Scanning tunneling spectroscopy to probe site-selection in heterovalent doping: Zn(II)-doped Cu(I)In(III)S2 as a case study

Abstract

We report scanning tunneling spectroscopy (STS) of a heterovalent-doped ternary compound semiconductors and their binary counterparts. The effect of dopants in the semiconductors that yielded a shift in Fermi energy has been found to be manifested in the density of states (DOS) spectrum. The shift infers the nature of doping, which the heterovalent dopants induce, and hence the site of the ternary system that the dopants occupy. For example, in the present case with Zn(II)-doped Cu(I)In(III)S2, the DOS spectra showed a shift in Fermi energy towards the conduction band and hence a n-type doping due to the introduction of electrons. Such a shift inferred that the bivalent dopants occupied the cuprous site. The results have been substantiated by STS studies of doped binary components, namely, Cu2S and In2S3 and shift in Fermi energy thereof. With the tuning in the Fermi energy, the homojunctions between undoped and doped semiconductors have a type-II band-alignment at the interface resulting in current rectification through the junctions. The band-diagram of the homojunctions formed through STS substantiated the direction of current-rectification in the junctions.