New insight into pressure-induced phase transitions of amorphous silicon: the role of impurities

The pressure-induced phase transformations of a form of amorphous silicon (a-Si) with well characterized impurity levels and structure are examined at pressures up to 40 GPa using in situ synchrotron X-ray radiation. At similar to 12 GPa crystallization commences, but it is not completed until similar to 16 GPa. At higher pressures, not all the crystalline phases observed for crystalline silicon (c-Si) appear. On pressure release, none of the metastable crystalline phases observed for c-Si nucleate. Instead an amorphous phase is re-formed. This is in contrast to all previous diamond-anvil studies on a-Si. If full pressure-induced crystallization occurred, the material remained crystalline on unloading. The formation of a-Si upon unloading was only observed when a high-density amorphous phase was reported on loading. The fully characterized nature of the a-Si used in this current study allows for the interpretation of this significant diversity in terms of impurity content of the a-Si used. Namely, this suggests that 'ideal' (pure, voidless, structurally relaxed) a-Si will follow the same transition pathway as observed for c-Si, while crystallization of a-Si forms with a high impurity content is retarded or even inhibited. The a-Si used here straddles both regimes and thus, although full crystallization occurs, the more complex crystalline structures fail to nucleate.