Disclosed herein are methods of self-assembling nanoparticles on specific sites of a substrate. The method generally includes introducing a p-type dopant species to at least a portion of an n-type substrate or introducing an n-type dopant species to at least a portion of a p-type substrate, wherein the dopant species creates a surface charge opposite in polarity to that of the substrate surface prior to the introducing; contacting the nanoparticles with the surface of the substrate; and self-assembling a layer of the nanoparticles on p-type regions of the substrate. The methods described herein may be used in the formation of sub-22 nanometer channels, which find use in field-effect transistors, electronic chips, nanoscale biosensors, photonic band gap devices, lasers in optoelectronics and photonics chips, as well as nano-electro-mechanical devices (NEMS).