n-ZnO/p-Si heterojunction light-emitting diodes ͑LEDs͒ show weak defect-related electroluminescence ͑EL͒. In order to analyze the origin of the weak EL, the energy band alignment and interfacial microstructure of ZnO/Si heterojunction are investigated by x-ray photoelectron spectroscopy. The valence band offset ͑VBO͒ is determined to be 3.15Ϯ 0.15 eV and conduction band offset is −0.90Ϯ 0.15 eV, showing a type-II band alignment. The higher VBO means a high potential barrier for holes injected from Si into ZnO, and hence, charge carrier recombination takes place mainly on the Si side rather than the ZnO layer. It is also found that a 2.1 nm thick SiO x interfacial layer is formed at the ZnO/Si interface. The unavoidable SiO x interfacial layer provides to a large number of nonradiative centers at the ZnO/Si interface and gives rise to poor crystallinity in the ZnO films. The weak EL from the n-ZnO/p-Si LEDs can be ascribed to the high ZnO/Si VBO and existence of the SiO x interfacial layer.

n-ZnO/p-GaN heterojunction light-emitting diodes with and without a sandwiched AlN layer were fabricated. The electroluminescence (EL) spectrum acquired from the n-ZnO/p-GaN displays broad emission at 650 nm originating from ZnO and weak emission at 440 nm from GaN, whereas the n-ZnO/AlN/p-GaN exhibits strong violet emission at 405 nm from ZnO without GaN emission. The EL intensity is greatly enhanced by inserting a thin AlN intermediate layer and it can be attributed to the suppressed formation of the GaOx interfacial layer and confinement effect rendered by the AlN potential barrier layer.