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.

Accurate potential energy surface calculations are presented for many of the key steps involved in diamond chemical vapor deposition on the [100] surface (in its 2 x 1 reconstructed and hydrogenated form). The growing diamond surface was described by using a large (approximately 1500 atoms) cluster model, with the key atoms involved in chemical steps being described by using a quantum mechanical (QM, density functional theory, DFT) method and the bulk of the atoms being described by molecular mechanics (MM). The resulting hybrid QM/MM calculations are more systematic and/or at a higher level of theory than previous work on this growth process. The dominant process for carbon addition, in the form of methyl radicals, is predicted to be addition to a surface radical site, opening of the adjacent C-C dimer bond, insertion, and ultimate ring closure. Other steps such as insertion across the trough between rows of dimer bonds or addition to a neighboring dimer leading to formation of a reconstruction on the next layer may also contribute. Etching of carbon can also occur; the most likely mechanism involves loss of a two-carbon moiety in the form of ethene. The present higher-level calculations confirm that migration of inserted carbon along both dimer rows and chains should be relatively facile, with barriers of approximately 150 kJ mol (-1) when starting from suitable diradical species, and that this step should play an important role in establishing growth of smooth surfaces.

This paper describes a three-pronged study of microwave (MW) activated B(2)H(6)/Ar/H(2) plasmas as a precursor to diagnosis of the B(2)H(6)/CH(4)/Ar/H(2) plasmas used for the chemical vapor deposition of B-doped diamond. Absolute column densities of B atoms and BH radicals have been determined by cavity ring-down spectroscopy as a function of height (z) above a molybdenum substrate and of the plasma process conditions (B(2)H(6) and Ar partial pressures, total pressure, and supplied MW power). Optical emission spectroscopy has been used to explore variations in the relative densities of electronically excited BH, H, and H(2) species as a function of the same process conditions and of time after introducing B(2)H(6) into a pre-existing Ar/H(2) plasma. The experimental measurements are complemented by extensive 2-D(r, z) modeling of the plasma chemistry, which results in refinements to the existing B/H chemistry and thermochemistry and demonstrates the potentially substantial loss of gas-phase BH(x) species through reaction with trace quantities of air/O(2) in the process gas mixture and heterogeneous processes occurring at the reactor wall.

CH4 and C2H2 molecules (and their interconversion) in hydrocarbon/rare gas/H2 gas mixtures in a microwave reactor used for plasma enhanced diamond chemical vapor deposition (CVD) have been investigated by line-of-sight infrared absorption spectroscopy in the wavenumber range of 1276.5−1273.1 cm−1 using a quantum cascade laser spectrometer. Parameters explored include process conditions [pressure, input power, source hydrocarbon, rare gas (Ar or Ne), input gas mixing ratio], height (z) above the substrate, and time (t) after addition of hydrocarbon to a pre-existing Ar/H2 plasma. The line integrated absorptions so obtained have been converted to species number densities by reference to the companion two-dimensional (r,z) modeling of the CVD reactor described in Mankelevich et al. [J. Appl. Phys. 104, 113304 (2008)] . The gas temperature distribution within the reactor ensures that the measured absorptions are dominated by CH4 and C2H2 molecules in the cool periphery of the reactor. Nonetheless, the measurements prove to be of enormous value in testing, tensioning, and confirming the model predictions. Under standard process conditions, the study confirms that all hydrocarbon source gases investigated (methane, acetylene, ethane, propyne, propane, and butane) are converted into a mixture dominated by CH4 and C2H2. The interconversion between these two species is highly dependent on the local gas temperature and the H atom number density, and thus on position within the reactor. CH4→C2H2 conversion occurs most efficiently in an annular shell around the central plasma (characterized by 1400

The plume of ejected material accompanying pulsed laser ablation of a ZnO target at 193 nm in vacuum has been investigated using wavelength and spatially resolved optical emission spectroscopy and Langmuir probes. All lines in the observed optical emission spectra are assignable to electronically excited Zn+* cations, and Zn* and O* neutrals, all of which emitting species we attribute to the result of electron–ion recombination processes in the gas phase following material ejection, laser–plume interactions, ionization, and thus, plasma formation. Various contributory components can be identified within the plume. Included among these are: a fast distribution of Zn2+ ions (observed via emission from highly excited states of Zn+*) together with an accompanying subset of fast electrons—the relative importance of which increases with increasing incident fluence on the target; a more abundant slower component involving both Zn+ and O+ ions, which expand in association with the main body of the electron distribution; and a slow moving component of Zn* emitters, which we suggest should be associated with material that has been backscattered from the expanding plasma ball towards the target surface and then rebounded or desorbed into the gas phase. The observation that the postablated target surface is substantially enriched in Zn provides additional support for the importance of material backscattering from within the dense plasma ball, accommodation, and in this case, recondensation on the target. The deduction that the target surface in the vicinity of the irradiated area is Zn rich after just a few laser shots provides an explanation for the oft-reported observation that ZnO films deposited by pulsed laser ablation of ZnO in vacuum are nonstoichiometric, with a Zn:O ratio greater than unity. Such backscattering from the plasma volume and selective recondensation of the less volatile component or components within the plume prior to the next ablation pulse being incident on the target surface appear to account for virtually all reported instances of nonstoichiometric film growth by pulsed laser deposition (PLD) in vacuum. Indeed, given the deduced area of the target surface affected by such redeposition and the target translation speeds typically employed in PLD studies, it would appear that nonstoichiometric film growth is likely to be the norm whenever PLD is carried out in vacuum and at wavelengths and fluences that lead to formation of a sufficiently dense plasma to cause material redeposition on the target.