Optical and electronic performances of CVD diamond film andits applications in radiation detectors

The outstanding properties of CVD diamond film such as electronic, optical, thermal and mechanical and the high radiation hardness have made it an ideal candidate material for radiation detectors in severe environments. Fabrication of ＇detector grade＇ CVD diamond films and development of CVD diamond detectors have been leading edge subjects. Micro-strip gas chamber （MSGC） fabricated on CVD diamond substrate would overcome the charge-up effect and the substrate instability, which has been a hotspot in the research of gas detectors.

Fabrication and Characterization of FeNiCr Matrix-TiC Composite for Polishing CVD Diamond Film

Dynamic friction polishing （DFP） is one of the most promising methods appropriate for polishing CVD diamond film with high efficiency and low cost. By this method CVD diamond film is polished through being simply pressed against a metal disc rotating at a high speed utilizing the thermochemical reaction occurring as a result of dynamic friction between them in the atmosphere. However, the relatively soft materials such as stainless steel, cast iron and nickel alloy widely used for polishing CVD diamond film are easy to wear and adhere to diamond film surface, which may further lead to low efficiency and poor polishing quality. In this paper, FeNiCr matrix-TiC composite used as grinding wheel for polishing CVD diamond film was obtained by combination of mechanical alloying （MA） and spark plasma sintering （SPS）. The process of ball milling, composition, density, hardness, high-temperature oxidation resistance and wear resistance of the sintered piece were analyzed. The results show that TiC was introduced in MA-SPS process and had good combination with FeNiCr matrix and even distribution in the matrix. The density of composite can be improved by mechanical alloying. The FeNiCr matrix-TiC composite obtained at 1273 K was found to be superior to at 1173 K sinterin8 in hardness, high-temperature oxidation resistance and wearability. These properties are more favorable than SUS304 for the preparation of high-performance grinding wheel for polishing CVD diamond film.

A CVD diamond film detector for pulsed proton detection

A chemical vapour deposition （CVD） diamond film detector was prepared and the main characteristics for pulsed proton detection were studied at Beijing Tandem Accelerator. The result shows that the charge collection efficiency of the detector increases with increasing electric field intensity and reaches to 9.44% at 5 V/μm with the charge collection distance of 15.9 μm. The relationship between the sensitivity of the detector and proton energy is consistent with the Monte Carlo （MC） simulation result. Its plasma time for a pulse with 4.85×10^5 protons is 1l.2ns. The dose threshold for onset of damage under 9MeV proton irradiation in the detector is about 10^13 cm^-2. All of the results show that a CVD diamond detector has fast time response and high radiation hardness, and can be used in pulsed proton detection.

Prediction of the Interface Temperature Rise in Tribochemical Polishing of CVD Diamond

Tribochemcial polishing is one of the most efficient methods for polishing CVD （Chemical Vapor Deposition） diamond film due to the use of catalytic metal. However the difficulty to control the interface temperature during polishing process often results in low material removal because of the unstable contact process. So this research investigates the contact process in the tribo- chemical polishing of CVD diamond film and proposes a dynamic contact model for predicting the actual contact area, the actual contact pressure, and the interface tem- perature in the polishing process. This model has been verified by characterizing surface metrology of the CVD diamond with Talysurf CLI2000 3D Surface Topography and measuring the polishing temperature. The theoretical and experimental results shows that the height distribution of asperities on diamond film surface in the polishing process is well evaluated by combining the height distribution of original and polished asperities. The modeled surface asperity height distribution of diamond film agrees with the actual surface metrology in polishing process. The actual contact pressure is very large due to the small actual contact area. The predicted interface temperature can reach the catalytic reaction temperature between diamond and polishing plate when the lowest rotation speed and load are 10 000 r/min and 50 N, respectively, and diamond material is significantly removed. The model may provide effective process theory for tribochemcial polishing.

Atomic scale KMC simulation of {100} oriented CVD diamond film growth under low substrate temperature—Part I Simulation of CVD diamond film growth under Joe-Badgwell-Hauge model

The growth of (100} oriented CVD (Chemical Vapor Deposition) diamond film under Joe-Badgwell-Hauge (J-B-H) model is simulated at atomic scale by using revised KMC (Kinetic Monte Carlo) method. The results show that: (1) under Joe's model, the growth mechanism from single carbon species is suitable for the growth of (100) oriented CVD diamond film in low temperature; (2) the deposition rate and surface roughness (Rq) under Joe's model are influenced intensively by temperature (Ta) and not evident bymass fraction W of atom chlorine; (3)the surface roughness increases with the deposition rate, i.e. the film quality becomes worse with elevated temperature, in agreement with Grujicic's prediction; (4) the simulation results cannot make sure the role of single carbon insertion.

Atomic scale KMC simulation of {100} oriented CVD diamond film growth under low substrate temperature-Part Ⅱ Simulation of CVD diamond film growth in C-H system and in Cl-containing systems

The growth of {100}-oriented CVD diamond film under two modifications ofJ-B-H model at low substrate temperatures was simulated by using a revised KMC method at atomicscale. The results were compared both in Cl-containing systems and in C-H system as follows: (1)Substrate temperature can produce an important effect both on film deposition rate and on surfaceroughness; (2) Aomic Cl takes an active role for the growth of diamond film at low temperatures; (3){100}-oriented diamond film cannot deposit under single carbon insertion mechanism, which disagreeswith the predictions before; (4) The explanation of the exact role of atomic Cl is not provided inthe simulation results.

A MONTE CARLO SIMULATION OF THE CVD DIAMOND FILM

A Monte Carlo algorithm has been developed by the authors to simulate the chemical vapor deposition (CVD) processes of diamond films. The method considers both the diffusion and the incorporation of the growth radicals on the growing surface in simulating the evolution of the morphology and microstructure. The calculation of configuration energy is used to determine the orientation of adsorbed growth radicals. The effect of processing variables such as nucleation density and substrate temperature on the morphology and microstructure is discussed. It is found that competitive characteristic and coarsening effect exist in the simulation results, which agree with the experimental observations.

A review on polishing technology of large area free-standing CVD diamond films

Recently,with the rapid development of chemical vapor deposition(CVD)technology,large area free-standing CVD diamond films have been produced successfully.However,the coarse grain size on the surface and the non-uniform thickness of unprocessed CVD diamond films make it difficult to meet the application requirement.The current study evaluates several existing polishing methods for CVD diamond films,including mechanical polishing,chemical mechanical polishing and tribochemical polishing technology.

The glass roller cutter made of CVD diamond film

As a cutting tool,diamond films made by chemical vapor deposition(CVD) outperformed polycrystalline diamond(PCD) sintered under ultrahigh pressure.For example,the longevity of the CVD tools may be 2～5 times that of PCD inserts.In addition,the former cutting paths are strainghter with less chipping on the edge.However,there have been no report on CVD diamond films that were used as a roller scriber for splitting large glass panels.Our research demonstrated that the CVD diamond film could concentrate the energy in a smaller area(about 1/4),so the glass compressed by the tip of the diamond film was under a larger tensile stress in perpendicular to the direction of compression.The tensile stress then initiated the microcracks that were more in line with the direction of the compression. The reason that CVD diamond film could concentrate the compressive stress was due to its 100%diamond content.The high diamond content could allow the tip to be polished sharper.In contrast,the PCD cutting tip contained micro grains of cobalt that were softer than glass.As a result,the compressional stress was spreading out due to the larger area of contact.Consequently,the microcracks initiated at the PCD tip were random and they might not propagate along the direction of cutting.

Investigation on the priming effect of a CVD diamond microdosimeter

CVD diamond microdosimeter is an ideal substitute of common Si.GaAs detector for extremely strong radiation experimental environment due to its high band gap energy, fast charge collection, low dielectric constant and hardness. In order to improve its character, a CVD diamond microdosimeter was irradiated by a proton dose of 46 Gy, and a lateral micro-ion beam induced charge (IBIC) technique was utilized to characterize it in low beam current (～fA). It was clearly shown that charge collection efficiency and energy resolution were greatly improved after proton irradiation of that dose. Moreover, the homogeneities of both its counting performance and collection efficiency were enhanced. Proton irradiation of 46 Gy has been proved to be an effective way to prime a CVD diamond.

Nitrogen Desorption and Positron Sensitive Defect of CVD Diamond

The chemical vapor deposition (CVD) process can produce single or poly-crystalline diamond samples of high purity or with controlled doping concentrations. The defect type in the CVD diamonds can be changed by heating the samples. Controlling the defect type can be used to create devices for quantum diamond switches that could be used in radiation sensors and quantum information technology. Eight samples of CVD diamonds were analyzed with Doppler broadening of positron annihilation radiation (DBAR) before and after annealing in high vacuum with an electron gun. Between temperatures of 1700 - 1850 K, nitrogen was liberated from the diamond sample. At these high temperatures, the surface was graphitized and a change in the color and transparency of the diamond was observed. Some of the samples were analyzed with DBAR during periods with and without light. The defect properties were observed to change depending on the time exposure to the positron beam and were then regenerated by exposure to light. The DBAR data is compared to photoluminescence data and a time varying defect state is discussed for detector and optical grade type II CVD diamonds.

Adhesive strength of CVD diamond thin films quantitatively measured by means of the bulge and blister test

Large advancement has been made in understanding the nucleation and growth of chemical vapor deposition （CVD） diamond, but the adhesion of CVD diamond to substrates is poor and there is no good method for quantitative evaluation of the adhesive strength. The blister test is a potentially powerful tool for characterizing the mechanical properties of diamond films. In this test, pressure was applied on a thin membrane and the out-of-plane deflection of the membrane center was measured. The Young＇s modulus, residual stress, and adhesive strength were simultaneously determined using the load-deflection behavior of a membrane. The free-standing window sample of diamond thin films was fabricated by means of photolithography and anisotropic wet etching. The research indicates that the adhesive strength of diamond thin films is 4.28±0.37 J/m^2. This method uses a simple apparatus, and the fabrication of samples is very easy.

C-H-F氛围下金刚石薄膜的低温CVD生长过程分析

基于第一性原理的密度泛函理论对C-H-F氛围下低温CVD金刚石薄膜的生长过程进行仿真分析,计算H、F原子在氢终止金刚石表面发生萃取反应的吸附能、反应热与反应能垒,并分析CF_(3)、CF_(2)、CF 3种生长基团在带有活性位点基底上的吸附。结果表明:与H原子相比,F原子更容易在氢终止金刚石表面萃出H,并以HF形式脱附,且在C-H-F氛围下有利于在低温时产生更多的活性位点;CF_(3)、CF_(2)、CF基团在吸附后的结构和吸附能绝对值都更有利于金刚石相的生成,适当提高CF_(3)、CF_(2)、CF基团的浓度有助于实现金刚石相的更高速率生长。

新型CVD金刚石涂层刀具铣削高性能各向同性石墨研究

利用自主研发的新型CVD金刚石复合涂层刀具对自行研制的高密高强各向同性石墨材料进行了铣削加工试验,对比测试了新型CVD金刚石复合涂层刀具与PCD刀具的切削性能。试验结果表明,PCD刀具铣削加工25min其后刀面磨损已超过磨钝标准0.3 mm,新型CVD金刚石复合涂层刀具加工到45 min时,其后刀面磨损量仅为0.25 mm,这说明新型CVD金刚石复合涂层刀具高速铣削石墨时表现出良好的耐磨性和使用寿命,可以适应高性能各向同性石墨的加工需求。铣削加工试验还发现新型CVD金刚石复合涂层刀具加工的石墨表面质量在初期不如PCD刀具,但在更长时间加工情况下,其加工表面质量优于PCD刀具。

WC-Co硬质合金/CVD金刚石涂层刀具研究现状

化学气相沉积(Chemical vapor deposition,CVD)金刚石涂层刀具具有高硬度、优异的耐磨性、良好的冲击韧性和化学稳定性,能满足高效率、高精度的加工要求,逐渐成为切削铝和高硅铝合金、碳纤维增强复合材料及石墨等轻质量高强度难加工材料的主流涂层刀具。基于WC-Co硬质合金为基体的CVD金刚石涂层刀具在切削加工过程中容易发生CVD金刚石涂层的剥落,自主研发结合性能优良、长时间加工稳定的WC-Co硬质合金/CVD金刚石涂层刀具仍是该领域国内外发展的必然趋势。目前,研究者为了提高WC-Co硬质合金/CVD金刚石涂层刀具的结合性能,采用化学刻蚀法和机械处理法相结合去除WC-Co硬质合金基体表层中的Co粘结相,发现其能增强涂层与基体的结合强度,但基体表层Co粘结相含量的减少容易导致基体中形成脆化层,降低基体的强度和韧性。为了减少基体的强度和韧性损失,研究者在WC-Co硬质合金基体和金刚石涂层之间制备稳定的含Co中间化合物或沉积中间层,成功阻挡Co粘结相的热扩散。除了上述方法外,研究者还通过调控金刚石涂层工艺参数和结构,将微米晶与纳米晶金刚石层叠相结合,来提高金刚石涂层刀具的摩擦学性能和涂层与基体间结合强度。本文综述了WC-Co硬质合金/CVD金刚石涂层刀具的应用进展,明确了WC-Co硬质合金与CVD金刚石涂层间附着失效是刀具切削加工中最主要的失效形式,详细分析了影响附着失效的主要原因。在此基础上,着重介绍了各种优化工艺对增强涂层刀具性能影响的最新研究进展;指出了WC-Co硬质合金/CVD金刚石涂层刀具的性能受化学刻蚀、机械刻蚀、形成含钴化合物层、沉积中间层等基体前处理以及金刚石涂层工艺参数和结构的影响较大,对于不同牌号或不同厂家生产的同种牌号的WC-Co硬质合金基材,需要进行不同的表面前处理,而针对不同的切削加工材料,需要采用合适的金刚石涂层沉积工艺和结构以提高涂层与基材之间的结合强度,进而提高刀具的性能;最后提出了研制一种普适性强的基体前处理、涂层工艺和结构创新策略,以实现不同应用场景下WC-Co硬质合金/CVD金刚石涂层刀具的高效长寿命切削,可能是未来的研究方向。

Growth behavior of CVD diamond films with enhanced electron field emission properties over a wide range of experimental parameters

In this study, diamond films were synthesized on silicon substrates by microwave plasma enhanced chemical vapor deposition（CVD） over a wide range of experimental parameters. The effects of the microwave power,CH;/H;ratio and gas pressure on the morphology, growth rate, composition, and quality of diamond films were investigated by means of scanning electron microscope（SEM）, X-ray diffraction（XRD）, Raman spectroscopy and X-ray photoelectron spectroscopy（XPS）. A rise of microwave power can lead to an increasing pyrolysis of hydrogen and methane, so that the microcrystalline diamond film could be synthesized at low CH;/H;levels. Gas pressure has similar effect in changing the morphology of diamond films, and high gas pressure also results in dramatically increased grain size. However,diamond film is deteriorated at high CH;/H;ratio due to the abundant graphite content including in the films. Under an extreme condition of high microwave power of 10 kW and high CH;concentration, a hybrid film composed of diamond/graphite was successfully formed in the absence of N;or Ar,which is different from other reports. This composite structure has an excellent measured sheet resistance of 10-100 Ω/Sqr. which allows it to be utilized as field electron emitter. The diamond/graphite hybrid nanostructure displays excellent electron field emission（EFE） properties with a low turn-on field of 2.17 V/μm and β= 3160, therefore it could be a promising alternative in field emission applications.

Preparation and Characterization of High Quality Diamond Films by DC ArcPlasma Jet CVD Method

Under optimal conditions free-standing high quality diamond films were prepared by DC arc plasma jet CVD method at a growth rate of 7-10 Pm/h. Surface and cross section morphologies of the diamond films were observed by SEM. Raman spectrometer wasused to characterize the quality of diamond films. The IR transmittivity measured by IR spectrometer is close to the theoretical value ofabout 71% in the far infrared band. The thermal conductivity measured by photothermal deflection exceeds 18 W/cm' K. <l 10> is thepreferential growth orientation of the films detected by X-ray diffractometer. As s result, the extremely high temperature of DC arc plasma jet can produce supersaturated atomic hydrogen, which played an important role in the process for the deposition of high quality diamond films.

CVD金刚石涂层前预处理对硬质合金基体强度的影响

CVD金刚石涂层硬质合金刀具是有色金属及合金、石墨、陶瓷和碳纤维增强塑料(CFRP)等复合材料机械加工的理想刀具。但金刚石涂层前对WC-Co硬质合金基体的预处理过程在消除表面Co改善涂层附着力的同时也降低了基体强度。通过正交试验并采用SEM和EDS分析试样表面形貌和Co含量,采用XRD分析试样表层的相组成,研究了预处理对两种WC晶粒度的WC-6Co硬质合金基体强度的影响机制。结果表明:酸、碱预处理均显著降低基体强度,热处理则可消除酸碱处理对强度的不利影响。预处理对不同WC晶粒度的硬质合金基体强度的影响明显不同。粗晶硬质合金预处理后抗弯强度降低幅度更大,其抗弯强度的Weibull模数减小也更显著。相对而言,粗晶硬质合金的抗弯强度对酸腐蚀时间tC更敏感,而细晶硬质合金则受碱腐蚀时间tM的影响更大。因此,金刚石涂层前,应根据不同硬质合金基体的成分和微观结构匹配合适的预处理制度。

Wear of CVD thick film diamond cutter while machining laminated flooring

The wide application of high pressure laminated (HPL) flooring has an insistent need for cutting tools with an excellent performance and fine cutting quality. Chemical vapor deposition (CVD) thick film diamond is a promising material for the machining of HPL flooring. In the present work, CVD thick film diamond tools were used to mill the wear resistance layer of HPL flooring. Wear volumes of flank face were examined by optical microscopy, and micro wear morphologies were observed by scanning electron microscopy (SEM). The experiments revealed that the predominant wear characteristics of CVD diamond tools were transgranular cleavage wear and intergranular peeling of the CVD diamond. Experimental results also showed that twin characteristic, cavity defect, micro crack and grain size of CVD thick film diamond contributed greatly to the wear process of CVD thick film diamond tools. The effects caused by the factors were also analyzed in detail in the paper.

基于第一性原理的CVD金刚石涂层表面氧原子作用分析

采用第一性原理方法研究了氧原子在CVD金刚石涂层表面吸附形成的两种氧掺杂结构的差异及脱附CO的难易程度.仿真计算结果表明:氧原子在金刚石表面顶位和桥位吸附形成C=O羰结构和C-O-C醚结构,改变与其直接成键的局部金刚石结构;C-O-C结构吸附能比C=O结构大,其结构更加稳定;C=O结构断键脱附形成CO的能垒比C-O-C结构更低,CVD金刚石涂层表面脱附CO主要是以C=O断键形成;氢终止表面能够增强碳原子之间成键,提高C=O脱附的能垒,而氧终止表面作用相反,降低脱附能垒.