Anomalies in the optical properties of nanocrystalline copper oxides CuO and Cu2O near the fundamental absorption edge

A 0.1-0.15-eV displacement of the fundamental absorption edge in the optical absorption spectra of nanocrystalline oxide n-CuO (relative to the position of the fundamental absorption edge in the spectra of CuO single crystals) towards lower energies (red shift) is observed against the background of strong blurring. Nanocrystalline n-Cu2O exhibits a displacement of the fundamental absorption edge towards higher energies (blue shift) by approximately 0.35 eV. The size of crystallites in n-CuO and n-Cu2O ranges from 10 to 90 nm. The blue shift of the fundamental absorption edge of n-Cu2O is typical of classical wide-gap semiconductors and can be explained by size quantization upon a change in the particle size. The anomalous red shift of the fundamental absorption edge of the strongly correlated nanocrystalline oxide n-CuO can be attributed to the highly defective structure of n-CuO, anomalies in the electronic structure of strongly correlated compounds based on 3d metals, and their tendency to electronic phase separation with the formation of metal-like inclusions.