Microscale
patterning of colloidal nanocrystal (NC) films is important
for their integration in devices. Here, we introduce the direct optical
patterning of all-inorganic NCs without the use of additional photosensitive
ligands or additives. We determined that photoexposure of ligand-stripped,
“bare” NCs in air significantly reduces their solubility
in polar solvents due to photo-oxidation of surface ions. Doses as
low as 20 mJ/cm2 could be used; the only obvious criterion
for material selection is that the NCs need to have significant absorption
at the irradiation wavelength. However, transparent NCs can still
be patterned by mixing them with suitably absorbing NCs. This approach
enabled the patterning of bare ZnSe, CdSe, ZnS, InP, CeO2, CdSe/CdS, and CdSe/ZnS NCs as well as mixtures of ZrO2 or HfO2 NCs with ZnSe NCs. Optical, X-ray photoelectron,
and infrared spectroscopies show that solubility loss results from
desorption of bound solvent due to photo-oxidation of surface ions.
We also demonstrate two approaches, compatible with our patterning
method, for modulating the porosity and refractive index of NC films.
Block copolymer templating decreases the film density, and thus the
refractive index, by introducing mesoporosity. Alternatively, hot
isostatic pressing increases the packing density and refractive index
of NC layers. For example, the packing fraction of a ZnS NC film can
be increased from 0.51 to 0.87 upon hot isostatic pressing at 450
°C and 15 000 psi. Our findings demonstrate that direct
lithography by photo-oxidation of bare NC surfaces is an accessible
patterning method for facilitating the exploration of more complex
NC device architectures while eliminating the influence of bulky or
insulating surfactants.