Robust and high-sensitivity thermal probing at the nanoscale based on resonance Raman ratio (R3)

Abstract Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber, linewidth and intensity, and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade. The temperature coefficients of these Raman properties are highly material-dependent, and are subjected to local optical scattering influence. As a result, Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity. Here, a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial (nm WS₂ film in this work) from 170 to 470 K. A 532 nm laser (2.33 eV photon energy) is used to conduct the Raman experiment. Its photon energy is very close to the excitonic transition energy of WS₂ at temperatures close to room temperature. A parameter, termed resonance Raman ratio (R3) Ω={{I}_A}_{{}_1g}/{{I}_E}_{{}_2g} is introduced to combine the temperature effects on resonance Raman scattering for the A_1g and E_2g modes. Ω has a change of more than two orders of magnitude from 177 to 477 K, and such change is independent of film thickness and local optical scattering. It is shown that when Ω is varied by 1%, the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures, respectively. Based on Ω, the in-plane thermal conductivity (k) of a ∼25 nm-thick suspended WS₂ film is measured using our energy transport state-resolved Raman (ET-Raman). k is found decreasing from 50.0 to 20.0 Wm⁻¹ K⁻¹ when temperature increases from 170 to 470 K. This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman. The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization, non-destructive evaluation, and manufacturing monitoring.