the influence of the recess depths and the crystallographic orientation of seed sides on the growth quality according to polarizing microscope, laser Raman spectroscopy, UV fluorescence imaging, and photoluminescence (PL) mapping measurements. The results demonstrate that as the recess depth increases, the amount of polycrystalline diamonds and the internal stress on the periphery are controlled effectively. The crystalline quality is improved, and the growth rate is decreased. In addition, compared to the periphery with {100} seed sides, the periphery with {110} seed sides displays better crystalline quality, lower internal stress, and fewer polycrystalline diamonds after growth, which is probably due to the intrinsic nature of the growth steps propagating on the {100} diamond surface and the effect of nitrogen atoms on the growing process in the diamond lattice.     

Electrochemical oxidation of water on synthetic boron-doped diamond thin film anodes

Electrolysis in aqueous 1 M HClO₄ and 1 M H₂SO₄ solutions has been carried out under galvanostatic conditions using boron-doped diamond electrodes (BDD). Analyses of the oxidation products have shown that in 1 M HClO₄ the main reaction is oxygen evolution, while in H₂SO₄ the main reaction is the formation of H₂S₂O₈. In both electrolytes small amounts of O₃ and H₂O₂ are formed. Finally, a simplified mechanism involving hydroxyl radicals formed by water discharge has been proposed for water oxidation on boron-doped diamond anodes.     

Photochemical attachment of amine-layers on H-terminated undoped single crystalline CVD diamonds

The initial nucleation and growth characteristics of amine layers photochemically attached from 10-amino-dec-1-ene molecules protected with tri-fluoroacetic acid group to H-terminated undoped single crystal CVD diamond surfaces are characterized by tapping and contact mode atomic force microscopy (AFM) and scanning tunneling microscopy (STM) with nanometer resolution. The diamond is atomically flat which allows attributing variations of tunneling currents in STM to amine grafted surface areas. Island formation and growth of islands with increasing photochemical attachment time is revealed by these experiments. This results support the growth model, where hydrogen cleavage reactions from the diamond surface by amine molecules bonded to diamond is the major growth mechanism. These reactions might be initiated by UV light illumination of pyrolysis of organic peroxides in the presence of the adsorbate, which are proposed to break H–C bonds to create surface dangling bonds. It occurs at the periphery of islands which gives rise to island growth.     

The effect of fast neutron irradiation on the performance of synthetic single crystal diamond particle detectors

Diamond is known for its extreme hardness which may allow it to operate as a particle detector in high fluence environments even after absorption of large radiation doses. We present a study of the deterioration of the charge collection efficiency (CCE) due to neutrons produced by ²³⁵U fission, with irradiation fluences up to 1 × 10¹⁶ n cm^?2. The planar devices were fabricated by thermal evaporation of Au onto approx. 300 μm thick high purity chemical vapour deposited diamond produced by Element Six Ltd., UK. The detector performance was investigated as a function of bias voltage at room temperature using ²⁴¹Am α-particles and minimum ionising particles (MIPs) of a ⁹⁰Sr source. At low fluences up to 2 × 10¹³ n cm^? 2, the detectors reach the initial saturated signal amplitude after irradiation. However, the signal is less stable and deteriorates due to polarisation. This effect can be reduced by initial priming with X-rays. No peak could be distinguished in the detector response in the unprimed state after 10¹⁶ n cm^? 2 with bias voltages up to 1000 V (equivalent to 32 kV cm^?1). However, a peak at about 18% CCE could be recovered after priming.     

碳源扩散不均一性对宝石级金刚石单晶生长的影响

高温高压温度梯度法生长优质宝石级金刚石单晶过程中,晶体生长主要由碳源在触媒中的扩散过程决定.本研究通过有限元对碳源对触媒的扩散过程进行了简单模拟,结果发现,受温度梯度法特定组装结构影响,实际晶体在生长过程中,由高温端扩散下来的碳源在触媒中的分布是相当不均匀的.对晶体生长来说,这种碳源扩散不均一性会直接影响晶体的生长过程.在籽晶粒度超过2mm时,晶体中心部位出现较多包裹体,或者生长表面无法生长愈合.     

Characterization of top-quality type IIa synthetic diamonds for new X-ray optics

We have performed a complex analysis of top-quality synthetic diamond HPHT type IIa single crystals in view of their potential application as X-ray optics elements, namely as free electron laser mirrors. We have employed X-ray topography and high-resolution diffractometry along with optical spectroscopy techniques for characterization of our synthetic diamonds.     

Optical evaluation of carrier lifetime and diffusion length in synthetic diamonds

The key electronic parameters of high-pressure-high-temperature and chemical-vapor-deposition grown diamonds have been determined at interband (hν = 5.82 eV) or below bandgap (hν = 4.68 eV) photoexcitation, using a picosecond transient grating (TG) technique. TG kinetics directly provided the values of ambipolar diffusion coefficient (6–10 cm²/s) and carrier lifetime (in a range from 0.17 to 2.8 ns) for crystals grown under different conditions. The carrier diffusion length was found to vary from 0.5 μm in CVD layers to 1.6 μm for IIa type HPHT diamond crystal. The carrier lifetimes correlated well with the nitrogen-related defect density in both types of diamonds.