Plastic Morphological Response to Spectral Shifts during Inorganic Phototropic Growth

Plants exhibit phototropism in which growth is directed toward sunlight and demonstrate morphological plasticity in response to changes in the spectral distribution of the incident illumination. Inorganic phototropic growth via template-free, light-directed electrochemical deposition of semiconductor material can spontaneously generate highly ordered mesostructures with anisotropic, nanoscale lamellar features that exhibit a pitch proportional to the wavelength (λ) of the stimulating illumination. In this work, Se–Te films were generated via a two-step inorganic phototropic growth process using a series of narrowband light-emitting diode sources with discrete output wavelengths (λ0 ≠ λ1). Analogous to the plasticity observed in plants, changes in illumination wavelength from λ0 to λ1 resulted in morphological changes including feature branching, termination, and/or fusion along the growth direction. The interfacial feature pitch changed with the growth duration, in some cases in a notably nonmonotonic fashion, and eventually matched that obtained for growth using only λ1. Simulated morphologies generated by modeling light–material interactions at the growth interface closely matched the evolved structures observed experimentally, indicating that the characteristics of the optical stimulation produce the observed plastic response during inorganic phototropic growth. Examination of the interfacial electric field modulation for λ1 illumination of simplified structures, representative of those generated experimentally, revealed the interfacial light scattering and concentration behavior that directed phototropic growth away from equilibrium, as well as the emergent nature of the phenomena that reestablish equilibrium.