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Al2O3 and ZnO/Al2O3 are prepared on silicon substrates via atomic layer deposition (ALD). Diethyl zinc (DEZ), trimethly aluminum (TMA) and deionized water are used as Zn, Al and oxidant precursors respectively. A sandwich structure of ZnO/Al2O3 stack is proposed for ZnO/Al2O3 intermixing. The Zn0.8Al0.2Oy composite thin film can be obtained by adjusting ZnO/Al2O3 ALD pulse sequence. The film thicknesses and microstructure are characterized by spectroscopy ellipsometry and X-ray diffraction. The band offset and alignment of atomic layer deposited Al2O3/Zn0.8Al0.2Oy hetero-interface are systematically studied in this paper.