Variations in the composition and structure of ZnO nanoparticle
interfaces have a key influence on the materials’ optoelectronic
properties and are responsible for high number of discrepant results reported
for ZnO-based nanomaterials. Here, we conduct a systematic study of the
room-temperature photoluminescence of anhydrous ZnO nanocrystals, as synthesized
in the gas phase and processed in water-free atmosphere, and of their colloidal
derivatives in aqueous dispersions with varying amounts of organic salt
admixtures. A free exciton band at
hv
= 3.3 eV is essentially
absent in the anhydrous ZnO nanocrystal powders measured in vacuum or in oxygen
atmosphere. Surface hydration of the nanoparticles during colloid formation
leads to the emergence of the free exciton band at
hv
= 3.3 eV
and induces a small but significant release in lattice strain as detected by
X-ray diffraction. Most importantly, admixture of acetate or citrate ions to the
aqueous colloidal dispersions not only allows for the control of the
ζ-potential but also affects the intensity of the free exciton emission
in a correlated manner. The buildup of negative charge at the
solid—liquid interface, as produced by citrate adsorption, increases the
free exciton emission. This effect is attributed to the suppression of electron
trapping in the near-surface region, which counteracts nonradiative exciton
recombination. Using well-defined ZnO nanoparticles as model systems for
interface chemistry studies, our findings highlight water-induced key effects
that depend on the composition of the aqueous solution shell around the
semiconducting metal oxide nanoparticles.