Nanoscale device fabrication technologies require toolsets for miniaturization and organization of materials at nanometer dimensions. Current toolsets have developed from two diametrically opposite strategies. The “top-down” strategy carves device structures into semiconductor wafers using deposition, lithography and etching. However, lithography at the nanometer scale is becoming exorbitantly costly. The “bottom-up” strategy synthesizes nanoscale molecules or polymers from smaller sub-units through thermodynamically driven self-assembly. However, device fabrication based primarily upon thermodynamic self-assembly has suffered grievously from high error rates. This laboratory is taking a different approach based on a new physical mechanism for photostimulated diffusion discovered here. This new strategy combines attractive features of top-down and bottom-up approaches by exploiting the self-organization capabilities latent in amorphous materials, but in a way that can be controlled by optical or electron beam exposure tools. We have developed a new surface self-assembly method at the 10-200 nm length scale using amorphous semiconducting materials. Patterned optical or electron beam exposure yields a spatially varying surface mass flux that, when performed at an annealing temperature just at the cusp of crystallization, provides the extra nudge to crystallize subcritical nuclei in regions dictated by the light flux. The full-fledged crystallites then grow by surface diffusion and Ostwald ripening until the desired fraction of the film has accreted onto the original nuclei. We have demonstrated this technique with titanium dioxide as the substrate material. This scheme should apply to a wide variety of semiconducting materials on nearly arbitrary substrates to form nanoarrays, nanowalls, and possibly three-dimensional structures. Possible applications include chalcogenide semiconductors for data storage media; nanoparticles arrays for direct use in sensors and solar cells; and semiconductor arrays for indirect use as seed layers for the subsequent deposition of sintered particle films in fabricating advanced ceramics and devices such as rechargeable batteries, solar cells, gas sensors, and photonic band gap materials in solar windowpanes.