Abstract
Diamond cubic silicon is widely used for electronic applications, integrated circuits, and photovoltaics, due to its high abundance, nontoxicity, and outstanding physicochemical properties. However, it is a semiconductor with an indirect band gap, depriving its further development. Fortunately, other polymorphs of silicon have been discovered successfully, and new functional allotropes are continuing to emerge, some of which are even stable in ambient conditions and could form the basis for the next revolution in electronics, stored energy, and optoelectronics. Such structures can lead to some excellent features, including a wide range of direct or quasi-direct band gaps allowed efficient for photoelectric conversion (examples include Si-III and Si-IV), as well as a smaller volume expansion as lithium-battery anode material (such as Si(24), Si(46), and Si(136)). This review aims to give a detailed overview of these exciting new properties and routes for the synthesis of novel Si allotropes. Lastly, the key problems and the developmental trends are put forward at the end of this article.