Reduced Binding Energy and Layer-Dependent Exciton Dynamics in Monolayer and Multilayer WS₂

The exciton dynamics in WS2 from monolayer to four-layer was investigated by using fluorescence lifetime imaging measurement (FLIM). The transition process of negatively charged trions is measured and detected using a fluorescence detection method. Compared with neutral excitons, negatively charged trions have a longer fluorescence lifetime. Further exploration illustrated that the fluorescence lifetime of both neutral excitons and trions get longer when the thickness increased. When WS2 was added from monolayer to four-layer, lifetimes of direct transition excitons and trions tended to increase over 10 and 2.5 times, separately, whereas the lifetime of indirect transition excitons tended to be reduced by nearly 2.5 times. This layer-dependent signature is ascribed to the reduced binding energy in thicker WS2 at room temperature, which is verified by density theory functional calculation. Although the direct transition exciton dominates the whole fluorescence decay process, it is influenced by trions and dark excitons. Based on the FLIM results, we proposed four main exciton transition channels during the fluorescence luminescence process. Such layer-dependent transition channel conception helps to control the fluorescence lifetime, which determines the efficiency of the carriers’ separation.