Modifying the Band Gap of Semiconducting Two-Dimensional Materials by Polymer Assembly into Different Structures.

Polyethylene glycol (PEG) assembled on the surface of two-dimensional tungsten disulfide (WS2) into a limited number of nanoislands (NIs), nanoshells (NSs), and granular nanoparticulates (GNPs) depending on its chain length. NI assemblies showed a nonmeasurable shift of photoluminescence (PL) and the A and B absorption peaks of WS2. This confirmed that the electronic doping by thiol is not effective. The PEG NS assembly displayed a smaller red shift of the PL and a slight decrease of the energy difference between the A and B absorption peaks of WS2. However, increasing the dielectric function on the surface of WS2 has a small influence on their optical properties. The PEG NP assembly on WS2 exhibited a significant red shift of the PL spectrum and a large decrease of the energy difference between A and B absorption peaks. Deforming the WS2 sheet by the PEG NP assembly decreased the orbital coupling and lowered the electronic direct band gap significantly. Raman bands of WS2 are shifted to a higher frequency on improving its mechanical strength after the PEG assembly.