Nanocrystal assemblies are being explored for a number of optoelectronic applications such as transparent conductors, photovoltaic solar cells, and electrochromic windows. Majority carrier transport is important for these applications, yet it remains relatively poorly understood in films comprised of touching nanocrystals. Specifically, the underlying structural parameters expected to determine the transport mechanism have not been fully elucidated. In this report, we demonstrate experimentally that the contact radius, between touching heavily doped ZnO nanocrystals, controls the electron transport mechanism. Spherical nanocrystals are considered, which are connected by a circular area. The radius of this circular area is the contact radius. For nanocrystals that have local majority carrier concentration above the Mott transition, there is a critical contact radius. If the contact radius between nanocrystals is less than the critical value, then the transport mechanism is variable range hopping. If the contact radius is greater than the critical value, the films display behavior consistent with metallic electron transport.

Thin films comprised of transparent conductive oxide (TCO) nanocrystals are attractive for a number of optoelectronic applications. However, it is often observed that the conductivity of such films is very low when they are in contact with air. It has recently been demonstrated, somewhat surprisingly, that filling in initially insulating films comprised of TCO nanocrystals with another insulator by atomic layer deposition (ALD) dramatically increases the conductivity by many orders of magnitude. This work aims to elucidate the mechanism by which the ALD coating increases conductivity. We examined the effect of removing two adsorbed oxygen species (physisorbed molecular water and chemisorbed hydroxide) on sheet resistance and compared this result to the results with thin films comprised of ZnO nanocrystals coated with Al2O3 and also HfO2 by ALD. Although both insulating infills decrease the sheet resistance and increase the stability of the films, there is a stark discrepancy between the two. From the in situ measurements, it was found that coating with Al2O3 removes both physisorbed water and chemisorbed hydroxide, resulting in a net reduction of the ZnO nanocrystals. Coating with HfO2 removes only physisorbed water, which was confirmed by Fourier transform infrared spectroscopy. A similar phenomenon was observed when thin films comprised of Sn-doped In2O3 nanocrystals were coated, suggesting Al2O3 can be used to reduce and stabilize metal oxide nanocrystals in general.

Lithium ion batteries have revolutionized portable electronics and have the potential to electrify the transportation sector.