Programmable Assembly of Semiconductor Mesostructures via Inorganic Phototropism

Plants exhibit a phototropic response and direct the addition of new biomass to optimize collection of solar insolation. Analogous inorganic phototropism growth enables the programmable assembly of complex 3D nanoarchitectures with instruction by an incoherent, unstructured, mW cm^-2 intensity light beam. Inorganic phototropism has been demonstrated via the light-mediated electrochemical assembly of semiconductor deposits from solution-phase precursor ions. No structured light field (no photomask), no lithographic processes and no templating agents (ligands, surfactants, etc.) are utilized. Nevertheless, ordered nanoscale features are conformally assembled over full macroscale (cm²) areas with feature heights on the order of several um with growth times < 5 min. In-plane anisotropy is a function of the input polarization. Isotropic morphologies consisting of ordered arrays of nanoscale holes were generated using unpolarized illumination whereas linearly polarized light resulted in anisotropic lamellar structures with in-plane orientations set by the polarization direction. The structure pitch was dependent on the spectral distribution of the input light with shorter wavelengths effecting higher feature densities. The out-of-plane growth direction is related to the propagation direction of the input light, mirroring the way in which palm trees develop an observable tilt toward the average position of the solar azimuth. Time-varying optical inputs enable programming of 3D intricacy by evolving the in-plane structure along the out-of-plane dimension, e.g. an abrupt reduction in the input wavelength results in a concomitant increase in the interfacial density resulting in tuning fork structures similar to how blue light effects branching in many shade-intolerant plants. Additional morphological control has also been effected by using multiple simultaneous illumination inputs. Modeling of the growth using a combination of full-wave electromagnetic simulations of light absorption and scattering coupled with Monte Carlo simulations of mass addition successfully reproduced the experimentally observed morphologies and indicated that assembly was directed by evolution of the growth front to maximize anisotropic light collection. The assembly was observed to be a highly emergent phenomenon involving optical communication between neighboring features including cooperative scattering and synergistic absorption and thus is similar to the manner in which neighboring plants exchange information and avoid competition for light resources.