Raman and X-ray Photoelectron Spectroscopic Study of Aqueous Thiol-Capped Ag-Zn-Sn-S Nanocrystals.

The synthesis of (Cu,Ag)-Zn-Sn-S (CAZTS) and Ag-Zn-Sn-S (AZTS) nanocrystals (NCs) by means of "green" chemistry in aqueous solution and their detailed characterization by Raman spectroscopy and several complementary techniques are reported. Through a systematic variation of the nominal composition and quantification of the constituent elements in CAZTS and AZTS NCs by X-ray photoemission spectroscopy (XPS), we identified the vibrational Raman and IR fingerprints of both the main AZTS phase and secondary phases of Ag-Zn-S and Ag-Sn-S compounds. The formation of the secondary phases of Ag-S and Ag-Zn-S cannot be avoided entirely for this type of synthesis. The Ag-Zn-S phase, having its bandgap in near infrared range, is the reason for the non-monotonous dependence of the absorption edge of CAZTS NCs on the Ag content, with a trend to redshift even below the bandgaps of bulk AZTS and CZTS. The work function, electron affinity, and ionization potential of the AZTS NCs are derived using photoelectron spectroscopy measurements.