Photoelectrochemical study of the band structure of Zn(2)SnO(4) prepared by the hydrothermal method.

It is fundamentally interesting to study the photoelectrochemical properties of complex oxides for applications in photovoltaics and photocatalysis. In this paper, we study the band gap (E(g)) and energetics of the conduction band (CB) and valence band (VB) for films of zinc stannate (Zn(2)SnO(4)) nanoparticles (ca. 25 nm) of the inverse-spinel structure prepared by the hydrothermal method. UV-vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemistry, and photoelectrochemistry were used to study the films. The fundamental E(g) for Zn(2)SnO(4) is proposed to be 3.6-3.7 eV with a direct-forbidden transition. The position of the CB was approximated from the flat band potential, E(fb), measured by the photocurrent onset potential. In aqueous and nonaqueous solutions the E(fb) of n-Zn(2)SnO(4) was found to be more positive than TiO(2) anatase in the electrochemical scale. In aqueous solutions E(fb) of Zn(2)SnO(4) was found to follow a 59 mV/pH slope with E(fb) extrapolated at pH 0 of 0.08 V vs NHE. In acetonitrile solutions that simulate the electrolyte for dye-sensitized solar cells (DSCs) the E(fb) of Zn(2)SnO(4) was found to be strongly dependent on electrolyte composition and more positive than TiO(2) vs the I(-)/I(3)(-) couple. The reverse trend observed for the open-circuit voltage in certain DSC electrolytes is explained in terms of the higher rates of electron-triiodide recombination of TiO(2) despite the lower position of the Zn(2)SnO(4) CB in the vacuum scale.