Thermal conductivity of Cu/diamond composites prepared by a new pretreatment of diamond powder

Cu/diamond composites were fabricated by spark plasma sintering (SPS) after the surface pretreatment of the diamond powders, in which the diamond particles were mixed with copper powder and tungsten powder (carbide forming element W). The effects of the pretreatment temperature and the diamond particle size on the thermal conductivity of diamond/copper composites were investigated. It was found that when 300 μm diamond particles and Cu–5 wt.% W were mixed and preheated at 1313 K, the composites has a relatively higher density and its thermal conductivity approaches 672 W (m K)⁻¹.     

Electrochemical polymerizatıon of hexachloroethane to form poly(hydridocarbyne): a pre-ceramic polymer for diamond production

Due to its structural similarity with diamond, poly(hydridocarbyne) (PHC), which is sp³-hybridized, is a unique polymer that can be easily converted to diamond and diamond-like-carbon ceramics upon heating. PHC can be easily synthesized via the electrochemical polymerization of chloroform as previously reported. Here, we report the electrosynthesis of PHC from hexachloroethane. Since hexachloroethane has six chlorine atoms in its structure, polymerization takes place through the carbons simultaneously. Thus, the polymer is bigger in chain length than PHC obtained from the polymerization of chloroform. UV-vis, FTIR, and NMR spectroscopy were utilized to determine the polymer structure. Conversion of the polymer to diamond was accomplished by heating at 1000 °C under a nitrogen atmosphere as confirmed by Optical Microscopy and Raman analysis. XRD studies showed that the product is an assortment of diamond forms.     

High dosage thermoluminescence diamond dosimeters

Diamond thin films have been irradiated with high doses (up to 12.8 kGy) of ⁹⁰Sr beta particles. The diamond thin films have been synthesized from commercial Tequila as a precursor using Pulsed Liquid Injection by the Chemical Vapor Deposition (PLICVD) technique reported recently. Thermoluminescence (TL) phenomena at these doses exhibit peak curve shift to higher temperatures (from 370 to 440 K) in the glow curve and the integrated TL curve show a linear behavior. Therefore, it has been considered that diamond thin films could be used as high doses dosimeters.     

Field emission from diamond and diamond-like carbon films

Field emission from diamond and diamond-like carbon thin films deposited on silicon substrates has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. The diamond-like carbon films were deposited using the radio frequency chemical vapor deposition method. Field emission studies were carried out using a sphere-to-plane electrode configuration. The results of field emission were analyzed using the Fowler-Nordheim model. It was found that the diamond nucleation density affected the field emission properties. The films were characterized using standard scanning electron microscopy, Raman spectroscopy, and electron spin resonance techniques. Raman spectra of both diamond and diamond-like films exhibit spectral features characteristic of these structures. Raman spectrum for diamond films exhibit a well-defined peak at 1333cm^?1. Asymmetric broad peak formed in diamond-like carbon films consists of D-band and G-band around 1550 cm^?1 showing the existence of both diamond (sp³ phase) and graphite (sp² phase) in diamond-like carbon films.     

Investigation of low-resistivity from hydrogenated lightly B-doped diamond by ion implantation

Abstract

We have implanted boron (B) ions (dosage: 5×10¹⁴ cm^-2) into diamond and then hydrogenated the sample by implantating hydrogen ions at room temperature. A p-type diamond material with a low resistivity of 7.37 mΩ cm has been obtained in our experiment, which suggests that the hydrogenation of B-doped diamond results in a low-resistivity p-type material. Interestingly, inverse annealing, in which carrier concentration decreased with increasing annealing temperature, was observed at annealing temperatures above 600 °C. In addition, the formation mechanism of a low-resistivity material has been studied by density functional theory calculation using a plane wave method.     

Plasma-enhanced chemical vapor deposition of nanocrystalline diamond

Nanocrystalline diamond films have attracted considerable attention because they have a low coefficient of friction and a low electron emission threshold voltage. In this paper, the author reviews the plasma-enhanced chemical vapor deposition (PE-CVD) of nanocrystalline diamond and mainly focuses on the growth of nanocrystalline diamond by low-pressure PE-CVD. Nanocrystalline diamond particles of 200–700 nm diameter have been prepared in a 13.56 MHz low-pressure inductively coupled CH₄/CO/H₂ plasma. The bonding state of carbon atoms was investigated by ultraviolet-excited Raman spectroscopy. Electron energy loss spectroscopy identified sp²-bonded carbons around the 20–50 nm subgrains of nanocrystalline diamond particles. Plasma diagnostics using a Langmuir probe and the comparison with plasma simulation are also reviewed. The electron energy distribution functions are discussed by considering different inelastic interaction channels between electrons and heavy particles in a molecular CH₄/H₂ plasma.     

Investigation of low-resistivity from hydrogenated lightly B-doped diamond by ion implantation

We have implanted boron (B) ions (dosage: 5×10¹⁴ cm^-2) into diamond and then hydrogenated the sample by implantating hydrogen ions at room temperature. A p-type diamond material with a low resistivity of 7.37 mΩ cm has been obtained in our experiment, which suggests that the hydrogenation of B-doped diamond results in a low-resistivity p-type material. Interestingly, inverse annealing, in which carrier concentration decreased with increasing annealing temperature, was observed at annealing temperatures above 600 °C. In addition, the formation mechanism of a low-resistivity material has been studied by density functional theory calculation using a plane wave method.     

Biological evaluation of ultrananocrystalline and nanocrystalline diamond coatings

Nanostructured biomaterials have been investigated for achieving desirable tissue-material interactions in medical implants. Ultrananocrystalline diamond (UNCD) and nanocrystalline diamond (NCD) coatings are the two most studied classes of synthetic diamond coatings; these materials are grown using chemical vapor deposition and are classified based on their nanostructure, grain size, and sp³ content. UNCD and NCD are mechanically robust, chemically inert, biocompatible, and wear resistant, making them ideal implant coatings. UNCD and NCD have been recently investigated for ophthalmic, cardiovascular, dental, and orthopaedic device applications. The aim of this study was (a) to evaluate the in vitro biocompatibility of UNCD and NCD coatings and (b) to determine if variations in surface topography and sp³ content affect cellular response. Diamond coatings with various nanoscale topographies (grain sizes 5–400?nm) were deposited on silicon substrates using microwave plasma chemical vapor deposition. Scanning electron microscopy and atomic force microscopy revealed uniform coatings with different scales of surface topography; Raman spectroscopy confirmed the presence of carbon bonding typical of diamond coatings. Cell viability, proliferation, and morphology responses of human bone marrow-derived mesenchymal stem cells (hBMSCs) to UNCD and NCD surfaces were evaluated. The hBMSCs on UNCD and NCD coatings exhibited similar cell viability, proliferation, and morphology as those on the control material, tissue culture polystyrene. No significant differences in cellular response were observed on UNCD and NCD coatings with different nanoscale topographies. Our data shows that both UNCD and NCD coatings demonstrate in vitro biocompatibility irrespective of surface topography.     

Silicon carbide and diamond for high temperature device applications

The physical and chemical properties of wide bandgap semiconductors silicon carbide and diamond make these materials an ideal choice for device fabrication for applications in many different areas, e.g. light emitters, high temperature and high power electronics, high power microwave devices, micro-electromechanical system (MEMS) technology, and substrates. These semiconductors have been recognized for several decades as being suitable for these applications, but until recently the low material quality has not allowed the fabrication of high quality devices. Silicon carbide and diamond based electronics are at different stages of their development. An overview of the status of silicon carbide's and diamond's application for high temperature electronics is presented. Silicon carbide electronics is advancing from the research stage to commercial production. The most suitable and established SiC polytype for high temperature power electronics is the hexagonal 4H polytype. The main advantages related to material properties are: its wide bandgap, high electric field strength and high thermal conductivity. Almost all different types of electronic devices have been successfully fabricated and characterized. The most promising devices for high temperature applications are pn-diodes, junction field effect transistors and thyristors. MOSFET is another important candidate, but is still under development due to some hidden problems causing low channel mobility. For microwave applications, 4H-SiC is competing with Si and GaAs for frequency below 10 GHz and for systems requiring cooling like power amplifiers. The unavailability of high quality defect and dislocation free SiC substrates has been slowing down the pace of transition from research and development to production of SiC devices, but recently new method for growth of ultrahigh quality SiC, which could promote the development of high power devices, was reported. Diamond is the superior material for high power and high temperature electronics. Fabrication of diamond electronic devices has reached important results, but high temperature data are still scarce. PN-junctions have been formed and investigated up to 400 ^∘C. Schottky diodes operating up to 1000 ^∘C have been fabricated. BJTs have been fabricated functioning in the dc mode up to 200 ^∘C. The largest advance, concerning development of devices for RF application, has been done in fabrication of different types of FETs. For FETs with gate length 0.2 μ m frequencies f_T = 24.6 GHz, f_{max (MAG)} = 63 GHz and f_{max (U)} = 80 GHz were reported. Further, capacitors and switches, working up to 450 ^∘C and 650 ^∘C, respectively, have also been fabricated. Low resistant thermostable resistors have been investigated up to 800 ^∘C. Temperature dependence of field emission from diamond films has been measured up to 950 ^∘C. However, the diamond based electronics is still regarded to be in its infancy. The prerequisite for a successful application of diamond for the fabrication of electronic devices is availability of wafer diamond, i.e. large area, high quality, inexpensive, diamond single crystal substrates. A step forward in this direction has been made recently. Diamond films grown on multilayer substrate Ir/YSZ/Si(001) having qualities close those of homoepitaxial diamond have been reported recently.     

Plasma-enhanced chemical vapor deposition of nanocrystalline diamond

Nanocrystalline diamond films have attracted considerable attention because they have a low coefficient of friction and a low electron emission threshold voltage. In this paper, the author reviews the plasma-enhanced chemical vapor deposition (PE-CVD) of nanocrystalline diamond and mainly focuses on the growth of nanocrystalline diamond by low-pressure PE-CVD. Nanocrystalline diamond particles of 200–700 nm diameter have been prepared in a 13.56 MHz low-pressure inductively coupled CH₄/CO/H₂ plasma. The bonding state of carbon atoms was investigated by ultraviolet-excited Raman spectroscopy. Electron energy loss spectroscopy identified sp²-bonded carbons around the 20–50 nm subgrains of nanocrystalline diamond particles. Plasma diagnostics using a Langmuir probe and the comparison with plasma simulation are also reviewed. The electron energy distribution functions are discussed by considering different inelastic interaction channels between electrons and heavy particles in a molecular CH₄/H₂ plasma.     

Dielectric and Raman spectroscopy of MWCVD diamond thin films

The dielectric properties of diamond thin films obtained on silicon substrates by microwave plasma-assisted chemical vapour deposition (MWCVD) have been measured in the frequency range from 0.1 to 10³ kHz at different temperatures up to 150 C. The experimental results have been discussed in terms of the many body theory for dielectric relaxation in solids. Dielectric parameters as well as the d.c. conductivity of the samples have been correlated with the morphology and diamond content in the films, respectively detected from scanning electron microscopy (SEM) and Raman spectroscopy. The calculated activation energies for the dielectric relaxation mechanism agree with those obtained from other measurement techniques used in the electrical characterization of diamond films.     

Simplified procedure for patterned growth of nanocrystalline diamond micro-structures

Two technological strategies to generate patterned diamond growth have been tested. The diamond micro-structures (i.e. linear stripes and 5 µm narrow channels) were grown in the thickness of 450 nm on Si/SiO₂ substrates by a microwave plasma chemical vapor deposition process. Strategy 1, employing a metal mask, resulted in unsatisfying patterned diamond growth due to instability of metal mask. Strategy 2 was based on a direct lithographic patterning of the seeding layer and resulted in a strongly selective, homogenous, and compact growth of diamond on the polymer-coated seeding patterns. This is assigned to the high seeding yield. The diamond micro-structures formed in this way exhibit surface conductivity of 10^− 7 (Ω/□)^− 1 as assessed by I–V characteristics. The observed results appear promising for the development of directly grown diamond-based transistors.     

Reaction sintering of diamond using a binary solvent-catalyst of the Fe-Ti system

Reaction sintering of diamond was investigated using a starting mixed powder of purified natural graphite and a binary solvent-catalyst of the Fe-Ti system under high pressure (7G Pa) and temperature (1700°C) conditions for e treatment time of 1 to 15 min. Diamond sintered compact of about 100% conversion ratio from graphite todiamond was obtained with the binary solvent-catalyst content: 11.4 to 17.0 vol% (30 to 40wt%) Fe and 6.6 to 7.7vol% (10wt%) Ti. The sintered compact having the bulk density of 4.1 to 5.5g cm^–3, consisted of diamond phase and metal carbide (Fe₃C and TiCx) phase. The Vickers microhardnesm (under 1000 g load) mfthesintered diamond phase was >8OO0, while that ofthe metal carbide phase was 1000 to 2000. The transformation from graphite to diamond proceeded in a short time (< 1 min), which was followed by a particle joining between the formed diamond grains, when the densification would be attained at the reaction time of 15 min by pooling out the melt of carbon and solvent-catalyst.     

CVD diamond layers for electrochemistry

Diamond electrodes of different morphologies and qualities were manufactured by hot filament chemical deposition (HF CVD) techniques by changing the parameters of diamond growth process. The estimation of diamond quality and identification of different carbon phases was performed by Raman spectroscopy measurements. The effect of diamond quality and amorphous carbon phase content on the electrochemical response of an obtained diamond electrode in 0.5 M H₂SO₄ as supporting electrolyte was investigated by cyclic voltammetry with [Fe(CN)₆]^4?/3? as a redox probe. The kinetic parameters such as catalytic reaction rate constant k₀ and electron transfer coefficient α were determined. The obtained results show that the analytical performance of undoped diamond electrodes can be implemented just by the change of diamond layers quality.     

Crystalline diamond/graphite nanoflake hybrid films

Freestanding crystalline diamond/graphite nanoflake hybrid films have been deposited in H₂/CH₄ gas mixtures using a high pressure (1.3 × 10⁴ Pa) direct current plasma discharge. Sacrificial layers of close-packed silica microspheres were used as a matrix to produce dual gas chemistries on the plasma-facing and reverse sides of the microspheres. A continuous polycrystalline diamond film was formed on the front surface whilst graphite was deposited in the form of nanoflakes as a thinner hemispherical layer on the reverse side of the silica spheres respectively. Chemical etching of the silica matrix yielded crystalline diamond/well-aligned graphite nanoflakes hybrid films.     

Characteristics of diamond regrowth in a synthetic diamond compact

A transmission electron microscopic study of a commercial sintered diamond compact is reported that identifies and characterizes the diamond that has regrown between the grains of the original diamond powder during the high-pressure, high-temperature manufacturing process of the compact. The majority of the original grains are strongly deformed whereas the regrown diamond shows little or no plastic deformation. The dislocations in diamond regrown between the original grains occur in low-angle boundaries and other configurations typical of grown-in dislocations in crystals. The manufacturing process involves infiltrating the diamond aggregate by molten cobalt, and the regrown diamond is characterized by the presence of cobalt inclusions in sizes ranging from a few tenths of a micrometre down to a few nanometres, possessing the same orientation and lattice parameter as the diamond host. Graphite inclusions also occur in regrown diamond, few in comparison with cobalt inclusions and in random orientation. The graphite crystals exhibit axial ratios, (c/a), lowered by several per cent due to the containment pressure exerted by the diamond host.     

Effect of ambient pretreatment of graphite and solvent-catalyst on diamond formation

Diamond was formed from purified natural graphite under high pressure and temperature conditions (7 G Pa, 1700° C) using a solvent-catalyst in the unary (Fe) or binary (Fe-Ti) system. The effect of an ambient pretreatment of the starting mixed powder (graphite and solvent-catalyst) was investigated in relation to the formation and grain growth of diamond. An initial desorption of adsorbed water vapour or harmful gases from the starting powder in vacuum (2 × 10^–5 torr) at higher temperatures (>400° C) was required in order to increase the conversion ratio from graphite to diamond. The subsequent ambient pretreatment at 1000° C in different atmospheres was found to affect the grain growth process of diamond. The depression of grain growth was confirmed in both cases of pretreatments in vacuum (2 × 10^–5 torr) and in an argon atmosphere (1 × 10^–3 or 760 torr). The diamond grains were discrete in the vacuum pretreatment, while a particle joining between the diamond grains was promoted in the argon pretreatment. The pretreatment in an N₂ atmosphere (1 × 10^–3 or 760 torr) tended to accelerate the grain growth of diamond.     

Polylysine-coated diamond nanocrystals for MALDI-TOF mass analysis of DNA oligonucleotides

A protocol based on aminated diamond nanocrystals has been developed to isolate, concentrate, purify, and digest DNA oligonucleotides in one microcentrifuge tube for matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry. It is shown that use of diamond nanocrystals as a solid-phase extraction support not only permits concentration of oligonucleotides in highly diluted solutions but also facilitates separation of oligonucleotides from proteins in heavily contaminated solutions. Enzymatic digestions can be conducted on particle, and additionally, the digests can be easily recovered from the solution for base sequencing. In this method, the aminated diamond nanocrystals ( approximately 100 nm in diameter) were prepared by noncovalent coating of carboxylated/oxidized diamonds with poly(L-lysines) (PL), which form stable complexes with DNA oligonucleotides. While the complexes are sufficiently stable to sustain repeated washing with deionized water, the DNA molecules can be readily eluted after incubation of the diamond adducts in aqueous ammonium hydroxide at elevated temperatures. No preseparation of PL or diamond nanocrystals is required for subsequent MALDI-TOF mass analysis.     

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.     

Structure and hardness of octahedral natural diamond single crystals depending on the HPHT treatment conditions

The structure evolution of octahedral natural diamond single crystals has been studied depending on the HPHT treatment using Raman scattering and infrared spectroscopy. It has been found that the formation of a polycrystalline diamond capsule around a single crystal at p = 8 GPa and T = 1500°C gives rise to a combined structural-stressed state in the single crystal due to its plastic strain. This state has been manifested by a significantly (more than double) broadening of the characteristic line of diamond (1332 cm^?1) in the Raman spectrum and the increase of a single crystal hardness from 105 to 120 GPa.