This paper reports the results of a detailed X-ray diffraction study of a new phase-transformation observed in SiC crystals grown by a vapour-liquid-solid mechanism involving the hydrogen-reduction of methyltrichlorosilane. The 10.ℓ reciprocal lattice rows of these crystals, as recorded on X-ray diffraction photographs, reveal sharp reflections corresponding to the hexagonal close-packed 2H (ABAB….) structure and sometimes also corresponding to the cubic close-packed 3C (ABCABC…) structure. These reflections are invariably connected by a diffuse but continuous streak whose intensity is a measure of the random faulting on the basal planes. The crystals were needle shaped and the structure sometimes varied along their length.
Several crystals were annealed in an inert atmosphere at progressively higher temperatures and their 10.ℓ reciprocal lattice row re-examined to determine the annealing behaviour as well as possible structural transformations. For a number of dark green needles having a faulted 2H structure the 2H reflections disappeared around 1400° C and the 10.ℓ reciprocal lattice row revealed only a continuous streak with increased intensity around positions for 3C reflections. On further heating the structure went over to a strongly faulted 3C. Around 1600°C the appearance of a 6H structure became discernible while highly diffuse 30 reflections still persisted. The reversible part of the transformations, if any, could not be observed. Some of the structures were, however, found to be much more stable and did not transform even up to 1650° C.
The above results, in particular the discovery of a 2H-3C phase-transformation around 1400°C, throw fresh light on the thermodynamic stability of the different SiC types. The mechanism of the 2H-3C transformation, the possible influence of faults and impurities and the thermal stability of various SiC structures are discussed on the basis of the experimental results stated above.