Assessing the role of plasma-engineered acceptor-like intra- and inter-grain boundaries of heterogeneous WS2–WO3 nanosheets for photocurrent characteristics†
High-temperature annealing in tungsten disulfide resulted in heterogeneous WS2–WO3 in which intra- (within WS2 and WO3) and inter- (between WS2 and WO3) grain boundaries were observed, which were highly critical for charge transport and recombination. The heterogeneous WS2–WO3 phase was evidenced by observing the coexistence of d-spacing values of 0.26 nm (WS2) and 0.37 nm (WO3) in transmission electron microscopic (TEM) studies. Further systematic high-resolution TEM studies elucidated that intra-grain boundaries separated crystallites within WS2 and WO3, while inter-grain boundaries separated WS2 from WO3. As WS2 and WO3 are both n-type, these defects are acceptor-like in the grain boundaries and they actively participate in the capture (trapping) process, which impedes charge transport characteristics in the heterogeneous WS2–WO3 films. Plasma treatment in the heterogeneous WS2–WO3 film, for 60 minutes using argon, energetically modulated the defects in the intra/inter-grain boundaries, as evidenced from detailed comparative photocurrent characteristics obtained individually in (i) pristine WS2, (ii) heterogeneous WS2–WO3 and (iii) Ar plasma-treated heterogeneous WS2–WO3 films under blue and green lasers, along with AM1.5 (1 sun) illumination. Detrimental roles (trapping/de-trapping and scattering) of grain boundary states on photoelectrons were seen to be significantly suppressed under the influence of plasma.