Surface-Enhanced Raman Scattering (SERS) of Nitrothiophenol isomers chemisorbed on TiO2

Surface-enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculations were used to investigate the nature of the charge-transfer (CT) process between nitrothiophenol (NTP) isomers and the n-type semiconductor, TiO2. The Raman signals of p-NTP and m-NTP that were chemisorbed onto TiO2 were significantly enhanced with respect to their corresponding neat compounds. In particular, an enhancement factor (EF) of 102–103 was observed for both p-NTP and m-NTP, with m-NTP displaying a larger EF compared to p-NTP. The Raman signal of o-NTP on TiO2 was not detectable, owing to interference from fluorescence emissions. A molecule-to-TiO2 charge-transfer mechanism was responsible for the enhanced Raman signals observed in p-NTP and m-NTP. This transfer was due to a strong coupling between the adsorbate and the metal oxide, which led to an optically driven CT transition from the HOMO of NTP into the conduction band of TiO2. Based on the mesomeric effect, the NO2 group para to the thiol had a stronger electron-withdrawing ability than the NO2 group at the meta position. A less-efficient CT transition from p-NTP to TiO2 in the surface complex resulted in a weaker Raman-signal enhancement for p-NTP compared to m-NTP. The DFT calculation determined that the HOMO and the LUMO of NTP bound to TiO2 were located entirely on the adsorbate and the semiconductor, respectively, thereby supporting the experimental findings that a molecule-to-TiO2 mechanism was the driving force behind the observed SERS effect

Plasma modified MoS2 nanoflakes for surface enhanced Raman scattering

Though the SERS effect based on pristine MoS2 is hardly observed, however, the plasma treated MoS2 nanoflakes can be used as an ideal substrate for surface enhanced Raman scattering. It is proved that the structural disorder induced generation of local dipoles and adsorption of oxygen on the plasma treated MoS2 nanosheets are the two basic and important driven forces for the enhancement of Raman signals of surface adsorbed R6G molecules

Ultrafast electron and hole relaxation pathways in few-layer MoS₂

Femtosecond optical pump–probe spectroscopy is employed to elucidate the band-selective ultrafast carrier dynamics of few-layer MoS2. Following narrowband resonant photoexcitation of the exciton A transition, the subpicosecond to picosecond relaxation dynamics of the electron and the hole at the K valley are separately interrogated by a broadband probe pulse. The temporal evolution of the spectral first moment reveals nonexponential intravalley relaxation dynamics in the conduction band. Fluence dependence measurements suggest that this relaxation process is predominantly mediated by acoustic phonon emission. Intervalley scattering of carriers from the K valley to the extrema of the conduction and valence bands is also observed via the decay of the spectral zeroth moment. In addition, second-order Raman scattering leads to the emergence of sidebands in the normalized differential transmission spectra. The observed two-phonon energies and the fluence-dependent time constants suggest that the E1g longitudinal optical (LO) phonon and the LA phonon participate in intervalley scattering in the conduction and valence bands, respectively. Ab initio nonadiabatic molecular dynamics simulations yield time constants of 0.80 and 0.72 ps for intra- and intervalley electronic relaxation, respectively; the latter agrees well with experiment. Finally, the normalized differential transmission spectra reveal a two-electron shake-up satellite that originates from band-edge radiative recombination and the simultaneous excitation of a hole from Kv1 to Kv2. From its spectral position, a Kv1–Kv2 spin–orbit splitting of 1166 ± 1 cm–1 is deduced. The observation of the two-electron transition points to the existence of strong electron correlation in photoexcited few-layer MoS2