Influence of Annealing Temperature on CZTS Thin Film Surface Properties

In this work, copper zinc tin sulfide (CZTS) films were deposited by direct current sputtering and the samples were annealed in different oven-set temperatures and atmosphere (Ar and H₂S). The surface evolution was investigated carefully by using scanning electron microscopy (SEM), Raman spectroscopy and x-ray photoelectron spectroscopy. The surface of the as-sputtered precursor contained little Cu and large amounts of Zn and Sn. The metallic precursor was continuous and compact without pinholes or cracks. With the increase of the temperature from room temperature to 250°C, Cu atoms diffused to the film surface to form Cu_1−xS and covered other compounds. Some small platelets were smaller than 500 nm spreading randomly in the holes of the film surfaces. When the temperature reached 350°C, Zn and Sn atoms began to diffuse to the surface and react with S or Cu_1−xS. At 400°C, SEM showed the melting of large particles and small particles with a size from 100 nm to 200 nm in the background of the film surface. Excess Zn segregated towards the surface regions and formed ZnS phase on the surface. In addition, the signal of sodium in the CZTS surface was observed above 400°C. At 600°C, a large amount of regular structures with clear edges and corners were observed in the film surface in SEM images. A clear recrystallized process on the surface was assumed from those observations.