Role of Nanocavity Plasmons in Tunneling Electron Induced Light Emission on and near a Molecule

By using a microscopic quantum model, we study theoretically different roles of nanocavity plasmons in scanning tunneling microscope(STM) induced light emission upon selective initial excitation of molecules or plasmons. The time evolution and spectroscopic properties of the emission from the coupled plasmon-molecule system in each case are studied using time-dependent quantum mater equations. When the STM tip is placed on the molecule to ensure direct carrier injection induced molecular excitation, the major role of the plasmons is to enhance the molecular emission via increasing its radiative decay rate, resulting in sharp molecule-specific emission peaks. On the other hand, when the STM tip is located in close proximity to the edge of the molecule but without direct carrier injection into the molecule, the role of the plasmon-molecule coupling is to cause destructive interferences between the two quantum objects, leading to the occurrence of Fano dips around the energy of the molecular exciton in the plasmonic emission spectra.

Bias-Polarity Dependent Electroluminescence from a Single Platinum Phthalocyanine Molecule

By using scanning tunneling microscope induced luminescence(STML)technique,we investigate systematically the bias-polarity dependent electroluminescence behavior of a single platinum phthalocyanine(PtPc)molecule and the electron excitation mechanisms behind.The molecule is found to emit light at both bias polarities but with different emission energies.At negative excitation bias,only the fluorescence at 637 nm is observed,which originates from the LUMOtHOMO transition of the neutral PtPc molecule and exhibits stepwise-like increase in emission intensities over three different excitation-voltage regions.Strong fluorescence in region(I)is excited by the carrier injection mechanism with holes injected into the HOMO state first;moderate fluorescence in region(II)is excited by the inelastic electron scattering mechanism;and weak fluorescence in region(III)is associated with an up-conversion process and excited by a combined carrier injection and inelastic electron scattering mechanism involving a spintriplet relay state.At positive excitation bias,more-than-one emission peaks are observed and the excitation and emission mechanisms become complicated.The sharp moleculespecific emission peak at〜911 nm is attributed to the anionic emission of PtPc-originated from the LUMO+1 tLUMO transition,whose excitation is dominated by a carrier injection mechanism with electrons first injected into the LUMO+1 or higher-lying empty orbitals.

Dispersion and STM Characterization of Au-CdSe Nanohybrids on Au（111）

We report the dispersion and scanning tunneling microscopy （STM） characterization of iso- lated Au-CdSe nanohybrids on atomically fiat Au（111） through surface modifications. The top terminal groups of spacer molecules self-assembled on the surface are found critical for locking the nanohybrids into a well-separated state. The STM results indicate that both thiol and carboxylic terminals are effective in this aspect by making strong interaction with the Au portions of the nanohybrids. An argon ion sputtering technique is also proposed to clean up organic contaminants on the surface for improved STM imaging of individual Au-CdSe nanohybrids. These observations help to enrich technical approaches to dispersing individual nanostructures on the surface and provide opportunities to explore their local electroluminescent and energy transfer properties at the nanoscale.

Scanning Raman Picoscopy: Angstrom-Resolved Tip-Enhanced Raman Spectromicroscopy

In this review,we present a brief overview on the recent advances in Angstr6m-resolved tip-enhanced Raman spectromicroscopy.We first introduce the theoretical understanding of the confinement of light at the atomistic scale,and explain how the Raman scattering from a single molecule happens under the“illumination”of such an atomically confined light.Then we describe the latest developments on Angstr6m-resolved tipenhanced Raman spectromicroscopy,particularly on a new methodology called“scanning Raman picoscopy”for visually cons true ting the chemical st ruc ture of a single molecule in real space.Finally,we give a perspective of this technique in various applications where iden ti fying the chemical st ruc tu res of mat erials at the chemical bond level is required.

Fast Fabrication and Judgement of Tip-Enhanced Raman Spectroscopy-Active Tips

The quality of the scanning tip is crucial for tip-enhanced Raman spectroscopy(TERS)experiments towards large signal enhancement and high spatial resolution.In this work,we report a controllable fabrication method to prepare TERS-active tips by modifying the tip apex at the atomic scale,and propose two important criteria to in-situ judge the tip’s TERS activity for tip-enhanced Raman measurements.One criterion is based on the downshift of the first image potential state to monitor the coupling between the far-field incident laser and near-field plasmon;the other is based on the appearance of the low-wavenumber Raman peaks associated with an atomistic protrusion at the tip apex to judge the coupling efficiency of emissions from the near field to the far field.This work provides an effective method to quickly fabricate and judge TERS-active tips before real TERS experiments on target molecules and other materials,which is believed to be instrumental for the development of TERS and other tip-enhanced spectroscopic techniques.

Site-Dependent TERS Study of a Porphyrin Molecule on Ag(100) at 7 K

Single-molecule tip-enhanced Raman spectroscopy(TERS)has emerged as an important technique for structural analysis at sub-molecular scale.Here in this work,we report a TERS study of an isolated free-base porphyrin molecule adsorbed on the Ag(100)surface at cryogenic temperature(~7 K).Site-dependent TERS spectra reveal distinct local vibrational information for the chemical constituents within a single molecule.Moreover,distinct spatial features among different Raman peaks can be resolved from the TERS mapping images.These images are found to associate with related vibrational modes,enabling to resolve the mode associated with N-H bonds at the sub-nanometer level.This study will provide deep insights into the symmetry of adsorption configurations and local vibrational information within a single molecule.