Silicon clathrates are allotropes of silicon that show great promises for optoelectronics and batteries.However silicon clathrates in the form of films are relatively new and devices based on this material still have to be engineered. In this work we present a protocol for silicon clathrates film fabrication that does not necessitate a glove box. We show that dense films can be obtained with a pressure annealing treatment and that the films can be measured by atomic force microscopy. Ion implantation of P, B and As is performed on the clathrate films. Early photovoltaic devices are presented, with a maximum short circuit current density of 0.11 mA/cm².

Type I and type II silicon clathrates are guest–host structures made of silicon polyhedral cages large enough to contain atoms that can be either inserted or evacuated with only a slight volume change of the structure. This feature is of interest not only for batteries or storage applications but also for tuning the properties of the silicon clathrate films. The thermal decomposition process can be tuned to obtain Na8Si46 and Na2<x<10Si136 silicon clathrate films on intrinsic and p-type c-Si (001) wafer. Here, from a unique synthesized NaxSi136 film, a range of resistivity of minimum four order of magnitude is possible by using post-synthesis treatments, switching from metallic to semiconductor behavior as the Na content is lowered. Extended exposition to sodium vapor allows us to obtain fully occupied Na24Si136 metallic films, and annealing under iodine vapor is a way to reach the guest-free Si136, a semiconducting metastable form of silicon with a 1.9 eV direct bandgap. Electrical measurements and resistance vs temperature measurements of the silicon clathrate films further discriminate the behavior of the various materials as the Na concentration is changing, additionally shouldered by density functional theory calculations for various guest occupations, further motivating the urge of an innovative pathway toward true guest-free type I and type II silicon clathrates.

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