Substrate impact on the thickness dependence of vibrational and optical properties of large area MoS2 produced by gold-assisted exfoliation

The gold-assisted exfoliation is a very effective method to produce large-area ($cm^2$-scale) membranes of molybdenum disulfide ($MoS_2$) for electronics. However, the strong $MoS_2/Au$ interaction, beneficial for the exfoliation process, has a strong impact on the vibrational and light emission properties of $MoS_2$. Here, we report an atomic force microscopy (AFM), micro-Raman ($\mu-R$) and micro-Photoluminescence ($\mu-PL$) investigation of $MoS_2$ with variable thickness exfoliated on Au and subsequently transferred on an $Al_2O_3/Si$ substrate. The $E_{2g}$ - $A_{1g}$ vibrational modes separation $\Delta\mu$ (typically used to estimate $MoS_2$ thickness) exhibits an anomalous large value ($\Delta\mu=21.2 cm^{-1}$) for monolayer (1L) $MoS_2$ on Au as compared to the typical one ($\Delta\mu=18.5 cm^{-1}$) measured on 1L $MoS_2$ on $Al_2O_3/Si$. Such substrate-related differences, explained in terms of tensile strain and p-type doping arising from the $MoS_2/Au$ interaction, were found to gradually decrease while increasing the number of $MoS_2$ layers. Furthermore, $\mu-PL$ spectra for 1L $MoS_2$ on Au exhibit a strong quenching and an overall red-shift of the main emission peak at 1.79 eV, compared to the 1.84 eV peak for 1L $MoS_2$ on $Al_2O_3$. After PL spectra deconvolution, such red shift was explained in terms of a higher trion/exciton intensity ratio, probably due to the higher polarizability of the metal substrate, as well as to the smaller equilibrium distance at $MoS_2/Au$ interface.