PART III - Nucleation and Crystal Growth of Silicon on Sapphire

When the nucleation of silicon on a sapphire substrate is accomplished by gradually decreasing the substrate temperature while subjecting it to a constant impingement rate of hydrogen and silicon tetrachloride, the resulting deposit is characterized by widely separated islands of silicon scattered over an "open sea" of sapphire. Analysis shows that nucleation takes place mainly on sites of large adsorption energy, about 85 kcal per mole, and small surface concentration, about 108 cm-2. Crystal growth proceeds rapidly on these nuclei and results in enough depletion of Sicl4 from the ambient gas to suppress further nucleation. The technological importance of single-crystal films on dielectric substrates has prompted considerable work on the deposition of silicon on sapphire. This paper is concerned with the deposition of silicon, by the reduction of silicon tetrachloride with hydrogen, onto heated sapphire substrates. The apparatus consisted of a temperature-controlled container for the silicon tetrachloride along with gas lines and flow meters necessary to convey a hydrogen-silicon tetrachloride mixture to a reaction chamber constructed of quartz tubing. Heat for the substrate was provided by means of an inductively heated graphite susceptor. The observations pertinent to the present discussion were made with an American Optical Co. high-temperature microscope which allowed us to make motion pictures of the deposition process at a magnification of approximately 50 times. Two main categories of experiments were carried out: one on determination of critical condensation temperatures and the other on the deposition of epitaxial silicon films on the sapphire substrates. Critical condensation temperatures were determined in the traditional way by raising the substrate temperature well above that at which condensation could be expected at the impingement rates being studied and then gradually lowering the temperature until the condensation of the first silicon was observed. This was done initially with ellipsometry-type detection but it was soon discovered that the deposits were occurring as widely separated islands and groups of islands scattered over an "open sea" of sapphire. We have called these archipelago formations. They were most easily detected by optical microscopy. Data gathered from experiments of this type have been collected in Table I. Motion pictures of the formation of archipelago patterns show that the nucleation period lasts about 10 sec if the substrate temperature and impingement rate are kept constant. Essentially all of the nuclei are formed in a few seconds and all subsequent silicon deposition merely adds to the size of the established nuclei. After an archipelago formation has matured at a given substrate temperature and impingement rate, it is very difficult to stimulate any further nucleation in the open space between islands. Lowering the substrate temperature will occasionally stimulate nucleation but increasing the impingement rate hardly ever produces any more new nuclei. It should also be emphasized that the nucleation rates appear to be very small, about 104 cm-2 sec-1. They will receive special attention in the analysis section. Another series of experiments was performed employing a systematic variation of substrate temperatures and impingement rates approximating those expected to produce epitaxy. Sapphire substrates with surfaces normal to the 2233 direction were used. In contrast to the procedure that produces archipelago patterns, these films were deposited by raising the substrate temperature to a desired value at which time the silicon tetrachloride and hydrogen flow was begun. Of course, these depositions produced mainly films that were continuous. After removal from the deposition chamber, the substrate and silicon film were examined microscopically to determine the nature of the deposit and by X-ray diffraction to determine the extent to which a single-crystal film had been achieved. Results of these experiments are summarized in Table 11. Of interest for the present analysis is the fact that epitaxy appears to be confined to a fairly narrow temperature range between about 1050" and 1150°C. This also will be discussed in the analysis section. ANALYSIS In this section we shall apply nucleation theory to the data presented above with the objective of testing