Phase-Controlled Synthesis of Alloyed (CdS)_x(CuInS₂)_1-x Nanocrystals with Tunable Band Gap

Phase and band gap engineering of (CdS)_x(CuInS₂)_1-x nanomaterials is critical for their potential applications in photovoltaics and photocatalysis, yet it remains a challenge. Here, we report a precursor-mediated colloidal method for phase-control synthesis of alloyed (CdS)_x(CuInS₂)_1-x nanocrystals with tunable band gap. When CuCl, InCl₃, and Cd(AC)₂·2H₂O are used as the respective cation sources, wurtzite-structured alloyed (CdS)_x(CuInS₂)_1-x nanocrystals can be synthesized with a tunable optical band gap ranging from 1.56 to 2.45 eV by directly controlling the molar ratio of the Cd precursor. Moreover, using Cu(S₂CNEt₂)₂, In(S₂CNEt₂)₃, and Cd(S₂CNEt₂)₂ as cation sources results in alloyed (CdS)_x(CuInS₂)_1-x nanocrystals with a zinc-blende structure, demonstrating that the optical band gap of these nanocrystals can be compositionally tuned from 1.50 to 1.84 eV through precisely adjusting the molar ratio of Cd precursor. The results were validated through a comprehensive characterization approach employing XRD, TEM, HRTEM, STEM-EDS, XPS, UV-vis-NIR absorption spectroscopy, and Mott-Schottky analysis.