Structure–Property Relationship of Low-Dimensional Layered GaSe_<i>x</i>Te_1–<i>x</i> Alloys

We report the growth of layered GaSe_<i>x</i>Te_1–<i>x</i> mesostructures across the whole composition range. For compositions up to <i>x</i> = 0.32 (the Te-rich region), mesocrystals form predominantly in the monoclinic structure, similar to naturally occurring GaTe. However, the hexagonal crystal structure, similar to naturally occurring GaSe, begins growing at the <i>x</i> = 0.28 composition and grows almost exclusively in the range of <i>x</i> = 0.32 to pure GaSe, establishing a region of composition where both monoclinic and hexagonal crystals exist. While the optical bandgap of the monoclinic phase increases linearly from 1.65 to 1.77 eV with increasing Se content, the incorporation of Te in the hexagonal phase reduces the optical gap from 2.01 (pure GaSe) to 1.38 eV (<i>x</i> = 0.28). Specifically, a bandgap difference of ∼0.35 eV between monoclinic and hexagonal crystals is observed in the composition range where both crystal structures can be grown. These observations are in good agreement with direct-gap trends calculated by density functional theory, which show a linear dependence on composition for the direct gap of the monoclinic phase and a considerable bowing of the direct gap of the hexagonal phase for Te-rich compositions. Our results show that layered semiconductor alloys are remarkably versatile systems in which electronic properties can be controlled by not only thickness but also structural phase and composition