Syntheses of Cu2SnSe3 and Their Transformation into Cu2ZnSnSe4 Nanoparticles with Tunable Band Gap under Multibubble Sonoluminescence Conditions

$Cu_2SnSe_3$ (CTSe) and $Cu_2ZnSnSe_4$ (CZTSe) nanoparticles were synthesized by sonochemical reactions under multibubble sonoluminescence (MBSL) conditions. First, $Cu_2SnSe_3$ nanoparticles were synthesized by the sonochemical method with an 85% yield, using CuCl, $SnCl_2$, and Se. Second, ZnSe was coated on the CTSe nanoparticles by the same method. Then, they were transformed into CZTSe nanoparticles of 5-7 nm diameters by heating them at $500^{\circ}C$ for 1 h. The ratios between Zn and Sn could be controlled from 1 to 3.75 by adjusting the relative concentrations of CTSe and ZnSe. With relatively lower Zn:Sn ratios (0.75-1.26), there are mostly CZTSe nanoparticles but they are believed to include very small amount of CTS and ZnSe particles. The prepared nanoparticles show different band gaps from 1.36 to 1.47 eV depending on the Zn/Sn ratios. In this sonochemical method without using any toxic or high temperature solvents, the specific stoichiometric element Zn/Sn ratios in CZTSe were controllable on demand and their experimental results were always reproducible in separate syntheses. The CZTSe nanoparticles were investigated by using X-ray diffractometer, a UV-Vis spectrophotometer, scanning electron microscope, Raman spectroscopy, and a high resolution-transmission electron microscope.