Emergent grain boundary phases in stressed polycrystalline thin films

Abstract

The grain boundary (GB) microstructure influences and is influenced by the development of residual stresses during synthesis of polycrystalline thin films. Recent studies have shown that the frustration between the preferred growth direction and rotations of abutting crystals to local cusps in GB energies leads to internal stresses localized within nanoscopic surface layers around the valleys and ridges that form at emergent boundaries (eGBs). Using a combination of continuum frameworks, numerical analyses, and all-atom simulations of bicrystal $\ensuremath{\langle}111\ensuremath{\rangle}$ copper films, we show that eGBs tune their surface morphology and rotation extent in response to external strains. Compression favors rotation to and growth of low-energy GB phases (complexions) at eGB valleys while tension favors the transitions at eGB ridges, a reflection of the stress-induced mass efflux/influx that changes the energetic balance between interfacial and deformation energies. Molecular dynamics simulations of strained and growing bicrystal films reveal that the eGB phase transition is coupled to island formation at the surface triple junctions, providing a direct link between eGB phases and surface step flow. The interplay between eGB structure, morphology, and mechanics emerges as a crucial ingredient for predictive understanding of stress and morphological evolution during film growth, with broad implications for multifunctional response of polycrystalline surfaces in a diverse range of surface phenomena such as surface-mediated deformation, interfacial embrittlement, thermal grooving, stress corrosion, surface catalysis, and topological conduction.