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An oxide p–n heterojunction composed of a 150-nm La0.67Ca0.33MnO3 (LCMO) film, 0.05 wt%Nb doped SrTiO3 substrate (STON), and sandwiched 5-nm LaAlO3 (LAO) thin film is fabricated with the pulsed laser deposition technique and the interfacial transport properties are experimentally studied. The rectifying behavior of the junction is in agreement with Newman’s equation, indicating that tunneling is the dominant process for the carriers to pass through the interface while thermal emission is the dominant transport model of an LCMO/STON heterojunction with no LAO buffer layer.