Liquid-liquid phase transition in supercooled silicon

Abstract

Silicon in its liquid and amorphous forms occupies a unique position among amorphous materials. Obviously important in its own right, the amorphous form is structurally close to the group of 4-4, 3-5 and 2-6 amorphous semiconductors that have been found to have interesting pressure-induced semiconductor-to-metal phase transitions. On the other hand, its liquid form has much in common, thermodynamically, with water and other 'tetrahedral network' liquids that show density maxima. Proper study of the 'liquid-amorphous transition', documented for non-crystalline silicon by both experimental and computer simulation studies may therefore also shed light on phase behaviour in these related materials. Here, we provide detailed and unambiguous simulation evidence that the transition in supercooled liquid silicon, in the Stillinger-Weber potential, is thermodynamically of first order and indeed occurs between two liquid states, as originally predicted by Aptekar. In addition we present evidence to support the relevance of spinodal divergences near such a transition, and the prediction that the transition marks a change in the liquid dynamic character from that of a fragile liquid to that of a strong liquid.