InAs nanocrystals field-effect transistors with an ON/OFF ratio of 105 are reported. By tailoring the interface regions in the active layer step-by-step, the evolution of the ON/OFF ratio can be followed from approximately 5 all the way to around 105. The formation of a semiconducting solid from colloidal nanocrystals is achieved through targeted design of the nanocrystal–nanocrystal interaction. The manipulation characteristics of the nanocrystal interfaces include the matrix surrounding the inorganic core, the interparticle distance, and the order of nanocrystals in the 3D array. Through careful analysis of device characteristics following each treatment, the effect of each on the physical properties of the films are able to be verified. The enhanced performance is related to interparticle spacing, reduction in sub-gap states, and better electronic order (lower σ parameter). Films with enhanced charge transport qualities retain their quantum-confined characteristics throughout the procedure, thus making them useful for optoelectronic applications.