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By means of x‐ray diffraction techniques, the presence of twin relationships in silicon epitaxially deposited on sapphire was demonstrated and the relative amounts determined in a semiquantitative manner. A correlation was made with the surface structure observed by means of replica electron microscopy and the twinning relationships. The minor twin relationships appear to be present as long thin microtwins. Besides the four silicon‐sapphire orientation relationships previously reported, a fifth relationship has been found. The density of twins deposited on substrates near the (1¯1¯23) orientation appears to be greatly dependent on the substrate orientation. Possible explanations for this phenomenon are discussed. Discrepancies with the work of other investigators are described.