Fabrication of high crystalline SnS and SnS2 thin films, and their switching device characteristics.

Representative tin sulfide compounds, tin monosulfide (SnS) and tin disulfide (SnS2) are strong candidates for future nanoelectronic devices, based on non-toxicity, low cost, unique structures and optoelectronic properties. However, it is insufficient for synthesizing of tin sulfide thin films using vapor phase deposition method which is capable of fabricating reproducible device and securing high quality films, and their device characteristics. In this study, we obtained highly crystalline SnS thin films by atomic layer deposition and obtained highly crystalline SnS2 thin films by phase transition of the SnS thin films. The SnS thin film was transformed into SnS2 thin film by annealing at 450 °C for 1 h in H2S atmosphere. This phase transition was confirmed by x-ray diffractometer and x-ray photoelectron spectroscopy, and we studied the cause of the phase transition. We then compared the film characteristics of these two tin sulfide thin films and their switching device characteristics. SnS and SnS2 thin films had optical bandgaps of 1.35 and 2.70 eV, and absorption coefficients of about 105 and 104 cm-1 in the visible region, respectively. In addition, SnS and SnS2 thin films exhibited p-type and n-type semiconductor characteristics. In the images of high resolution-transmission electron microscopy, SnS and SnS2 directly showed a highly crystalline orthorhombic and hexagonal layered structure. The field effect transistors of SnS and SnS2 thin films exhibited on-off drain current ratios of 8.8 and 2.1 × 103 and mobilities of 0.21 and 0.014 cm2 V-1 s-1, respectively. This difference in switching device characteristics mainly depends on the carrier concentration because it contributes to off-state conductance and mobility. The major carrier concentrations of the SnS and SnS2 thin films were 6.0 × 1016 and 8.7 × 1013 cm-3, respectively, in this experiment.

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.

Photocurrent detection of chemically tuned hierarchical ZnO nanostructures grown on seed layers formed by atomic layer deposition.

We demonstrate the morphological control method of ZnO nanostructures by atomic layer deposition (ALD) on an Al2O3/ZnO seed layer surface and the application of a hierarchical ZnO nanostructure for a photodetector. Two layers of ZnO and Al2O3 prepared using ALD with different pH values in solution coexisted on the alloy film surface, leading to deactivation of the surface hydroxyl groups. This surface complex decreased the ZnO nucleation on the seed layer surface, and thereby effectively screened the inherent surface polarity of ZnO. As a result, a 2-D zinc hydroxyl compound nanosheet was produced. With increasing ALD cycles of ZnO in the seed layer, the nanostructure morphology changes from 2-D nanosheet to 1-D nanorod due to the recovery of the natural crystallinity and polarity of ZnO. The thin ALD ZnO seed layer conformally covers the complex nanosheet structure to produce a nanorod, then a 3-D, hierarchical ZnO nanostructure was synthesized using a combined hydrothermal and ALD method. During the deposition of the ALD ZnO seed layer, the zinc hydroxyl compound nanosheets underwent a self-annealing process at 150 °C, resulting in structural transformation to pure ZnO 3-D nanosheets without collapse of the intrinsic morphology. The investigation on band electronic properties of ZnO 2-D nanosheet and 3-D hierarchical structure revealed noticeable variations depending on the richness of Zn-OH in each morphology. The improved visible and ultraviolet photocurrent characteristics of a photodetector with the active region using 3-D hierarchical structure against those of 2-D nanosheet structure were achieved.