James E. Butler

Infrared detection of gaseous species during the filament‐assisted growth of diamond

Infrared diode laser absorption spectroscopy is employed as an in situ method to examine gas phase species present during filament‐assisted deposition of diamond films. From a reactant mixture of 0.5% methane in hydrogen, methyl radical (CH3 ), acetylene (C2H2), and ethylene (C2H4 ) are detected above the growing surface, while ethane (C2H6 ), various C3 hydrocarbons, and methylene (CH2) radicals are below our sensitivity levels. The growth of polycrystalline diamond films on Si wafers and polycrystalline Ni is confirmed with x‐ray and Raman scattering, scanning electron microscopy, and Auger electron spectroscopy.

Elastic, mechanical, and thermal properties of nanocrystalline diamond films

Nanocrystalline columnar-structured diamond films with column diameters less than 100 nm and thicknesses in the range of 1–5 μm were grown on silicon substrates by chemical vapor deposition (CVD) in a microwave plasma reactor with purified methane and hydrogen used as the reactants. Uniform conformal nucleation densities in excess of 1012 cm−2 were accomplished prior to growth by seeding with explosively formed nanodiamonds, which resulted in good optical quality films. The film thickness was measured in situ by the laser reflectometry method. The grain size and optical quality of the films were characterized by scanning electron microscopy and Raman measurements. Broadband surface acoustic wave pulses were used to measure the anomalous dispersion in the layered systems. The experimental dispersion curves were fitted by theory, assuming the diamond film as an isotropic layer on an anisotropic silicon substrate, to determine mean values of the density and Young’s modulus of the diamond films. The density w...

Thin Film Diamond Growth Mechanisms [and Comment]

The principal chemical mechanisms relevant to the growth of diamond from gaseous hydrogen and hydrocarbon species are presented. The kinetic processes occurring during the activation and transport of the gaseous species to the growing surface are described, with the key processes being the generation and subsequent reactions of gaseous atomic hydrogen. The structure, composition, and dynamics of the growing surface are discussed. A simple, non-stereospecific model of the surface growth process is presented which reveals most of the general characteristics of the growth process, such as the H atom flux dependence of growth rate and quality. A detailed model of growth at the (110) surface sites from single carbon reactants then follows, which highlights the key role of gaseous atomic hydrogen abstractions of hydrogen from the surface. The extension of this understanding to chemistries containing oxygen and halogen species is indicated.

Hydrogen atom detection in the filament‐assisted diamond deposition environment

The resonance‐enchanced multiphoton ionization (REMPI) technique was employed for detection of gas phase atomic hydrogen in the filament‐asisted diamond growth environment. The H atom REMPI signal varied significantly with the reactant CH4/H2 fraction as well as with the filament temperature. We interpret these observations as evidence for the surface role of atomic hydrogen in the diamond growth mechanism. The spatial resolution of the REMPI technique allowed us to confirm that hydrogen atom transport in the deposition region occurs by diffusion.

Nanomechanical resonant structures in nanocrystalline diamond

We report the fabrication and the operation of nanomechanical resonant structures in nanocrystalline diamond. For this purpose, continuous diamond films as thin as 80 nm were grown using microwave plasma enhanced chemical vapor deposition. The lateral dimensions of the fabricated structures were as small as 50 nm and the measured mechanical resonant frequencies were up to 640 MHz. The mechanical quality factors were in the range of 2500–3000 at room temperature. The elastic properties of these films obtained via the resonant measurements indicate a Young’s modulus close to that of single-crystal diamond.

Fabrication and characterization of two-dimensional photonic crystal microcavities in nanocrystalline diamond

Diamond-based photonic devices offer exceptional opportunity to study cavity QED at room temperature. Here we report fabrication and optical characterization of high quality photonic crystal (PC) microcavities based on nanocrystalline diamond. Fundamental modes near the emission wavelength of negatively charged nitrogen-vacancy (N-V) centers (637 nm) with quality factors (Qs) as high as 585 were observed. Three-dimensional Finite-Difference Time-Domain (FDTD) simulations were carried out and had excellent agreement with experimental results in the values of the mode frequencies. Polarization measurements of the modes were characterized; their anomalous behavior provides important insights to scattering loss in these structures.

Diamond synthesis using an oxygen-acetylene torch

Diamond microcrystallites and polycrystalline films were grown on various substrates in the ambient atmosphere with an oxygen-acetylene welding torch. Growth is examined as a function of substrate position and temperature, and gas flow ratio. The deposited material was analyzed with Raman spectroscopy, X-ray diffraction and electron microscopy.

A kinetic Monte Carlo method for the atomic-scale simulation of chemical vapor deposition: Application to diamond

We present a method for simulating the chemical vapor deposition(CVD) of thin films. The model is based upon a three-dimensional representation of film growth on the atomic scale that incorporates the effects of surface atomic structure and morphology. Film growth is simulated on lattice. The temporal evolution of the film during growth is examined on the atomic scale by a Monte Carlo technique parameterized by the rates of the important surface chemical reactions. The approach is similar to the N-fold way in that one reaction occurs at each simulation step, and the time increment between reaction events is variable. As an example of the application of the simulation technique, the growth of {111}-oriented diamondfilms was simulated for fifteen substrate temperatures ranging from 800 to 1500 K. Film growth rates and incorporated vacancy and H atom concentrations were computed at each temperature. Under typical CVD conditions, the simulated growth rates vary from about 0.1 to 0.8 μm/hr between 800 and 1500 K and the activation energy for growth on the {111}: H surface between 800 and 1100 K is 11.3 kcal/mol. The simulations predict that the concentrations of incorporated point defects are low at substrate temperatures below 1300 K, but become significant above this temperature. If the ratio between growth rate and point defect concentration is used as a measure of growth efficiency, ideal substrate temperatures for the growth of {111}-oriented diamondfilms are in the vicinity of 1100 to 1200 K.

Understanding the chemical vapor deposition of diamond: recent progress

In this paper we review and provide an overview to the understanding of the chemical vapor deposition (CVD) of diamond materials with a particular focus on the commonly used microwave plasma-activated chemical vapor deposition (MPCVD). The major topics covered are experimental measurements in situ to diamond CVD reactors, and MPCVD in particular, coupled with models of the gas phase chemical and plasma kinetics to provide insight into the distribution of critical chemical species throughout the reactor, followed by a discussion of the surface chemical process involved in diamond growth.

Electrochemical study of diamond thin films in neutral and basic solutions of nitrate

Abstract The electrochemical behavior of boron-doped diamond films has been investigated in a number of neutral and alkaline solutions with and without nitrate ions. Two kinds of diamond electrode were studied: self-supported film (100 μm) (sample A) and diamond film (10 μm) supported on a Si substrate (sample B). It was found that water oxidation and reduction appear at much larger polarizations for diamond electrodes, as compared with platinum and platinized platinum electrodes. In particular, the higher (cathodic) overpotential for hydrogen reduction permits efficient nitrate reduction to ammonia. The underlying Si substrate is shown to take part in the electrochemistry of the diamond electrodes. In the case of the Si-supported electrode (sample B) the reaction with the Si substrate was imminent. For the free-standing diamond electrode (sample A) various impurities in the grain boundaries and at the back of the electrode, including the back metallic contact, intervened with the electrochemistry of the diamond electrode, but to a much lesser extent than with sample B. Meticulous cleaning and careful working practices permitted this interference to be excluded altogether in sample A.