Analyzing and Tuning the Chalcogen-Amine-Thiol Complexes for Tailoring of Chalcogenide Syntheses

The amine-thiol solvent system has been used extensively to synthesize metal chalcogenide thin films and nanoparticles because of its ability to dissolve various metal and chalcogen precursors. While previous studies of this solvent system have focused on understanding the dissolution of metal precursors, here we provide an in-depth investigation of the dissolution of chalcogens, specifically Se and Te. Analytical techniques, including Raman, X-ray absorption, and NMR spectroscopy and high-resolution tandem mass spectrometry, were used to identify pathways for Se and Te dissolution in butylamine-ethanethiol and ethylenediamine-ethanethiol solutions. Se in monoamine-monothiol solutions was found to form ionic polyselenides free of thiol ligands, while in diamine-monothiol solutions, thiol coordination with polyselenides was predominately observed. When the relative concentration of thiol is increased to that of Se, the chain length of polyselenide species was observed to shorten. Analysis of Te dissolution in diamine-thiol solutions also suggested the formation of relatively unstable thiol-coordinated Te ions. This instability of Te ions was found to be reduced by codissolving Te with Se in diamine-thiol solutions. Analysis of the codissolved solutions revealed the presence of atomic interaction between Se and Te through the identification of Se-Te bonds. This new understanding then provided a new route to dissolve otherwise insoluble Te in butylamine-ethanethiol solutions by taking advantage of the Se^2- nucleophile. Finally, the knowledge gained for chalcogen dissolutions in this solvent system allowed for controlled alloying of Se and Te in PbSeTe_1- material and also provided a general knob to alter various metal chalcogenide material syntheses.