Role of zinc interstitials and oxygen vacancies of ZnO in photocatalysis: a bottom-up approach to control defect density

Oxygen vacancies (VOs) in ZnO are well-known to enhance photocatalytic activity (PCA) despite various other intrinsic crystal defects. In this study, we aim to elucidate the effect of zinc interstitials (Zni) and VOs on PCA, which has applied as well as fundamental interest. To achieve this, the major hurdle of fabricating ZnO with controlled defect density requires to be overcome, where it is acknowledged that defect level control in ZnO is significantly difficult. In the present context, we fabricated nanostructures and thoroughly characterized their morphological (SEM, TEM), structural (XRD, TEM), chemical (XPS) and optical (photoluminescence, PL) properties. To fabricate the nanostructures, we adopted atomic layer deposition (ALD), which is a powerful bottom-up approach. However, to control defects, we chose polysulfone electrospun nanofibers as a substrate on which the non-uniform adsorption of ALD precursors is inevitable because of the differences in the hydrophilic nature of the functional groups. For the first 100 cycles, Znis were predominant in ZnO quantum dots (QDs), while the presence of VOs was negligible. As the ALD cycle number increased, VOs were introduced, whereas the density of Zni remained unchanged. We employed PL spectra to identify and quantify the density of each defect for all the samples. PCA was performed on all the samples, and the percent change in the decay constant for each sample was juxtaposed with the relative densities of Znis and VOs. A logical comparison of the relative defect densities of Znis and VOs suggested that the former are less efficient than the latter because of the differences in the intrinsic nature and the physical accessibility of the defects. Other reasons for the efficiency differences were elaborated.