化学气相沉积光学级金刚石薄膜的研究进展

化学气相沉积（CVD））金刚石薄膜优异的光学性能在近几年得到了广泛的重视,关于它的研究也在近几年取得了较大的突破。综述了CVD金刚石薄膜的光学性能,着重从成核、生长和后期处理三个方面对光学级CVD金刚石薄膜的制备进行了讨论,并对今后的研究作了展望。     

Non-equilibrium thermodynamics and the vapor phase preparation of diamond for electronic applications

Bulk diamond is unstable relative to bulk graphite except at high pressure and temperature. In spite of this, well crystallized diamond has been grown using numerous CVD methods, many of which have in common the production of atomic hydrogen and hydrocarbon radicals in regimes where solid carbon is expected to be a stable product. Several fundamentally different points of view have emerged in the effort to explain why well crystallized diamond, and not graphite or vitreous carbon, is observed in these experiments. One of the earliest argues that graphite is “etched” by atomic hydrogen at a rate higher than diamond and hence diamond is kinetically stable with respect to graphite. If diamond formation is kinetically controlled the deposition mechanism is critical and much debate has centered on the mechanism and species involved. Alternatively it can be argued that at the growth interface, diamond surfaces are stabilized by termination with hydrogen. If this is correct, and bulk reorganization ignored, then it is shown that a global understanding of the parameters important to the growth of diamond can be obtained without detailed kinetic analyses. Thus it is argued that single crystal diamond films of arbitrarily high purity and perfection are theoretically possible by CVD in spite of the bulk instability of diamond. It is also suggested that general principles exist which might be applied to the growth of other well crystallized metastable phases-notably cubic boron nitride.     

Growth and Isolation of Large Area Boron‐Doped Nanocrystalline Diamond Sheets: A Route toward Diamond‐on‐Graphene Heterojunction

Many material device applications would benefit from thin diamond coatings, but current growth techniques, such as chemical vapor deposition (CVD) or atomic layer deposition require high substrate and gas‐phase temperatures that would destroy the device being coated. The development of freestanding, thin boron‐doped diamond nanosheets grown on tantalum foil substrates via microwave plasma‐assisted CVD is reported. These diamond sheets (measuring up to 4 × 5 mm in planar area, and 300–600 nm in thickness) are removed from the substrate using mechanical exfoliation and then transferred to other substrates, including Si/SiO₂ and graphene. The electronic properties of the resulting diamond nanosheets and their dependence on the free‐standing growth, the mechanical exfoliation and transfer processes, and ultimately on their composition are characterized. To validate this, a prototypical diamond nanosheet–graphene field effect transistor‐like (DNGfet) device is developed and its electronic transport properties are studied as a function of temperature. The resulting DNGfet device exhibits thermally activated transport (thermionic conductance) above 50 K. Below 50 K a transition to variable range hopping is observed. These findings demonstrate the first step towards a low‐temperature diamond‐based transistor.     

RF化学气相淀积金刚石薄膜

本文论述了金刚石薄膜的优点，比较了化学淀积金刚石薄膜的常用方法的优缺点，主要介绍了电容耦合射频化学气相淀积金刚石薄膜的原理和近期国际对典型电容耦合气相淀积设备的改进研究。     

Molecular view of diamond CVD growth

In this paper, we discuss the simulation of the chemical vapor deposition (CVD) of diamond films on the molecular scale. These simulations are performed using a kinetic Monte Carlo method that combines the surface chemistry that is important to diamond growth with an atomic-scale picture of the diamond surface and its evolving atomic structure and morphology. We address the determination of surface reaction kinetics and growth conditions from experiments and reactor-scale models, and the prediction of polycrystalline film texture and morphology from the molecular-scale results. The growth rates and the concentrations of incorporated point defects as a function of substrate temperature for {100}- and {111}-oriented diamond films are obtained from the molecular-scale growth simulations. The {100} growth rates increase with temperature up to 1200K and then decrease above this value. The {111} growth rates increase with temperature at all of the temperatures studied. The concentrations of point defects in the {100} and {111} films are low at substrate temperatures below 1200K, but increase substantially at higher temperatures. The growth efficiency, measured as the ratio of film growth rate to defect concentration, is maximum between 1100–1200K for both film orientations, suggesting that this temperature range is ideal for CVD diamond growth under the simulated growth conditions.     

新型半导体光电材料—CVD金刚石

综述了近年来 CVD 金刚石作为新型半导体光电材料的研究进展。主要包括:p型、n 型掺杂 CVD 金刚石的制备和性能;CVD 金刚石的发光特性;由 CVD 金刚石制备的发光器件。指出了目前 CVD 金刚石工业也所急待解决的一些问题。     

Combined single-crystalline and polycrystalline CVD diamond substrates for diamond electronics

The fabrication of diamond substrates in which single-crystalline and polycrystalline CVD diamond form a single wafer, and the epitaxial growth of diamond films on such combined substrates containing polycrystalline and (100) single-crystalline CVD diamond regions are studied.     

金刚石薄膜高温器件

本文详细地论述了低压气相生长的金刚石薄膜作为一种新型半导体材料的研究进展,讨论了金刚石薄膜与金属的欧姆接触和整流接触,以及可以在高温区工作的金刚石薄膜Schottky二极管和MESFET器件。最后,讨论了目前金刚石薄膜作为半导体材料所遇到的两个尚无法实现的问题:n型掺杂和异质外延单晶膜的生长。     

CVD金刚石（膜）制备技术及应用进展

化学气相沉积（CVD）方法是金刚石（膜）制备的主流技术,经过多年的发展,已从最初的微米金刚石膜发展到纳米金刚石膜,至目前高质量的单晶金刚石,应用领域不断扩展。除了工业和民用领域外,纳米金刚石膜在MEMS／NEMs、生物医学的应用进展引起业界关注,其中大尺寸单晶金刚石的制备是推动这些应用的关键。本文分析了MPCVD金刚石成膜特点,讨论了现阶段CVD金刚石膜商业化推广应用的制约因素,展望了今后金刚石膜的发展前景。     

金刚石薄膜的结构特征与电导率的相关性

讨论了ＣＶＤ金刚石薄膜作为半导体材料的一些基本特性，主要叙述了金刚石薄膜的生长习性和结构特征对其电性能的影响，即其电导率的“尺度交 ”和“晶面效应”，以及这些效应对由金刚薄膜制备的半导体器件性能的影响。     

Electronic properties of diamond for high-power device applications

The generation and transport of impact-ionized electrons in diamond are investigated using secondary electron emission spectroscopy. By studying secondary electron emission from diamond surfaces having a negative electron affinity (NEA), the total transmitted intensity and the full energy spectrum of the internal electrons are revealed in the measurements. Electron yield and energy distribution measurements from C(100) and CVD diamond samples are analyzed as a function of incident beam energy and information is obtained on both the internal gain and electron energy distribution following impact ionization as well as the effects of the transport process on the internal electron distribution. High internal gain and efficient electron transport are inferred from an analysis of the very high yields measured from both samples. In fact, by fitting calculated yield curves to the measured yield data, we deduce a lower limit on the electron escape depth of 5 μm and 1.3 μm in the C(100) and CVD diamond samples, respectively. Energy spectra measured from the diamond samples contain an intense, low-energy peak whose energy position and width are independent of incident beam energy. Based on an analysis of the energy distribution data, a model of the impact-ionization process in diamond is presented.     

Thermal CVD of homoepitaxial diamond using CF/sub 4/ and F/sub 2/

For the first time, diamond has been grown using low-pressure thermal CVD. No additional excitation such as plasmas or filaments was used. The authors report the homoepitaxial growth of diamond on type II-A diamond     

金刚石电子器件的研究进展

简述了金刚石半导体电气性质,即高击穿电场、宽带隙、高载流子饱和速度、高载流子迁移率和高热导率。回顾了金刚石器件的研究进程。讨论了器件的工作机理,包括掺杂和空穴积累层。详细描述了几种具有潜力的金刚石电子器件,如高压二极管和功率场效应管。尽管金刚石器件研究仍存在一些问题,如掺杂机理复杂,金刚石的单晶尺寸太小等,严重制约金刚石电子的进展,但是由于金刚石是超高功率和高温器件的优良半导体材料,具有替代行波管技术的潜力。当前,CVD金刚石已经大量用于微电子和光电子,包括激光二极管、微波器件、半导体散热器等。     

Full-Wafer Characterization of AlGaN/GaN HEMTs on Free-Standing CVD Diamond Substrates

We report on electrical characterization and uniformity measurements of the first conventionally processed AlGaN/GaN high electron mobility transistors (HEMTs) on free-standing chemical-vapor-deposited (CVD) diamond substrate wafers. DC and RF device performance is reported on HEMTs fabricated on $sim!!hbox{130-}muhbox{m}$-thick and 30-mm round CVD diamond substrates without mechanical carrying wafers. A measured $f_{T} cdot L_{G}$ product of 12.5 $hbox{GHz} cdot muhbox{m}$ is the best reported data for all GaN-on-diamond technology. X-band power performance of AlGaN/GaN HEMTs on diamond is reported to be 2.08 W/mm and 44.1% power added efficiency. This letter demonstrates the potential for GaN HEMTs to be fabricated on CVD diamond substrates utilizing contact lithography process techniques. Further optimization of the epitaxy and diamond substrate attachment process could provide for improvements in thermal spreading while preserving the electrical properties.      

Microwave and hot filament chemical vapour deposition of diamond multilayers on Si and WC-Co substrates

A serious problem in the use of chemical-vapour-deposited polycrystalline diamond coatings in electronics, optics as well as in cutting tools is the high surface roughness. In our work, microcrystalline and nanocrystalline diamond films with a thickness of 0.5-5 μm were deposited using microwave chemical vapour deposition (MW CVD), and with a thickness of 1-4 μm by hot filament chemical vapour deposition (HF CVD). For both deposition technologies, we investigated the effect of a negative bias upon the formation of microcrystalline and nanocrystalline diamond multilayers. In the cases of smooth Si and relief WC-Co substrate surfaces, the multilayers were found to have a “cauliflower” look. The structure and composition of deposited layers were checked by scanning electron microscopy and Raman spectroscopy.     

CVD金刚石膜用作TaN2热敏打印头表面保护层的研究

报道了用微波等离子体化学气相淀积技术在ＴａＮ２电阻材料上淀积高质量金刚石薄膜的制备工艺，以及扫描电镜、Ｘ射线衍射、拉曼光谱、压痕测试的测试结果。探讨了提高金刚石膜在非金刚石衬底成核密度与粘附性的实验方法，从实验上证实了ＣＶＤ金刚石膜可以用作ＴａＮ２热敏打印头表面保护层。     

高质量CVD金刚石自支撑膜的连续激光损伤研究

利用HJ - 4型连续CO2 激光对金刚石膜进行了激光损伤阈值的研究,损伤后的金刚石膜用SEM和Raman进行了表征。研究结果表明,高质量CVD自支撑金刚石膜具有较高的 激光损伤阈值,金刚石膜抗连续激光损伤阈值的范围是在1. 15 ×106 ～2. 26 ×106W / cm2。金刚石膜激光损伤主要是由于热震损伤,其机制属于热- 力耦合机制。     

金刚石膜表面微结构红外增透性能研究

CVD金刚石是一种性能优异的红外光学窗口材料，但其在红外波段的理论透过率仅能实现约71%。通过表面亚波长结构设计可进一步增强CVD金刚石膜的光学透过性能。该研究首先通过理论模拟，建立了金刚石微结构特征与光学增透之间的定量关系。基于此为指导，探讨了在具有微结构硅片表面，采用MPCVD方法复制生长出具有微结构的金刚石自支撑光学级薄膜，用于提升金刚石膜在红外波段的透过率。采用扫描电镜（SEM）观察了原始硅片和金刚石表面及微结构形貌，通过拉曼散射光谱评估了金刚石的生长质量及形核层影响，采用红外光谱仪测试了金刚石红外透过率。结果显示，单面构筑微结构后，金刚石膜在8~12 μm波段的透过率可从70%提升至76%，说明表面微结构能显著提升金刚石膜的光学透过性能。非金刚石形核层以及表面微结构的完整性不足可能是导致实验结果与理论模拟结果具有一定偏差的主要原因。     

C-H体系CVD金刚石薄膜取向生长的热力学分析

化学气相淀积金刚石薄膜过程中 ,CH3 和C2 H2 是金刚石生长的主要前驱基团。C2 H2 与CH3 浓度比 ( [C2 H2 ]/[CH3 ])的变化将影响金刚石薄膜的生长取向。用非平衡热力学耦合模型计算了C H体系CVD金刚石薄膜生长过程中C2 H2 浓度和CH3浓度随淀积条件的变化 ,并进一步获得了 [C2 H2 ]/[CH3 ]随衬底温度和CH4浓度的变化关系 ,从理论上探讨了金刚石薄膜 ( 1 1 1 )面和 ( 1 0 0 )面取向生长与淀积条件的关系。在衬底温度和CH4浓度由低到高的变化过程中 ,[C2 H2 ]/[CH3 ]逐渐升高 ,导致金刚石薄膜的形貌从 ( 1 1 1 )晶面转为 ( 1 0 0 )晶面。     

High electrical resistivity of CVD-diamond

Due to its combination of excellent thermo-mechanical properties and electrical properties such as the high electrical resistivity and high dielectric strength, diamond seems a promising material for specialized dielectric applications. Due to the great advances in the growth technology of diamond films by chemical vapour deposition (CVD) on e.g. Si-substrates, new applications can be expected in microelectronics. An important technological result for dielectric applications is that high electrical resistivity diamond films can be obtained after an appropriate heat treatment of the as-grown films.