As the technology for diamond film preparation by plasma-assisted CVD and related procedures has advanced, Raman spectroscopy has emerged as one of the principal characterization tools for diamond materials. Cubic diamond has a single Raman-active first order phonon mode at the center of the Brillouin zone. The presence of sharp Raman lines allows cubic diamond to be recognized against a background of graphitic carbon and also to characterize the graphitic carbon. Small shifts in the band wavenumber have been related to the stress state of deposited films. The effect is most noticeable in diamond films deposited on hard substrates such as alumina or carbides. The Raman line width varies with mode of preparation of the diamond and has been related to degree of structural order. The Raman spectrum of hexagonal diamond (lonsdaleite) is distinct from that of the cubic diamond and allows it to be recognized.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S0884291400004441

Characterization of diamond films by Raman spectroscopy

Atomic-scale control and manipulation of the microstructure of polycrystalline thin films during kinetically limited low-temperature deposition, crucial for a broad range of industrial applications, has been a leading goal of materials science during the past decades. Here, we review the present understanding of film growth processes—nucleation, coalescence, competitive grain growth, and recrystallization—and their role in microstructural evolution as a function of deposition variables including temperature, the presence of reactive species, and the use of low-energy ion irradiation during growth.

Microstructural evolution during film growth

Diamond may be grown at low pressures where it is the metastable form of carbon. Recent advances in a wide variety of plasma and electrical discharge methods have led to dramatic increases in growth rates. All of these methods have certain aspects in common, namely, the presence of atomic hydrogen and the production of energetic carbon-containing fragments under conditions that support high mobilities on the diamond surface. Some understanding of the processes taking place during nucleation and growth of diamond has been achieved, but detailed molecular mechanisms are not yet known. Related research has led to the discovery of a new class of materials, the "diamondlike" phases. Vapor-grown diamond and diamondlike materials may have eventual applications in abrasives, tool coatings, bearing surfaces, electronics, optics, tribological surfaces, and corrosion protection.

https://science.sciencemag.org/content/sci/241/4868/913.full.pdf

Low-Pressure, Metastable Growth of Diamond and "Diamondlike" Phases

Current issues and problems in the chemical vapor deposition (CVD) of diamond are those which relate to its characterization, its nucleation on foreign surfaces, the question of its formation in preference to the other phases of solid carbon (for example, graphite, chaoite, or lonsdaleite), why different morphologies and crystallographic orientations (textures) are seen in different experiments or with different parameters in the same experiment, and finally whether well-crystallized metastable phases can be obtained by CVD in other material systems or are only a peculiarity of carbon chemistry. Whether a given carbon coating is justly described as diamond has been such an issue, and coatings should clearly show evidence for diamond by x-ray diffraction and Raman spectroscopy before the claim of diamond is made. Experimental results have not been consistent in many cases, and much work remains to be done before an accurate assessment can be made of the technological impact of the development.

https://science.sciencemag.org/content/sci/247/4943/688.full.pdf

Current Issues and Problems in the Chemical Vapor Deposition of Diamond

On etudie le depot chimique en phase vapeur et la croissance cristalline de revetement de diamant

/pdf/diamond-ceramic-coating-of-the-future-31m184yw0t.pdf

Diamond—Ceramic Coating of the Future

Crystallization of diamond from the gas phase; Part 1

A mass of diamond crystals contacting a mass of elemental silicon are confined within a pressure-transmitting medium. The resulting charge assembly is subjected to a pressure of at least 25 kilobars causing application of isostatic pressure to the contacting masses which dimensionally stabilizes them and increases the density of the mass of diamond crystals. The resulting pressure-maintained charge assembly is heated to a temperature sufficient to melt the silicon and at which no significant graphitization of the diamond occurs whereby the silicon is infiltrated through the interstices between the diamond crystals producing, upon cooling, an adherently bonded integral body.

Silicon carbide and silicon bonded polycrystalline diamond body and method of making it

Plastic deformation and “work-hardening” of diamond

The purpose of this study was to try to find out why BaTiO3 (essentially a cubic structure) can consistently be grown from KF solutions as large flat plates when a more equant morphology is expected. It is suggested that the size, shape, and perfection of the platelike “butterfly” twin crystals can be qualitatively related to the re-entrant angles which result from {111} twinning of crystals of {100} habit. The re-entrant angles form permanent steps for both the advancing crystal tip and for the growth layers of the wings. The amount of twinning is related to the cooling rate and to the presence of certain impurities. Thus it can be shown that increasing the cooling rate increases the number of {111} twins (essentially a hexagonal stacking fault); the extreme case is the metastable formation of hexagonal barium titanate by quenching. Evidence is presented for the stabilization of the Ti2O9 group of the hexagonal structure by substitution of ions of lower polarizing power.

Observations on Growth of BaTiO3, Crystals from KF Solutions

A mass of diamond crystals in contact with a mass of eutectiferous silicon-rich alloy and a silicon carbide ceramic substrate are disposed in a container and placed within a pressure transmitting powder medium. Pressure is applied to the powder medium resulting in substantially isostatic pressure being applied to the container and its contents sufficient to dimensionally stabilize the container and its contents. The resulting shaped substantially isostatic system of powder-enveloped container is hot-pressed whereby fluid eutectiferous silicon-rich alloy is produced and infiltrated through the interstices between the diamond crystals and contacts the contacting face of the silicon carbide substrate sufficiently producing, upon cooling, an adherently bonded integral composite.

Polycrystalline diamond body/silicon carbide substrate composite

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