Correlative and in situ microscopy investigation of phase transformation, crystal growth and degradation of antimony sulfide thin films

Antimony sulfide (Sb$_2$S$_3$), a compound of earth-abundant elements with highly anisotropic, quasi-layered crystal structure, triggered growing interest as a solar absorber in photovoltaics and as a phase change material in memory devices, yet challenges remain in achieving high-quality thin films with controlled nucleation and growth for optimal performance. Here, we investigate the phase transformation, crystal structure and properties, growth and degradation of atomic layer deposited Sb$_2$S$_3$ thin films using in situ TEM and correlative ex situ analysis. The as-deposited amorphous films crystallized at 243{\deg}C, forming grains with an [100] out-of-plane texture and developed into tens to hundreds of micrometer, leaves-shaped grains. Introducing an ultra-thin ZnS interfacial layer increased nucleation density, and resulted in a few micrometer-sized, more uniform grains while retaining the overall [100] texture. In situ observations and subsequent crystal orientation analysis with cutting-edge 4D-STEM and EBSD revealed that the grains grew faster along the [010] ribbon direction and that the bare films underwent early-stage degradation, forming holes in amorphous regions during annealing. The ZnS interlayer mitigated degradation, stabilizing the films and improving their uniformity. These findings offer valuable insights for optimizing Sb$_2$S$_3$ thin films for applications both as solar cell materials and phase change materials.