Role of chlorine in In2S3 for band alignment at nanoporous-TiO2/In2S3 interfaces

Coatings of Cl-free and Cl-containing In2S3 (In2S3:Cl) layers were prepared by spray ion layer gas reaction on nanoporous TiO2 (np-TiO2). Charge separation in FTO/np-TiO2/In2S3:Cl, FTO/In2S3:Cl, FTO/np-TiO2/In2S3:acac, and FTO/In2S3:acac systems has been investigated by modulated surface photovoltage spectroscopy (SPV). The exponential defect tails below the band gap of In2S3 were reduced for In2S3:Cl. The analysis of the SPV spectra allowed to distinguish different mechanisms of charge separation and to deduce the conduction band offsets (about 0.3 eV and 0.05 eV for np-TiO2/In2S3:Cl and np-TiO2/In2S3:acac, respectively) in correlation with photoelectron measurements.