Electrical, Photoelectrochemical, and Photoelectron Spectroscopic Investigation of the Interfacial Transport and Energetics of Amorphous TiO₂/Si Heterojunctions

Solid-state electrical, photoelectrochemical, and photoelectron spectroscopic techniques have been used to characterize the behavior and electronic structure of interfaces between n-Si, n⁺-Si, or p⁺-Si surfaces and amorphous coatings of TiO₂ formed using atomic-layer deposition. Photoelectrochemical measurements of n-Si/TiO₂/Ni interfaces in contact with a series of one-electron, electrochemically reversible redox systems indicated that the n-Si/TiO₂/Ni structure acted as a buried junction whose photovoltage was independent of the formal potential of the contacting electrolyte. Solid-state current-voltage analysis indicated that the built-in voltage of the n-Si/TiO₂ heterojunction was 0.7 V, with an effective Richardson constant 1/100th of the value of typical Si/metal Schottky barriers. X-ray photoelectron spectroscopic data allowed formulation of energy band-diagrams for the n-Si/TiO₂, n⁺-Si/TiO₂, and p⁺-Si/TiO₂ interfaces. The XPS data were consistent with the rectifying behavior observed for amorphous TiO₂ interfaces with n-Si and n⁺-Si surfaces and with an ohmic contact at the interface between amorphous TiO₂ and p⁺-Si.