Photoluminescence from Liquid-Exfoliated WS₂ Monomers in Poly(Vinyl Alcohol) Polymer Composites

While liquid phase exfoliation can be used to produce nanosheets stabilized in polymer solutions, very little is known about the resultant nanosheet size, thickness, or monolayer content. The present study uses semiquantitative spectroscopic metrics based on extinction, Raman, and photoluminescence (PL) spectroscopy to investigate these parameters for WS₂ nanosheets exfoliated in aqueous poly(vinyl alcohol) (PVA) solutions. By measuring Raman and PL simultaneously, the monolayer content can be tracked via the PL/Raman intensity ratio while varying processing conditions. The PL is found to be maximized for a stabilizing polymer concentration of 2 g L^-1. In addition, the monolayer content can be controlled via the centrifugation conditions, exceeding 5% by mass in some cases. These techniques have allowed tracking the ratio of PL/Raman in a droplet of polymer-stabilized WS₂ nanosheets as the water evaporates during composite formation. No evidence of nanosheet aggregation is found under these conditions although the PL becomes dominated by trion emission as drying proceeds and the balance of doping from PVA/water changes. Finally, bulk PVA/WS₂ composites are produced by freeze drying where >50% of the monolayers remain unaggregated, even at WS₂ volume fractions as high as 10%.