Tuning the Electronic Structure of Tin Sulfides Grown by Atomic Layer Deposition

In this study, tin sulfide thin films were obtained by atomic layer deposition (ALD) using Tetrakis(dimethylamino)tin (TDMASn, [(CH3)2N]4Sn) and hydrogen sulfide (H2S). The growth rate of the tin sulfides (SnSx) was shown to be highly dependent on the deposition temperature, and reaction times of 1 second for the TDMASn and H2S were required to reach the saturation regime. Surface morphologies were smooth or rectangular with rounded corners as observed by a field emission scanning electron microscope (FE-SEM) and were dependent on temperature. X-ray diffraction results confirmed that the crystal structure of SnSx can be tuned by changing the ALD temperature. Below 120 °C, SnSx films appeared to be amorphous. In addition, SnSx films were SnS2 hexagonal at 140 and 150 °C and SnS orthorhombic above 160 °C. Similarly, the values of the optical band gap and binding energy showed significant differences between 150 and 160 °C. The electronic structures of SnSx were extracted by UPS and absorption spectroscopy, and the unsaturated Sn 3d molecular orbital (MO) states in the band edge were found to be responsible for the great improvement in electrical conductivity. This study shows that TDMASn-H2S ALD is an effective deposition method for SnSx films, offering a simple approach to tune the physical properties.This study was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean Government (MEST) (No. 2012-0005474). We appreciate Sanghun Lee's assistance with the SEM measurements