PART III - Electron-Microscope Replica Study of Epitaxial Silicon Nucleation on Silicon

Direct platinum carbon replicas have been used to study substrates prior to growth and after initial nu-cleation of the layer. Replicas have been directly stripped and correlations have been made with other replica techniques. Mechanically polished substrates are very flat with occasional areas of "dirt", which is apparently silicon. When such substrates are etched in hydrochloric acid gas, scratches and hexagonal defects (thought to be polishing compound) are revealed, together with areas of apparent redeposition. Chemically polished substrates are much less flat although much more homogeneous in appearance. Heat treat)nents have no effect. Nuclei deposited on these surfaces, using a normal silicon tetrachloride system, have been examined. Nuclei on mechanically polished subsrates occur in random areas only, whereas on chemically polished surfaces they are more uniformly distributed. THE interest in the study of thin films and now their rapidly expanding use in many fields has increased over a period of years. Much of this current interest, particularly in the field of single-crystal or epitaxial thin films, has derived its stimulus not only from possibilities for application but also from fundamental electron-microscope studies which have indicated the manner of growth of such layers from the initial nuclei.1-5 Previous work involving study of growth processes may be divided into three categories. First, vacuum deposition, primarily of metals, on a variety of substrates has been studied by electron microscopy and electron-diffraction techniques. These have shown the three-dimensional aspect of nucleation and the remarkable liquidlike behavior of the growing nuclei which coalesce to form a complete layer. More recently this work has been expanded in two ways: by growth inside the electron microscope this has obvious advantages for kinetic studies; and by growth in ultrahigh vacuum—much of this work has been done on semiconductors.8-11 It is of interest to note that metals, specifically gold deposited on rock salt, will form only polycrystalline layers in ultrahigh vacuum unless the substrate surface is contaminated.12 In general the mode of growth for vacuum-deposited semiconductor films is the same as that for metal films. The second method of growth that has been studied is that of electrodeposition.13,14 The little that has been published suggests that the mode of growth is similar to the vacuum case, except that irregularities may perturb the electric field and disturb the growth process. The third and last primary method of growing epitaxial layers is by use of chemical methods. These techniques have generated much interest and much has been published on them. Considerable electron-microscope work has been done on the defects in the layers; however comparatively little work has been undertaken on the initial nucleation and early stages of growth. Confining ourselves now exclusively to the case of silicon, Charig et a1.15 have considered the growth of silicon on silicon substrates by hydrogen reduction of trichlorosilane, and studied the films by means of replica and transmission techniques. Subsequently they have studied the same system for growth on quartz,16 and with the addition of pyrolysis of silane on quartz and alumina.17 Also Manasevit el al. have studied deposits using silane and silicon tetrachloride on sapphire.18-14 Finally, in this volume studies of deposition on beryllia and sapphire are reported. Although Revesz and Evans20 have examined complete layers, grown by means of the widely used silicon tetrachloride reaction, no detailed examination similar to that published by Charig and Joyce21 for the trichlorosilane system has been given. Therefore this investigation has examined substrate surfaces prior to growth and then nucleation on these surfaces for the silicon tetrachloride system. EXPERIMENTAL In this work the surfaces have been studied by means of standard replica techniques. Because of the very real problems associated with artifacts introduced,22 different replicas and different cleaning