Tunable electrical properties of silicon nanowires via surface-ambient chemistry.

p-Type surface conductivity is a uniquely important property of hydrogen-terminated diamond surfaces. In this work, we report similar surface-dominated electrical properties in silicon nanowires (SiNWs). Significantly, we demonstrate tunable and reversible transition of p(+)-p-i-n-n(+) conductance in nominally intrinsic SiNWs via changing surface conditions, in sharp contrast to the only p-type conduction observed on diamond surfaces. On the basis of Si band energies and the electrochemical potentials of the ambient (pH value)-determined adsorbed aqueous layer, we propose an electron-transfer-dominated surface doping model, which can satisfactorily explain both diamond and silicon surface conductivity. The totality of our observations suggests that nanomaterials can be described as a core-shell structure due to their large surface-to-volume ratio. Consequently, controlling the surface or shell in the core-shell model represents a universal way to tune the properties of nanostructures, such as via surface-transfer doping, and is crucial for the development of nanostructure-based devices.