Anisotropic crystallization in solution processed chalcogenide thin film by linearly polarized laser

The low activation energy associated with amorphous chalcogenide structures offers broad tunability of material properties with laser-based or thermal processing. In this paper, we study near-bandgap laser induced anisotropic crystallization in solution processed arsenic sulfide. The modified electronic bandtail states associated with laser irradiation lead to a distinctive photoluminescence spectrum, compared to thermally annealed amorphous glass. Laser crystalized materials exhibit a periodic subwavelength ripple structure in transmission electron microscopy experiments and show polarization dependent photoluminescence. Analysis of the local atomic structure of these materials using laboratory-based X-ray pair distribution function analysis indicates that laser irradiation causes a slight rearrangement at the atomic length scale, with a small percentage of S-S homopolar bonds converting to As-S heteropolar bonds. These results highlight fundamental differences between laser and thermal processing in this important class of materials.