Luo, YangMartin-Jimenez, AlbertoGutzler, RicoGarg, ManishKern, Klaus2022-07-182022-07-182022-07-182022-06-1510.1021/acs.nanolett.2c00485https://infoscience.epfl.ch/handle/20.500.14299/189289WOS:000820513600001Vibrational fingerprints of molecules and lowdimension materials can be traced with subnanometer resolution by performing Tip-enhanced Raman spectroscopy (TERS) in a localization of light in the plasmonic nanocavity of the STM enables high spatial resolution in STM-TERS; however, the temporal resolution is so far limited. Here, we demonstrate stable TERS measurements from subphthalocyanine (SubPc) molecules excited by similar to 500 fs long laser pulses in a low-temperature (LT) ultrahigh-vacuum (UHV) STM. The intensity of the TERS signal excited with ultrashort pulses scales linearly with the increasing flux of the laser pulses and exponentially with the decreasing gap-size of the plasmonic nanocavity. Furthermore, we compare the characteristic features of TERS excited with ultrashort pulses and with a continuous-wave (CW) laser. Our work lays the foundation for future experiments of time-resolved femtosecond TERS for the investigation of molecular dynamics with utmost spatial, temporal, and energy resolutions simultaneously.Chemistry, MultidisciplinaryChemistry, PhysicalNanoscience & NanotechnologyMaterials Science, MultidisciplinaryPhysics, AppliedPhysics, Condensed MatterChemistryScience & Technology - Other TopicsMaterials SciencePhysicstip-enhanced raman spectroscopyultrafast raman spectroscopyfemtosecond pulsesstmmolecular vibrationssingle-moleculenanoscaledynamicstext::journal::journal article::research article