Application of N- and B-doped CVD diamond layers for cyclic voltammetry measurements

Conductive polycrystalline diamond layers prepared by the CVD process have received attention from electrochemists owing to such superior electrochemical properties as the wide potential window, the very low background current, the stability of chemical and physical properties.In this paper, the cyclic voltammetry application using N- and B-doped diamond electrodes was studied. Diamond layers, doped with boron and nitrogen, were synthesized on a silicon substrate in a hot-filament CVD reactor. The obtained diamond layers were characterized using Raman spectroscopy and scanning electron microscopy (SEM).The electrochemical properties of diamond layers were measured in KCl and NaCl basic solutions to gain knowledge about their potential application as an electrode material.It was found that boron doped diamond electrodes showed potential windows up to about 7 V which were almost twice wider than those observed for conventional Pt electrodes.     

Application of N- and B-doped CVD diamond layers for cyclic voltammetry measurements

Conductive polycrystalline diamond layers prepared by the CVD process have received attention from electrochemists owing to such superior electrochemical properties as the wide potential window, the very low background current, the stability of chemical and physical properties.In this paper, the cyclic voltammetry application using N- and B-doped diamond electrodes was studied. Diamond layers, doped with boron and nitrogen, were synthesized on a silicon substrate in a hot-filament CVD reactor. The obtained diamond layers were characterized using Raman spectroscopy and scanning electron microscopy (SEM).The electrochemical properties of diamond layers were measured in KCl and NaCl basic solutions to gain knowledge about their potential application as an electrode material.It was found that boron doped diamond electrodes showed potential windows up to about 7 V which were almost twice wider than those observed for conventional Pt electrodes.     

Broad band photoluminescence studies of diamond layers grown by hot-filament CVD

Photoluminescence and Raman spectroscopy were employed to investigate the broad band luminescence in thin diamond films grown on a silicon substrate by the HF CVD technique. The broad band luminescence with a maximum emission at 1.8–2 eV observed for CVD diamonds is characteristic for amorphous carbon with sp²-hybridized carbon bonds. As was shown by the Raman spectroscopy our diamond layer contained certain amounts of amorphous carbon phase and diamond nanocrystals which were the source of an additional energy state within the diamond energy gap. The experimental results precluded the possibility of broad band luminescence being due to the electron–lattice interaction. The amorphous carbon and diamond nanocrystals admixture in polycrystalline diamond layer introduced a defect state in the energy gap not in the form of point defects but rather in the form of a line or extended defects. In consequence these extended defects were responsible for the broad PL spectrum in the CVD diamond films.     

CVD金刚石紫外探测器

CVD金刚石紫外探测器有极强的辐射硬度及耐腐蚀性,在宽禁带半导体紫外探测器中占有重要地位.本文主要对金刚石紫外探测器的发展进展、探测机理、电极模式及应用领域做了简要回顾.     

Improvements in CVD diamond properties for radiotherapy dosimetry

The goal of this work was to compare the behaviour of a chemical vapour deposited (CVD) diamond sample, grown at the University of Florence using a local procedure, with that of a commercial CVD diamond. The comparison was performed exposing both systems to 25 MV photons and measuring the current response during irradiation. Properties of dosimetric interest such as stability of response, dose rate dependence and rise time were investigated. After a preliminary study, which evidenced better performances of the commercial device with respect to the local CVD diamond, the latter was irradiated with a high fluence of fast neutrons. As a result of the neutron treatment, the quality of the CVD home-made diamond has been improved to match with that of the commercial dosemeter.     

Thermal conductivity of CVD diamond films

Diamond films 60 and 170 µm in thickness were grown by PACVD (plasma-assisted chemical vapor deposition) under similar conditions. The thermal diffusivity of these freestanding films was measured between 100 and 300 K using AC calorimetry. Radiation heat loss from the surface was estimated by analyzing both the amplitude and the phase shift of a lock-in amplifier signal. Thermal conductivity was calculated using the specific heat data of natural diamond. At room temperature, the thermal conductivity of the 60 and 170 m films is 9 and 16 W-cm^–1. K^–1 respectively, which is 40–70% that of natural diamond, The temperature dependence of thermal conductivity of the CVD diamond films is similar to that of natural diamond, Phonon scattering processes are considered using the Debye model, The microsize of the grain boundary has a significant effect on the mean free path of phonons at low temperatures. The grain in CVD diamond film is grown as a columnar structure, Thus, the thicker film has the larger mean grain size and the higher thermal conductivity. Scanning electron microscopy (SEM) and Raman spectroscopy were used to study the microstructure of the CVD diamond films. In this experiment, we evaluated the quality of CVD diamond film of the whole sample by measuring the thermal conductivity.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

High-temperature Raman study in CVD diamond

Measurements of the Raman spectra in chemical vapour deposition (CVD) diamond films at temperatures up to 1200 K are presented. Specifically, the evolution of Raman line position, line width, and intensity were monitored as a function of heating time. The red shifting and the line width broadening of CVD diamond's Raman line with temperature are very similar to that of natural diamond's. However, the detailed temperature dependence of Raman line width depends on the orientation of the CVD diamond crystal and the ambient gas used during thermal treatment. Since the CVD diamond usually exhibited a broader Raman spectra than natural diamond, the evolution of the line width upon heating is thus expected to depend on the origins and the annealing effects of the residual stress. For (111) CVD diamond subjected to annealing in air at 973 K, the line width decreased by more than one wavenumber while the line intensity increased by more than an order of magnitude before it decreased subsequently. In contrast, there is hardly any observable changes of the line width for (100) CVD diamond heated in air at 1173 K. Measurements conducted in He versus in air suggested that the reduction of the non-diamond carbon phase (therefore, the reduction of stress) is likely due to oxidation, which occurs more readily in (111) than in (100).     

Porous silicon capping by CVD diamond

In the last few years important research efforts were put concerning the optical properties of porous silicon (PS). Some interesting devices can be made using this new material (ex: L.E.D.s and micro cavities). However, a set of unsolved problems is keeping some distance between PS and its applications. Among these problems are the chemical instability and mechanical weakness.In this work, we attempted a CVD diamond protective layer deposition on PS. The optical properties of PS were preserved, as confirmed by photoluminescence (PL). The diamond film adhesion was checked by microhardness testing showing no crack propagation with a load of 200 gf. Nanoindentation measurements with 0.1 gf on the resulting surface showed a ten fold increase in hardness with respect to the uncoated material.     

The toughness of free-standing CVD diamond

A four-point bend test was used to determine the fracture toughness of mechanical grade and di-electric (optical) grade chemical vapour deposited (CVD) diamond. The validity of the test was first confirmed by measuring the toughness of alumina and confirming the results with literature values. The toughnesses of both types of CVD were similar; 8.5 ± 1.0 and 8.3 ± 0.4 MPa respectively. This is higher than the value of 3 4 ± 0 5 MPa measured for good quality natural diamond by Field and Freeman, [1] using an indentation technique. It is suggested that this is primarily due to differences in surface roughness. There were enough samples to make a preliminary study of the effect of temperature and these data are reported.     

Twin quintuplet surfaces in CVD diamond

Chemical vapor deposition (CVD) of diamond films and wafers is a well established and flexible technology in which deposition parameters control the deposition rate as well as diamond properties, quality and shape. This article deals with surface morphology and crystallography of wafers, with emphasis on twin blocks and twin quintuples. In the study described here we have determined surface facet crystallography of two diamond wafers groups, one that contains Σ3 twin blocks and the other that has a large population of twin quintuplets. The tool used for the study is a scanning electron microscope (SEM) and the technique to identify surface crystallography involves only accurate tilting and surface observation. A basic knowledge of the twin structure enables accurate determination of surface crystallography.     

Thermoluminescence properties of CVD diamond for clinical dosimetry use

The application of diamond to dosimetry is desirable because of its tissue equivalence, chemical inertness and small size, but this has not been commercially viable owing to the non-reproducible response of natural diamond. The chemical vapour deposition (CVD) of diamond permits controlled, reproducible and large-scale production of this material at potentially low cost. An investigation of some clinically relevant features like the depth-dose distribution as well as the absorbed dose profile, obtained using thermoluminescence (TL), is reported for several CVD diamond films. The TL characterisation presented here shows that CVD diamond films should be excellent TL-mode detectors in instances of radiotherapy and in vivo radiation dosimetry.     

CVD金刚石膜的场发射机制

利用热灯丝化学气相沉积方法在光滑的钼上沉积了金刚石膜,用扫描电子显微镜和Raman谱对金刚石膜进行了分析。结果表明金刚石膜是由许多金刚石晶粒组成,晶粒间界主要是石墨相,并且在膜内有许多缺陷。金刚石膜的场发射结果表明高浓度CH4形成的金刚石膜场发射阈位电场较低浓度CH4形成的金刚石为低。这意味着杂质（如石墨）和缺陷（悬挂键）极大地影响了膜的场发射性能。根据以上结果,提出了一种CVD金刚石膜的场发射机制即膜内的缺陷增强膜内的电场,石墨增大电子的隧穿系数以增强CVD金刚石膜的场发射。     

n-Type CVD diamond: Epitaxy and doping

Diamond is a semiconductor with superlative properties in terms of operating temperature, breakdown voltage and thermal dissipation for high power electronic applications. The p-type doping is currently controlled but it is not the case for the n-type doping. In spite of the low solubility of substitutional donors bigger than carbon, n-type material can be achieved via impurity doping during the growth of diamond with phosphorus dopant (E_c = 0.6 eV). Theoretical studies also predict arsenic as a shallower dopant (E_c = 0.4 eV). This paper outlines the n-type doping issues with phosphorus and explores the arsenic doping.     

CVD diamond films with hydrophilic micro-patterns for self-organisation of human osteoblasts

Nanocrystalline diamond (NCD) films were prepared by microwave plasma-enhanced chemical vapour deposition (CVD) on Si substrates of different roughness (1 and 500 nm). Diamond nano-crystals are up to 50 nm in size and RMS surface roughness is less than 20 nm. The NCD films were cleaned chemically and terminated by hydrogen using plasma treatment (800 °C, 10 min) to generate a hydrophobic surface. Photolithography mask and oxygen plasma (300 W r.f. power, 3 min) were used to generate O-terminated (hydrophilic) patterns (30-200 μm wide) separated by a H-terminated (hydrophobic) surface. Osteoblast-like human cells were seeded on the patterned flat and rough NCD films in McCoy's 5A medium supplemented with 15% fetal bovine serum (FBS). After two days incubation the cells preferentially adhered on the O-terminated stripes. This phenomenon is not suppressed by the surface roughness and is general for other cell types (fibroblast and cervical carcinoma cells), too. The data are discussed with view to further application of NCD thin films in biotechnology and bio-electronics applications.     

Gamma sensitivity of single-crystal CVD diamond neutron detectors

We have studied the gamma sensitivity of single-crystal CVD diamond neutron detectors using a ²⁵²Cf neutron source placed in a moderator. It has been shown that a major contribution to the count rate of the detectors is made by the gamma rays from the source. We have compared the count rates of a detector with a ¹⁰B boron isotope-based slow-neutron converter and without it. With allowance for the theoretically calculated detection efficiency, the difference between the count rates is consistent with the fraction of slow neutrons measured using a scintillation detector.     

Photoelectron spectroscopy of ion-irradiated B-doped CVD diamond surfaces

Chemical vapour deposition (CVD) diamond films were irradiated by 1 keV argon ions at room temperature with doses ranging from 3.6 × 10¹² to 1.1 × 10¹⁶ Ar⁺ cm². The influence of sputtering on the valence band density of states of a boron-doped CVD diamond film was investigated by ultraviolet photoelectron spectroscopy and the changes in the plasmon features were observed by X-ray photoelectron spectroscopy of the carbon Is core level and its loss region. A gradual change from typical diamond features to amorphous carbon was observed after prolonged bombardment times. Above a critical dose D_crit of 5.8 × 10¹⁴ Ar⁺ cm² the damaged surface layer is characterized by a splitting of the C Is bulk peak into two components: a bulk-like diamond peak at 285.3 eV binding energy and a defect peak with 1 eV lower binding energy, which is attributed to the production of an amorphous sp²-rich carbon matrix. Moreover additional occupied states in the range of 0–4 eV binding energy, completely different to those observed on reconstructed diamond surfaces, were observed in the valence band spectra of the ion-irradiated diamond surface. These filled states can also be attributed to the amorphous carbon matrix which is formed at high doses. At very low doses (< 3 × 10¹⁴ ions cm²) only a band bending of the C Is diamond core level peak, along with the formation of some occupied states in the band structure at around 3.8 eV binding energy was observed. A comparison with annealed hydrogen-free CVD diamond surfaces shows some similarities concerning these filled states. The obtained spectra are compared with other crystalline and amorphous forms of carbon and the results are discussed in terms of an irradiation-induced change in the atomic structure of the surface. A comparison of ion bombarded and annealed diamond samples clearly shows that no graphitization takes place in the latter case.     

Growth, processing and properties of CVD diamond for optical applications

In recent years there has been an increased need for optical materials for use in adverse chemical, thermal, abrasive, and/or radiation environments. Diamond is a natural candidate for many of these applications because of its radiation hardness, superb resistance to chemical attack and abrasive wear, high thermal conductivity, and low absorption coefficient throughout the visible and much of the infrared. The use of synthetic (high pressure-high temperature) and natural diamond in optical components has been limited by the size and shapesof available crystals, and the inability to coat optical elements. The chemical vapor deposition (CVD) of polycrystalline diamond does not suffer the same limitations, and is therefore the focus of an expanding worldwide research effort. CVD diamond is not without its own shortcomings, however, and in this paper a status report is given on the obstacles and current research related to using CVD diamond as an optical material. Natural diamond's relevant physical properties and the optical applications envisioned for CVD diamond are also discussed.     

Investigation into polishing process of CVD diamond films

A new technique used for polishing chemical vapor deposition (CVD) diamond films has been investigated, by which rough polishing of the CVD diamond films can be achieved efficiently. A CVD diamond film is coated with a thin layer of electrically conductive material in advance, and then electro-discharge machining (EDM) is used to machine the coated surface. As a result, peaks on the surface of the diamond film are removed rapidly. During machining, graphitization of diamond enables the EDM process to continue. The single pulse discharge shows that the material of the coated layer evidently affects removal behavior of the CVD diamond films. Compared with the machining of ordinary metal materials, the process of EDM CVD diamond films possesses a quite different characteristic. The removal mechanism of the CVD diamond films is discussed.     

CVD金刚石厚膜晶格缺陷分析

应用X射线衍射仪的薄膜附件对热丝化学气相沉积金刚石厚膜的成核面和生长面进行分析,结果表明,金刚石厚膜的晶格常数从生长面到形核面沿深度方向是逐渐变小的.化学气相沉积金刚石初期生长的晶体存在大量的空位等缺陷,晶格松弛,在金刚石膜持续生长过程中,形核面和膜内部在高温下发生长时间的自退火,缺陷浓度下降,晶格松弛现象消除,晶格常数变小并趋于理论值.试验表明,经长时间高温自退火的金刚石厚膜比薄膜具有更高的耐磨性.