Investigation of non-diamond carbon phases and optical centers in thermochemically polished polycrystalline CVD diamond films

Polycrystalline chemical vapor deposition (CVD) diamonds films grown on silicon substrates using the microwave-enhanced CVD technique were polished using the thermochemical polishing method. The surface morphology of the samples was determined by optical and scanning electron microscopes before and after polishing. The average surface roughness of the as-grown films determined by the stylus profilometer yielded 25 μm on the growth side and about 7 μm on the substrate side. These figures were almost uniform for all the samples investigated. Atom force microscopic measurements performed on the surface to determine the average surface roughness showed that thermochemical polishing at temperatures between 700 °C and 900 °C reduced the roughness to about 2.2 nm on both the substrate and growth sides of the films. Measurements done at intermittent stages of polishing using confocal micro-Raman spectroscopy showed that thermochemical polishing is accompanied by the establishment of non-diamond carbon phases at 1353 cm⁻¹ and 1453 cm⁻¹ at the initial stage of polishing and 1580 cm⁻¹ at the intermediate stage of polishing. The non-diamond phases vanish after final fine polishing at moderate temperatures and pressures. Photoluminescence of defect centers determined by an Ar⁺ laser (λl_exct= 514.532 nm) showed that nitrogen-related centers with two zero-phonon lines at 2.156 eV and 1.945 eV and a silicon-related center with a zero-phonon line at 1.681 eV are the only detectable defects in the samples. Received: 26 July 1999 / Accepted: 15 November 1999     

Synthetic diamond electrodes: Photoelectrochemical behavior of vacuum-annealed undoped polycrystalline diamond films

The photocurrent and photopotential for undoped polycrystalline diamond film electrodes prepared by chemical vapor deposition and annealed in vacuum at 1500–1640°C are measured. The metal-like samples (annealed at 1630°C) have a negligible photosensitivity. Judging from the positive sign of the photopotential and the cathodic direction of the photocurrent, the material under study formally behaves as a p-type semiconductor. The photoeffects are presumably caused by structure defects, in particular, the dislocations in diamond crystallites formed close to intercrystalline boundaries during the high-temperature annealing.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 343–349.Original Russian Text Copyright © 2005 by Pleskov, Krotova, Ralchenko, Khomich, Khmelnitskii.     

Quantitative investigation of boron incorporation in polycrystalline CVD diamond films by SIMS

Polycrystalline diamond films have been produced on pre-treated silicon substrate by CVD hot filament method, with B(C₂H₅)₃ added to the gas phase. However, under identical surface conditions, boron incorporation is not homogeneous. In {111} growth sectors, the boron concentration is found to be about 5 times higher than in {100} growth sectors. Moreover, a marked increase in contaminating elements such as aluminium and sodium in regions with higher boron concentrations is detected. Under SIMS fine focus conditions it can be shown that the interface between these two different facet regions is smaller than 0.5 μm. With 3D-depth profile images it can also be shown that the carbon distribution in the diamond layer is not totally homogeneous.     

Quantitative investigation of boron incorporation in polycrystalline CVD diamond films by SIMS

Polycrystalline diamond films have been produced on pre-treated silicon substrate by CVD hot filament method, with B(C₂H₅)₃ added to the gas phase. However, under identical surface conditions, boron incorporation is not homogeneous. In {111} growth sectors, the boron concentration is found to be about 5 times higher than in {100} growth sectors. Moreover, a marked increase in contaminating elements such as aluminium and sodium in regions with higher boron concentrations is detected. Under SIMS fine focus conditions it can be shown that the interface between these two different facet regions is smaller than 0.5?μm. With 3D-depth profile images it can also be shown that the carbon distribution in the diamond layer is not totally homogeneous.     

Spectroelectrochemical responsiveness of a freestanding, boron-doped diamond, optically transparent electrode toward ferrocene

The spectroelectrochemical responsiveness of an optically transparent diamond electrode (OTE) toward ferrocene was investigated. A freestanding, mechanically polished, boron-doped diamond disk (0.38 mm thick and 8 mm in diameter) served as the OTE for UV-Vis transmission spectroelectrochemical measurements. A specially designed, thin-layer spectroelectrochemical cell was constructed for the measurements in which ferrocene was electrooxidized to ferricinium ion via a one-electron redox reaction. The oxidation reaction product was spectroscopically monitored in the ultraviolet (λ=252, 285 nm) region of the electromagnetic spectrum. Well-defined and highly stable spectroelectrochemical responses were observed for this type of diamond OTE. The results indicate that diamond is a useful OTE material for spectroelectrochemically studying nonaqueous redox reactions.     

Preparation of boron-doped semiconducting diamond films using BF3 and the electrochemical behavior of the semiconducting diamond electrodes

Boron-doped semiconducting diamond films were prepared using BF₃ by microwave plasma assisted chemical vapor deposition. B-doping was confirmed by SIMS and Raman spectroscopic measurements and the B-doping levels were estimated. Electrochemical behaviors of boron-doped diamond thin-film electrodes prepared using B₂H₆ and BF₃ were studied by measuring cyclic voltammograms for anodic oxidation of 1,4-difluorobenzene in the liquid electrolyte, neat Et₄NF·4HF. The results of the direct thermal interaction of elemental fluorine with hydrogenated and oxidized diamond surfaces are also presented.     

Simultaneous growth of diamond and nanostructured graphite thin films by hot-filament chemical vapor deposition

Diamond and graphite films on silicon wafer were simultaneously synthesized at 850 °C without any additional catalyst. The synthesis was achieved in hot-filament chemical vapor deposition reactor by changing distance among filaments in traditional gas mixture. The inter-wire distance for diamond and graphite deposition was kept 5 and 15 mm, whereas kept constant from the substrate. The Raman spectroscopic analyses show that film deposited at 5 mm is good quality diamond and at 15 mm is nanostructured graphite and respective growths confirm by scanning auger electron microscopy. The scanning electron microscope results exhibit that black soot graphite is composed of needle-like nanostructures, whereas diamond with pyramidal featured structure. Transformation of diamond into graphite mainly attributes lacking in atomic hydrogen. The present study develops new trend in the field of carbon based coatings, where single substrate incorporate dual application can be utilized.     

Sonoelectrochemistry at highly boron-doped diamond electrodes: silver oxide deposition and electrocatalysis in the presence of ultrasound

The use of boron-doped diamond has a considerable impact in electrochemistry owing to the wide potential range accessible, low background currents, extreme hardness, and the ease of chemical modification of diamond surfaces. It is shown here that, although the electrodeposition of silver metal is known to yield very poorly adhering films with a poor electrical contact, a silver oxysalt deposit formed on anodically pre-treated diamond surfaces adheres strongly with good electrical contact. The deposit is stable even in the presence of ultrasound. Voltammetric and XPS studies reveal that the silver oxide deposit, in contrast to the silver metal deposit, is efficiently stripped from the diamond surface by applying a sufficiently negative potential. The silver oxysalt Ag₇O₈NO₃, deposited onto two types of boron-doped diamond electrodes, a 50 μm thick polycrystalline thin film deposited on a tungsten substrate and a polished free standing diamond plate, is shown to act as an electrocatalyst for oxygen evolution and for the oxidation of toluene. This development opens up the possibility of boron-doped diamond being applied as an inert and conducting substrate material for a wide range of oxidic materials, which can then be utilised as active electrocatalysts at high applied potentials. Received: 17 March 2000 / Accepted: 10 April 2000     

Differential pulse voltammetric determination of dopamine with the coexistence of ascorbic acid on boron-doped diamond surface

Electrochemical determination of dopamine (DA) in the presence of ascorbic acid (AA) was achieved on boron-doped diamond (BDD) film electrode by differential pulse voltammetry. The experimental results indicated that the oxidative peaks of DA and AA could be separated completely on anodically-treated (BDD) electrode without further modification, although these two peaks can not be separated on glassy carbon electrode. The peak separation of DA and AA was developed to be 0.44 V. High sensitivity was obtained to determine DA selectively with the coexisting of a large excess of AA in acidic media by DPV. The detection limit of DA was achieved to be 1.1 × 10^-6 M in the presence of AA with the concentration of 200 times more than DA. This technique was also applied to the determination of DA in real samples.      

Thin films of mesoporous silica: preparation and characterization

Preparation of mesoporous materials in a thin film geometry was first reported in 1996. Recently, improvement of the preparation methods yielded stable films with well-defined symmetries, controlled pore orientation, continuity and film thickness. The ability to tailor film properties is important for their utilization in applications ranging from catalysis to microelectronics, where morphological control in the meso-domain is vital.     

Raman imaging and Kelvin probe microscopy for the examination of the heterogeneity of doping in polycrystalline boron-doped diamond electrodes

The issue of the heterogeneity of boron doping in microcrystalline diamond films was addressed by four different methods: micro-Raman spectroscopy and Raman imaging, Kelvin probe force microscopy, conducting atomic force microscopy, and scanning electrochemical microscopy. The samples were commercially available films from Windsor Scientific, with an average boron concentration of about 5 x 10(20) cm(-3). In agreement with previous works, all of the methods showed that the boron uptake was nonuniform across the surface of the electrode. Two different types of regions were evidenced, with metallic or semiconducting properties that were characterized with different types of Raman spectra. The line shape of these spectra was strongly dependent on the excitation wavelength. Local variations in electroactivity were evidenced by the SECM curves, which are related to the electronic properties of the individual grains, which, in turn, are governed by the boron content of the individual crystallites. In this study, two different micro-Raman imaging techniques were used that reveal the grain structure of the films: the images constructed from the diamond line intensity perfectly reproduced the optical image obtained by illuminating the sample in reflection. The method also allows detection of the presence of nondiamond carbon, especially in the metallic parts of the samples. Other spectral features (intensity of the boron-related broad lines, as well as the frequency and width of the diamond line) were used to construct images. In every case, the grain structure of the film was revealed, as well as twinning within individual crystallites. All approaches revealed that no enhanced doping or boron depletion occurred at the grain boundaries.     

Si-N membrane-based microcalorimetry: Heat capacity and thermal conductivity of thin films

We have used silicon micromachining techniques to fabricate devices for measuring specific heat or other calorimetric signals from microgram-quantity samples over a temperature range from 1.7 to at least 525 K in magnetic fields to date up to 8 T. The devices are based on a robust silicon-nitride membrane with thin film heaters and thermometers. Different types of thermometers are used for different purposes and in different temperature ranges. These devices are particularly useful for thin film samples (typically 100-400 nm thick at present) deposited directly onto the membrane through a Si micromachined evaporation mask. They have also been used for small bulk samples attached by conducting grease, Ga or In, and for powder samples dissolved in a solvent and dropped onto devices. The measurement technique used (relaxation method) is particularly suited to high field measurements because the thermal conductance can be measured once in zero field and is field independent, while the time constant of the relaxation does not depend on thermometer calibration.     

Influence of the type of foam films and the type of surfactant on foam stability

The behaviour and the life time ( _p) of different types of foam films (thin liquid films, for which DLVO-theory is valid; common black films, Newton black films) have been studied as a function of external pressure (P), applied in the Plateau-Gibbs-borders of the foam. The foam stability and the course of thep/P-dependence are determined mainly by the type of the foam films. A criterion for estimation of foam stability is proposed on the base of the obtained experimental results.     

X-ray and Raman study of spray pyrolysed vanadium oxide thin films

Vanadium oxide thin films were prepared by spray pyrolysis using solutions of vanadium chloride (VCl₃) with different concentrations on glass substrates heated at 200 and 250 °C. The influence of substrate temperature (T_s) and solution concentration (molarity) on structural and vibrational properties is discussed by using X-ray diffraction and Raman spectroscopy. The results revealed that at 0.05 M and T_s = 200 °C, V₄O₉ thin films are obtained. At 250 °C, V₂O₅ phases with preferential orientation are observed and the films become polycrystalline when the molarity increases.     

CE coupled with amperometric detection using a boron-doped diamond microelectrode: validation of a method for endogenous norepinephrine analysis in tissue

The level of endogenous norepinephrine (NE) in several tissue types was determined by CE with amperometric detection. We report herein on the method validation by HPLC using both amperometric and coulometric detection (CD). Keys to the method were the use of a diamond microelectrode for detection and off-line SPE for sample preparation. The run buffer was a 250 mM borate solution adjusted to pH 8.8 with potassium hydroxide. The diamond microelectrode exhibited a low and stable background current, and a low peak-to-peak noise < or =0.65 pA at the detection potential of +0.86 V versus Ag/AgCl. For standard solutions, the detector signal (i.e., oxidation current) changed linearly with the NE concentration (r(2) = 0.999) between 60 and 1000 nmol/L with an estimated LOD of 51 nmol/L (S/N = 3) and a response variability of 4.5% (RSD, n = 5). An Oasis MCX sorbent was used for SPE and the procedure produced an NE recovery of 95.1 +/- 5.6% (n = 6) from tissue homogenates. NE levels in the spleen, small intestine, and heart of a normotensive rat were found to be in the range of 0.77-0.97, 0.22-0.32, and 0.29-0.45 microg/g tissue (n = 3), respectively.     

Thermoelectric properties of photo- and thermal CVD boron and boron phosphide films

The electrical properties of n-BP films newly prepared by thermal CVD in the B₂H₆-PH₃-H₂ system were improved by a deuterium lamp excitation. High-temperature electrical conductivity and thermoelectric power of amorphous boron and polycrystalline boron phosphide films grown on silica glass were measured to evaluate the thermoelectric figure-of-merit (Z). In particular, the Z-value for photo-thermal BP films was higher (10⁻⁴/K) than that of boron films, indicating that they are promising for high-temperature thermoelectric materials.     

CO-sensing properties of undoped and doped tin oxide thin films prepared by electron beam evaporation

Undoped thin films of tin oxide and those doped with indium oxide and nickel oxides were deposited by electron beam evaporation. The effects of the film thickness and preparation conditions (films prepared with or without the presence of oxygen environment during deposition) on the optical and carbon monoxide sensing properties of the films were studied. The films were characterized using X-ray diffraction and X-ray photoelectron spectroscopy and optical spectroscopy techniques. All the films were found to be amorphous. It was found that the sensitivity of the films to CO increased with the thickness and the porosity of the films. It was found that their selectivity to CO gas relative to CO₂ and SO₂ gases could be improved upon doping the films with indium (or nickel) oxide.     

Process study of thermal plasma chemical vapor deposition of diamond,part II: Pressure dependence and effect of substrate pretreatment

The effect of pressure during thermal plasma chemical vapor deposition of diamond films has been investigated for a pressure range from 100 to 760 Torr. The maximum growth rate in our experiments occurs at 270 Torr for substrate temperatures around 1000°C. The existence of an optimum pressure for diamond deposition may he related to the balance between generation and recombination of atomic hydrogen and carbon-containing active species in front of the substrate. To estimate the concentrations of atomic hydrogen and methyl radicals under thermal plasma conditions, calculations based on thermodynamic equilibrium have been performed. This approximate evaluation provides useful guidelines because rapid diffusion results in a near frozen chemistry within the boundary layer. The effect of substrate pretreatment on diamond deposition depends on the type of substrate used. Two growth modes have been observed-layer growth and island growth of diamond crystals on various substrates. Screw dislocations have been observed in diamond deposition in thermal plasmas, and defects such as secondary nucleations are more concentrated along (III) directions than along (100) directions.     

Film thickness dependence of the domain size in weakly incompatible thin polymer blend films

The surface morphology of thin polymer blend films of deuterated polystyrene (dPS) and polyparamethylstyrene (PpMS) is investigated with scanning force microscopy (SFM) and optical microscopy. From a statistical analysis of the data the most prominent in-plane length picturing the domain size as a function of the blend film thickness is determined. In ultra-thin films surface patterns directly after preparation are absent, whereas for thicker films a linear dependence is observed. After a relaxation towards equilibrium, resulting from annealing or storage under toluene vapor, the power law observed changes for ultra-thin films and remains unchanged for thicker films. Received: 27 July 2000 Accepted: 30 October 2000     

Probing the in-plane composition of thin polymer films with grazing-incidence small-angle neutron scattering and atomic force microscopy

The surface morphologies of confined, dewetted polymer films were investigated with atomic force microscopy (AFM) and grazing-incidence small-angle neutron scattering (GISANS). On examining homopolymer films of deuterated polystyrene (dPS) both techniques reveal the resulting droplet structure which is described by one most prominent in-plane length. Due to the contrast resulting from deuteration in the case of polymer blend films of dPS and poly(p-methyl styrene) GISANS is able to probe the in-plane composition of the dewetting structure. An additional phase separation process at different length scales gives rise to a sub- and superstructure which is not detectable by AFM. In addition, the influence of the wavelength used in the GISANS experiments on the structures observed is discussed. Received: 13 April 1999 Accepted in revised form: 29 June 1999