Anomalous thickness-dependent optical energy gap of ALD-grown ultra-thin CuO films

Usually an inverse square relation between the optical energy gap and the size of crystallites is observed for semiconducting materials due to the strong quantum localization effect. Coulomb attraction that may lead to a proportional dependence is often ignored or considered less important to the optical energy gap when the crystallite size or the thickness of a thin film changes. Here we report a proportional dependence between the optical energy gap and the thickness of ALD-grown CuO thin films due to a strong Coulomb attraction. The ultrathin films deposited in the thickness range of 9-81 nm show a p-type semiconducting behavior when analyzed by Seebeck coefficient and electrical resistivity measurements. The indirect optical energy gap nature of the films is verified from UV-vis spectrophotometric measurements. A progressive increase in the indirect optical energy gap from 1.06 to 1.24 eV is observed with the increase in the thickness of the films. The data are analyzed in the presence of Coulomb attractions using the Brus model. The optical energy gap when plotted against the cubic root of the thickness of the films shows a linear dependence.