Template-Free Synthesis of Periodic Three-Dimensional PbSe Nanostructures via Photoelectrodeposition.

Highly periodic, geometrically directed, anisotropic Se-Pb films have been synthesized at room temperature from an isotropic aqueous solution without the use of physical templates by photoelectrodeposition using a series of discrete input illumination polarizations and wavelengths from an unstructured, uncorrelated, incoherent light source. Dark growth did not generate deposits with substantial long-range order, but growth using unpolarized illumination resulted in an ordered, nanoscale, mesh-type morphology. Linearly polarized illumination generated Se-Pb deposits that displayed an ordered, highly anisotropic lamellar pattern wherein the long axes of the lamellae were aligned parallel to the light polarization vector. The pitch of the lamellar features was proportional to the input light wavelength, as confirmed by Fourier analysis. Full-wave electromagnetic and Monte Carlo growth simulations that incorporated only the fundamental light-matter interactions during growth successfully reproduced the experimentally observed morphologies and quantitatively matched the pattern periodicities. Electrochemical postprocessing of the as-deposited Se-Pb structures resulted in the generation of stoichiometric, crystalline PbSe while preserving the nanopatterned morphology, thus broadening the genus of materials that can be prepared with controlled three-dimensional morphologies through maskless photoelectrodeposition.