Mechanistic study of the gas-phase chemistry during the spray deposition of Zn(O,S) films by mass spectrometry

Abstract

The mass spectrometer, is a powerful tool to identify species and investigate reactions in the gas phase. In this work, the mechanism of aerosol assisted chemical vapor deposition (AACVD) of Zn(O,S) films prepared from H2S and zinc acetylacetonate (Zn(acac)2) precursor solutions is elucidated by mass spectrometry. The thermochemical behavior of Zn(acac)2 is investigated by characterizing the influence of the solvent (H2O or ethanol), the pH value of the precursor solution and the effect of the reactant H2S, and by tracking gaseous intermediate products using mass spectrometry. Based on these results, a proton-promoted thermolysis mechanism for the AACVD Zn(O,S) film formation is then proposed, which is initiated by the hydrolysis with H2O as the first stage, followed either by the rearrangement with an intramolecular proton or by the reaction with an extramolecular proton to produce ZnO or Zn(O,S). A real time mass tracking of the AACVD process reveals that only an adequate amount of H2S promotes the chemical gas-phase decomposition and sulfurization process, while an excess of H2S depletes the gaseous Zn(acac)2 concentration and consequently reduces the film growth rate. The knowledge of the thermal decomposition process helps to optimize synthesis conditions and to adjust film properties to meet the requirement of the application in chalcopyrite or kesterite thin film solar cells.