Not yet reviewed by Pith; the record is open.

Non-linear absorption phenomena induced by controlled irradiation with a femtosecond laser beam can be used to tailor materials properties within the bulk of substrates. One of the most successful applications of this technique is the ability to fabricate three-dimensional micro-devices integrating optical, mechanical or fluid handling functions in a single substrate. In this context, amorphous SiO2 is the most widely studied material. Here we show that short (50-fs) femtosecond pulses induce the separation of Si and O ions in SiO2 substrates, leading to the formation of micro-crystallites that we identify as pure crystalline phase of Si. Interestingly, this polymorphic phase transformation occurs in the absence of laser-induced confined microexplosion and with moderate numerical aperture. These findings not only unravel a key mechanism related to the transformation of the material and its subsequent properties, but also pave the road for the development of three-dimensional Si-rich structures embedded in a pure silica phase, eventually leading to novel disruptive approaches for fabricating three- dimensional micro-devices. For instance, one could imagine a silica-host substrate, in which arbitrary three-dimensional silicon-based components are direct-write using a femtosecond laser, rather than through assembly of components coming out of different substrates or using multiple processing steps.