Sudden stress relaxation in compound semiconductor thin films triggered by secondary phase segregation

In polycrystalline compound semiconductor thin films, structural defects such as grain boundaries as well as lateral stress can form during film growth, which may deteriorate their electronic performance and mechanical stability. In Cu-based chalcogenide semiconductors such as $\mathrm{Cu}(\mathrm{In},\mathrm{Ga}){\mathrm{Se}}_{2}$ or ${\mathrm{Cu}}_{2}\mathrm{ZnSn}{(\mathrm{S},\mathrm{Se})}_{4}$, temporary Cu excess during film growth leads to improved microstructure such as a reduced grain boundary density, a strategy that has been used for decades for high-efficiency chalcopyrite thin film solar cells. However, the mechanisms responsible for the beneficial effect of Cu excess are yet not fully clarified. Here, we investigate the evolution of lateral stress, grain growth, and Cu-Se segregation during Cu-Se deposition onto Cu-poor ${\mathrm{CuInSe}}_{2}$. Real-time x-ray diffraction and fluorescence analysis with a double-detector setup reveals that sudden stress relaxation occurs shortly prior to Cu-Se segregation at the surface and precisely coincides with domain growth and change of texture. Numerical reaction-diffusion modeling provides an explanation for the observed delay of Cu-Se segregation. Our results show that partial recrystallization of the film can be already reached without the necessity of an overall Cu-rich film composition and thus suggest a new synthesis route for the fabrication of high-quality chalcopyrite absorber films.