The distribution of hydrogen in polycrystalline CVD diamond

The location of the hydrogen prevalent in chemical vapor deposition (CVD) diamond has long been of much interest, not least because of the information it reveals about the H-driven growth mechanism. We have used micro-scanning elastic recoil detection analysis to map the hydrogen distribution in three dimensions in polycrystalline CVD diamond. The interface between two CVD layers, one grown with, and one grown without oxygen in the growth mixture has been studied for its hydrogen concentration. An upper limit on bulk hydrogen concentration has been determined. The possibility of hydrogen trapping in the bulk is also discussed.     

Pulse height defect in pCVD and scCVD diamond based detectors

Polycrystalline (pCVD) and single crystal (scCVD) diamond films grown from Chemical Vapour Deposition (CVD), if sufficiently pure at Raman analysis, are very good materials for beam or flux monitors inside accelerators or nuclear reactors. This is because they are very hard to damage in high radiation fields and very resistant to high temperatures. Films of pCVD diamond are, however, not so good as spectroscopy detectors due to inhomogeneities induced by their growth in grains with the consequent presence of grain boundaries which worsen their energy resolution. The latter can be significantly improved by growing scCVD diamond films onto HPHT synthetic diamond substrates. We have shown that it is possible to measure the density of defects inside diamond specimens using as probes suitable penetrating nuclear radiations. With the preliminary results reported here we'll show that, bombarding CVD diamond films grown at Roma “Tor Vergata” with energetic protons and ⁴He, ⁶Li and ¹²C ions produced in the accelerators of Catania laboratories, the pulse height defects are higher than those in silicon detectors and likewise well described by a power law in the deposited energy. Furthermore, we'll show that pulse heights for the same particles seem to depend on the duration of the measurement, thus exhibiting a sort of depolarization of the insulator when exposed to the electric voltage which makes it a particle detector.     

Effect of hydrogen implantation on the graphite used in high pressure diamond synthesis

The objective of the present work is to investigate the effect of hydrogen implantation on graphite in the high pressure diamond synthesis. A comparison of the graphite/diamond conversion for different fluences of hydrogen implantation revealed that the diamond nucleation and the total mass yield are always higher (up to 46%) than in experiments without implantation. The maximum nucleation for the studied cases occurred at a fluence of 1×10¹⁷ hydrogen ions/cm². This behavior is not observed when other ions, such as krypton and argon, are implanted on the graphite, or when hydrogen is present in the reaction cell but not implanted on the graphite. The results were interpreted as a consequence of the creation of additional tetrahedral sp³ bonded carbon atoms when the graphite is hydrogen implanted, which would act as effective diamond nucleation sites in the high pressure synthesis.     

Diamond overgrown InAlN/GaN HEMT

In this work the technology and characterization of nanocrystalline diamond (NCD) films directly grown on InAlN/GaN HEMTs is presented. Optimization of GaN based HEMT process steps including metallization stacks is discussed. A fully processed InAlN/GaN HEMT structure with 7 nm barrier has been overgrown in a temperature range of 750 °C to 800 °C with a 500 nm thick nanocrystalline diamond film in a Hot Filament CVD system. First results of semi-enhancement mode of DC and RF HEMT operation are reported. The grown NCD films were characterized by SEM, TEM, and Raman spectroscopy. Although no direct thermal conductivity measurements are conducted yet; the performed experiments shows the compatibility of growing high quality NCD films, several microns thick, on InAlN/GaN HEMTs as a potential material for heat extraction purposes.     

Electrochemical behavior of Au nanoparticle deposited on as-grown and O-terminated diamond electrodes for oxygen reduction in alkaline solution

Au nanoparticle was electrochemically deposited on both as grown and oxygen-terminated (O-terminated) boron-doped diamond (BDD) films. The surface coverages of Au nanoparticle were 0.07 and 0.18 corresponding to the areas of Au 0.012 and 0.029 cm², respectively, as noted from linear sweep voltammetry. The SEM studies indicated different morphologies of Au deposition such as random distribution of small spherical particles at both the grain boundaries and the facets on the as grown diamond film and clusters principally on the cross edges of two facets on the O-terminated diamond. The electrochemical behavior for oxygen reduction was examined using differential pulse voltammetry (DPV), which confirmed the higher catalytic efficiencies of Au deposited as grown and O-terminated BDD electrodes when compared to a polycrystalline Au electrode. Moreover, the mechanism of Au nanoparticle deposited BDD films for the oxygen reduction was investigated by ac impedance and hydrodynamic voltammetric methods.     

Diamond nucleation and growth under very low-pressure conditions

The synthesis of thin diamond films using various chemical vapor deposition methods has received significant attention in recent years due to the unique characteristic of diamond, which make it an attractive candidate for a wide range of applications. In order to grow diamond epitaxially, the proper control of diamond nucleation on mirror-polished Si is essential. Adding the negative bias voltage to the substrate is the most popular method. This paper has proposed a new method to greatly enhance the nuclear density. Under very low pressure (1 torr), the high-density nucleation of diamond is achieved on mirror-polished silicon in a hot-filament chemical vapor deposition (HFCVD). Scanning electron microscopy has demonstrated that the nuclear density can be as high as 10¹⁰–10¹¹ cm⁻². Raman spectra of the sample have shown a dominant diamond characteristic peak at 1332 cm⁻¹. The pressure effect has been discussed in detail and it has been shown that the very low pressure is a very effective means to nucleate and grow diamond films on mirror-polished silicon. Extraordinary pure hydrogen (purity=99.9999%) was used as the source. Compared with the highly pure hydrogen (purity=99.99%), we found that the density of nucleation was greatly increased. The residual oxygen in the hydrogen displayed a very obvious negative effect on the nucleation of diamond, although it can accelerate the growth of diamond. Based on these results, it was suggested that the enhanced nucleation at very low pressure should be attributed to an increased mean free path, which induced a high density of atomic hydrogen and hydrocarbon radicals near the silicon surface. Atomic hydrogen can effectively etch the oxide layer on the surface of silicon and so greatly enhance the nucleation density.     

Electron microscopy profiling of ion implantation damage in diamond: Dependence on fluence and annealing

The doping of diamond by ion implantation has been feasible for 25 years, but with the proviso that low dose implants can be annealed whereas high dose implants “graphitize”. An understanding of the types of defects, and their depth profiles, produced during the doping/implantation of diamond remains essential for the optimization of high-temperature, high-power electronic applications. This study focuses on investigating the nature of the radiation damage produced during the implantation of carbon ions into synthetic type Ib and natural diamonds using a spread of 4 energies, corresponding to typical doping energies, according to the CIRA (Cold-Implantation-Rapid-Annealing) routine, as well as a single energy implantation at room temperature. Both conventional and high resolution cross-sectional electron microscopies were achieved and used to analyze the implanted diamonds in conjunction with electron energy loss spectroscopy (EELS) and selected area diffraction (SAD). The cross sections were obtained using two different preparation methods.For low fluence implantations, using the CIRA routine, it is confirmed that the damaged diamond regains its crystallinity after annealing at 1600 K. However, above the amorphization threshold fluence, followed by rapid annealing at 1600 K, the whole implanted layer consisted of primarily amorphous carbon. High resolution TEM shows that the implanted layer consists of nano-regions with bent (002) graphitic planes and regions of amorphous carbon. The interface between the implanted layer and the diamond substrate near end of range shows diamond nanocrystallites, interspersed between regions of amorphous carbon and with bent (002) graphitic planes. There is no evidence for epitaxial regrowth. For high dose single energy ion implantation at room temperature, the unannealed layer shows a high degree of disorder at the maximum ion range, with some alignment of basal planes related to graphitic carbon, but with some of the diamond structure still partially intact. The implanted range included a diamond layer above the damaged region. This diamond layer showed no evidence of amorphous carbon.     

Incorporation of hydrogen in diamond thin films

In this investigation, diamond thin films with grain size ranging from 50 nm to 1 µm deposited using hot filament chemical vapor deposition (HFCVD) have been analyzed by elastic recoil detection analysis (ERDA) for determining hydrogen concentration. Hydrogen concentration in diamond thin films increases with decreasing grain size. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) results showed that part of this hydrogen is bonded to carbon forming C–H bonding. Raman spectra also indicated the increase of non diamond phase with the decrease in crystallite size. Incorporation of hydrogen in the samples and increase of hydrogen content in nanocrystalline sample are discussed. Large separation between filament and substrate used for the synthesis of nanocrystalline film helped to understand the large incorporation of hydrogen in nanocrystalline diamond films during growth. The study addresses the hydrogen trapping in different samples and higher hydrogen concentration in nanocrystallites by considering the synthesis conditions, growth mechanisms for different grain sized diamond films and from the quality of CVD diamond films.     

Properties of large area diamond membranes for X ray lithography

Over the past 20 years a wide variety of materials have been evaluated for use as x-ray mask support membrane. Reference 1 presents a comprehensive list of materials investigated to date. Besides x-ray and optical transparency an important requisite for a mask material is dimensional stability. Since the Young's modulus of elasticity is a measure of the atomic bond strength, the covalently bonded refractory materials such as BN or SiC, and diamond, which have large moduli, are more stable than polymers or metals. BN has been the material of choice for x-ray masks in the United States and Europe for the past 10 years; however, CVD BN contains a significant amount of hydrogen in the as-deposited state and is not sufficiently stable under prolonged x-ray exposure. On the other hand, it has been shown by nuclear reaction analysis that diamond films contain less than 1% hydrogen, despite being synthesized in a predominantly hydrogen gas mixture. The low residual hydrogen content, combined with diamond's other unique characteristics such as high mechanical stiffness and high x-ray transparency, makes it an attractive candidate for an x-ray mask material.     

Ni-P-纳米金刚石化学复合镀研究

采用制备的粒度150 nm以内的复合镀用纳米金刚石悬浮液进行了Ni-P-纳米金刚石化学复合镀研究,研究了工艺条件包括纳米金刚石加入量、搅拌方式、离子型和非离子型表面活性剂及其组合的加入对复合镀镀速和镀层性能的影响。结果表明:纳米化学复合镀要求镀液有更好的稳定性;镀速与搅拌方式有关,并且随纳米金刚石的加入而提高;组合型表面活性剂对复合镀层性能提高明显;表面形貌分析观察到镀层中纳米金刚石分布均匀,颗粒在100~200 nm左右。     

Wettability of HF-CVD diamond films

Wettability of HF-CVD diamond films grown in different conditions has been investigated. Wettability depends on surface tension: solids with high surface tension, as diamond, should be hydrophilic, while solids with low surface tension should be hydrophobic. In spite of these arguments, natural diamond exhibits a moderate hydrophobicity [J. Coll. Inter. Sci. 130 (1999) 35], depending on surface termination (hydrogen or oxygen terminated). In this work we find that CVD diamond films show wettability behaviours ranging from a small, up to clear hydrophobicity, probably according to surface carbon termination functionalities. Wettability does not seem to be influenced by characteristics as film structural morphology or growth orientation direction, which were analysed by SEM, while it seems dependent on surface reconstruction, as detected by Raman and XPS analysis. Moreover, in contrast with natural diamond [J. Coll. Inter. Sci. 130 (1999) 35] we found an enhancement to water wettability when CVD diamond films were treated in a hot filament activated hydrogen atmosphere. We argue that this effect may be due to the hydrogen etching of reconstructed surface layers with lower surface tension.     

Fabrication of graphitic layers in diamond using FIB implantation and high pressure high temperature annealing

We have used high pressure high temperature annealing (HPHT) for graphitisation of implanted layers in diamond created by 30 keV Ga⁺ focused ion beam. Electron microscopy has been used to investigate the implanted layers. It has been revealed that, unlike annealing at vacuum pressure, the graphitization during HPHT annealing occurred through epitaxial growth of graphite (002) planes parallel to (111) diamond planes. High quality of graphite was confirmed by high resolution electron microscopy and electron energy loss spectroscopy.     

Development of Titanium Coatings on Particulate Diamond

The performance of many wear-resistant materials can be improved further by incorporating diamond into the structure. Diamond that has been coated with titanium is known to adhere well to the matrix particles and also prevents reaction with H₂, which often is used in the sintering atmosphere. Two coating methods of coating diamond with titanium have been explored in this study: a sputtering method and a procedure that involves heating the diamond in a mixture of salt and titanium. The latter, which uses a salt mix of NaCl, KCl, and CaCl₂ and metallic titanium particles 3 μm in size, heated at a temperature of 750°C in an argon atmosphere, is determined to be the best method.     

金刚石薄膜取向性和后处理对其辐X射响应性能的影响

采用微波等离子体化学气相沉积合成金刚石薄膜,通过优化工艺参数和原位等离子后处理等方法来提高金刚石薄膜的质量和辐射响应灵敏度.制作出三明治结构的辐射剂量计.研究了金刚石薄膜取向性和后处理对X射线辐射响应灵敏度的影响.结果表明:薄膜取向性和后处理对X辐射响应性能有很大影响.提高金刚石薄膜的纯度和取向性是提高X射线响应灵敏度的有效途径.制作的金刚石薄膜辐射剂量计的X射线响应电流与辐射剂量率间有良好的线性关系.在电阻率相近的情况下,[100]取向金刚石薄膜制成的器件X射线响应灵敏度比[111]取向的高,取向度越高,其辐射响应灵敏度也越高.原位氧等离子后处理金刚石薄膜剂量计的X射线响应灵敏度比原位氮、氢等离子后处理的高,薄膜表面金刚石的含量由69.9%提高到93.5%,辐射响应灵敏度较未处理的膜提高1倍以上.     

CVD diamond for spintronics

The ability to minimise, control and manipulate defects in CVD diamond has grown rapidly over the last ten years. The application which best illustrates this is probably that of quantum information processing (QIP) or ‘diamond spintronics’. QIP is a rapidly growing area of research, covering diverse activities from computing and code breaking to encrypted communication. All these applications need ‘quantum bits’ or qubits where the quantum information can be maintained and controlled. Controlled defects in an otherwise high perfection diamond lattice are rapidly becoming a leading contender for qubits, and offer many advantages over alternative solutions. The most promising defect is the NV⁻ defect whose unique properties allow the state of its electron spin to be optically written to and read from. Substantial developments in the synthesis of CVD diamond have produced diamond lattices with a high degree of perfection, such that the electron spin of this centre exhibits very long room temperature decoherence times (T₂) in excess of 1 ms. This paper gives a brief review of the advantages and challenges of using CVD diamond as a qubit host. Lastly the various qubit applications being considered for diamond are discussed, highlighting the current state of development including the recent development of high sensitivity magnetometers.     

Dependence of diamond nucleation and growth through graphite etching at different temperatures

Diamond films have been grown on silicon substrate from graphite etching as a carbon source with atomic hydrogen instead of using conventional hydrocarbon in the feed gas. A graphite plate was used as sample support in a hot filament chemical vapor deposition reactor. Graphite temperature demonstrated to have a strong dependence with the diamond nucleation and growth rate. Scanning electron microscopy (SEM) images of graphite targets associated with their Raman spectra were used to analyze their graphite morphology and structural properties before and after etching process for each graphite temperature studied. The results showed that chemical erosion intrinsically induces graphite surface changes that influence Raman spectra. The disorder behavior from the I_D/I_G ratio presented a maximum value at 900 °C, for 60 min of etching time, when compared with graphite surface at room temperature before atomic hydrogen etching. SEM diamond images were also used to analyze the nucleation rate. Diamonds grown during 15 min at 600 and 700 °C presented the higher nucleation rate. For growth time of 30 min the diamonds are continuous, covering the entire Si substrate surface, with submicrometer grain size. Raman spectra showed good quality diamond coating. Diamond content or diamond purity values, evaluated for growth time of 15, 30 and 60 min increases with the increase of the graphite temperature confirming the high carbon content in the first stage of diamond growth.     

Synthesis of CVD diamond at atmospheric pressure using the hot-filament CVD method

At low pressure, chemical vapor deposition (CVD) diamond growth by conventional techniques such as micro-wave plasma and hot-filament have been achieved by metastable precursor species. Moreover, bulk diamond at extremely high pressures and temperatures was consistently originated by the nature of diamond-graphite phase transition. CVD diamond growth has four problems with these conventional techniques. Excluding contaminated air from low pressure reactive systems has been problematic. It is very difficult to control the concentration of atomic hydrogen at high pressures. The growth rate is unsatisfactory and the running cost of gases are high.However, the hot-filament CVD technique at atmospheric pressure overcomes these problems. We have found that in order to control the concentration of atomic hydrogen, the residence time of the input gas and the methane-hydrogen concentration ratio needed to be varied at each pressure. The relationship between the quality of deposited diamond and the pressure have been also investigated by Raman spectroscopy and X-ray diffraction patterns (XRD).The growth rate at atmospheric pressure (106 000 Pa) was found to be greater than that at the conventional pressure (5000 Pa). At atmospheric pressure, the growth rate abruptly increases with the residence time. XRD analysis revealed that the quality of diamonds grown at atmospheric pressure was higher than that of diamonds produced at low pressures. Furthermore, high quality diamond growth was achieved with a long residence time of the input gas at atmospheric pressure.     

Ex-situ spectroscopic ellipsometry studies of micron thick CVD diamond films

Micron thick diamond films have been studied by spectroscopic ellipsometry (SE). The films were grown, on previously prepared Si(100) substrates, by the plasma enhanced chemical vapor deposition (PECVD) technique. Ex situ SE measurements were carried out on samples grown under different conditions, such as substrate temperature and methane fraction in the gas mixture. An optical model consisting of five layers was constructed in order to explain the SE spectra and to provide the optical and structural parameters of the films. This model was deduced from results of various measurements performed by other characterization techniques (Raman spectroscopy, scanning electron microscopy, atomic force microscopy and positron annihilation spectroscopy) which have revealed the optical and structural parameters of the samples. Its sensitivity to the surface and interface roughness as well as to the absorption of the nondiamond phase of the film is demonstrated. Several values of the percentage of the nondiamond phase can be obtained, with the same fit quality, however, depending on the amorphous carbon reference used in the model. These references were obtained by performing SE measurements on various amorphous carbon films. Finally, our SE analysis has allowed us to monitor the lateral homogeneity of the thickness, surface and interface roughness and nondiamond phase concentration over the diamond film.     

Nitrogenated nanocrystalline diamond films: Thermal and optical properties

Ultrananocrystalline diamond films have been grown by microwave plasma CVD using CH₄/H₂/Ar mixtures with N₂ added in plasma in amounts up to 25%. The films were characterized with AFM, Raman, XRD, and UV–IR optical absorption spectroscopy mainly focusing on optical and thermal properties. In comparison with polycrystalline CVD diamond the UNCD are very smooth (R_a < 10 nm), have low thermal conductivity ( 0.10 W/cm K), high optical absorption ( 10³ cm^− 1 at 500 nm) and high concentration of bonded hydrogen ( 9 at.%). The nitrogen presence in the plasma has a profound impact on UNCD structure and properties, particularly leading to a decrease in resistivity (by 12 orders of magnitude), thermal conductivity, Tauc band gap, optical transmission and H content. The UNCD demonstrated rather good thermal stability in vacuum: the diamond phase still was present in the films subjected to annealing to 1400 °C.     

Antibacterial properties of polycrystalline diamond films

Electronic and mechanical properties, and their biocompatibility, make diamond-based materials promising biomedical applications. The cost required to produce high quality single crystalline diamond films is still a hurdle to prevent them from commercial applications, but the emergence of polycrystalline diamond (PCD) films grown by chemical vapour deposition (CVD) method has provided an affordable strategy. PCD films grown on silicon wafer have been used throughout and were fully characterised by SEM, XPS, Raman spectroscopy and FTIR. The samples contain nearly pure carbon, with impurities originated from the CVD growth and the silicon etching process. Raman spectroscopy revealed it contained tetrahedral amorphous carbon with small tensile stress. The sp² carbon content, comprised between 16.1 and 18.8%, is attributed to the diamond grain boundaries and iron-catalysed graphitisation. Antibacterial properties of PCD films were performed with two model bacteria, i.e. Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) using direct contact and shaking flask methods. The samples showed strong bacteriostatic properties against S. aureus and E. coli with the direct contact method and no influence on planktonic bacterial growth. These results suggest that the bacteriostatic mechanism of PCD films is linked to their surface functional groups (carbon radicals and –NH₂ and –COOH groups) and that no diffusible molecules or components were involved.