Composition and Structure Control of Cu–Al–O Films Prepared by Reactive Sputtering and Annealing

Abstract

Cu–Al–O films were prepared on quartz glass substrates at 500–700 °C by sputtering the Cu and Al targets alternately on atomic-layer scale under an Ar-diluted O2 (5–20%) gas atmosphere, and then annealed at 1050 °C under a nitrogen atmosphere. The [Cu]/[Al] ratio was controlled by changing the Cu and Al deposition periods. The composition of as-deposited films corresponded to the slightly oxygen-rich region of the CuO–CuAl2O4–Al2O3 system. Films as-deposited at 500 °C had an amorphous structure, while films as-deposited at 700 °C had CuAl2O4 and CuO phases. After thermal annealing in a nitrogen atmosphere, the composition of the films approached that of the Cu2O–CuAlO2–Al2O3 system line, causing a noticeable appearance of the CuAlO2 phase along with the disappearance of the CuAl2O4 and CuO phases. Cu- and Al-rich annealed films had in addition a Cu2O phase and an amorphous Al2O3 phase, respectively. All annealed films exhibited p-type conductivity. The annealed films with [Cu]/[Al]≈1 had an absorption edge corresponding to the energy gap of CuAlO2. These results indicate that the change in the Cu ion from divalent to monovalent through nitrogen annealing results in the preparation of transparent conductive films dominated by CuAlO2.