Colloidal CuInSe2 nanocrystals: from gradient stoichiometry toward homogeneous alloyed structure mediated by...

We report, for the first time, the synthesis of colloidal copper indium selenide (CuInSe2) nanocrystals (NCs) possessing a gradient stoichiometry that is potentially tunable by the presence of a conducting polymer, i.e., poly(3-hexyl thiophene) (P3HT) in the synthesis medium. Dibenzyl ether (DBE) was used as a reaction medium, whereas copper acetylacetonate (Cu(acac)2), indium acetylacetonate (In(acac)3), and selenium powder were used as Cu, In, and Se sources, respectively. The Se precursor was tri-n-octylphosphine selenide (TOP-Se). Without the presence of P3HT, the resulting NCs consist of a p-type (Cu(1+) rich) core and an n-type (In(3+) rich) shell. Such a gradient stoichiometry was moderated to be substantially more homogeneous because the presence of P3HT is believed to have significantly reduced the reactivity difference between Cu(acac)2 and In(acac)3, as well as and their respective monomers. Furthermore, the P3HT also acts as a surface coordination species, contributing to the readily preparation of conducting polymer-NCs hybrids by a single-step synthesis. The understandings of this work can serve as a guide for design and synthesis of conducting polymer-NCs hybrids based on various ternary or quaternary compound semiconductors with different core-shell composition gradient.