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.

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.

Recent advances in tip-enhanced Raman spectroscopy probe designs

Tip-enhanced Raman spectroscopy(TERS)imaging is a super-resolution imaging technique that features the merits of both surface-enhanced Raman spectroscopy(SERS)and scanning probe microscopy(SPM),such as the high chemical sensitivity from the former and the nanoscale spatial resolution from the latter.These advantages make TERS an essential nanospectroscopic characterization technique for chemical analysis,materials science,bio-sensing,etc.TERS probes,the most critical factor determining the TERS imaging quality,are expected to provide a highly confined electromagnetic hotspot with a minimized scattering background for the generation of Raman signals with high spatial resolution.After two decades of development,numerous probe design concepts have been proposed and demonstrated.This review provides a comprehensive overview of the state-of-the-art TERS probe designs,from the working mechanism to the practical performance.We start with reviewing the recent development of TERS configurations and the corresponding working mechanisms,including the SPM platforms,optical excitation/collection techniques,and probe preparation methods.We then review the emerging novel TERS probe designs,including the remote-excitation probes,the waveguide-based nanofocusing probes,the metal-coated nanofocusing probes,the nanowire-assisted selective-coupling probes,and the tapered metal-insulator-metal probes.Our discussion focuses on a few critical aspects,including the surface-plasmon-polariton(SPP)hotspot excitation technique,conversion efficiency,working frequency,and controllability.In the end,we review the latest TERS applications and give a perspective on the future of TERS.

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.

Probing On-Surface Chemistry at the Nanoscale Using Tip-Enhanced Raman Spectroscopy

Chemistry on solid surfaces is central to many research areas of practical interest,such as synthesis,catalysis,electrochemistry,photochemistry,and materials science.A comprehensive understanding of the nanoscale on-surface chemistry involved in these areas is important for establishing composition-structure-performance relationships.With the rapid development of tip-enhanced Raman spectroscopy(TERS),it has become possible to investigate physical and chemical processes on suitable surfaces at the nanoscale level and in real space.In this review,after a brief introduction of the background of onsurface chemistry and TERS,we systematically discuss the progress in the application of TERS in this field.Our focus is the applications of TERS to nanoscale coordination processes,decomposition reactions,polymerization processes,electrochemical reactions,catalytic chemistry,and functionalization chemistry on solid surfaces.We conclude by discussing the future challenges and development of TERS techniques and related applications in on-surface chemistry.

Subnanometer-resolved chemical imaging via multivariate analysis of tip-enhanced Raman maps

Tip-enhanced Raman spectroscopy(TERS)is a powerful surface analysis technique that can provide subnanometer-resolved images of nanostructures with site-specific chemical fingerprints.However,due to the limitation of weak Raman signals and the resultant difficulty in achieving TERS imaging with good signal-to-noise ratios(SNRs),the conventional single-peak analysis is unsuitable for distinguishing complex molecular architectures at the subnanometer scale.Here we demonstrate that the combination of subnanometer-resolved TERS imaging and advanced multivariate analysis can provide an unbiased panoramic view of the chemical identity and spatial distribution of different molecules on surfaces,yielding high-quality chemical images despite limited SNRs in individual pixel-level spectra.This methodology allows us to exploit the full power of TERS imaging and unambiguously distinguish between adjacent molecules with a resolution of~0.4 nm,as well as to resolve submolecular features and the differences in molecular adsorption configurations.Our results provide a promising methodology that promotes TERS imaging as a routine analytical technique for the analysis of complex nanostructures on surfaces.

Surface bonding on silicon surfaces as probed by tip-enhanced Raman spectroscopy

Tip-enhanced Raman spectroscopy (TERS) has been used to obtain the Raman signal of surface species on silicon single crystal surfaces without the necessity for surface enhancement by addition of Ag nanoparticles. By illuminating the hydrogen terminated silicon surface covered with a droplet of 4-vinylpyridine with UV light, a 4-ethylpyridine modified silicon surface can be easily obtained. By bringing a scanning tunneling microscope (STM) Au tip with a nanoscale tip apex to a distance of ca. 1 nm from the modified silicon surface, enhanced Raman signals of the silicon phonon vibrations and the surface-bonded 4-ethylpyridine were obtained. The Raman enhancement factor was estimated to be close to 107. By comparing the surface enhanced Raman scattering (SERS) signal obtained after surface enhancement with Ag nanoparticles and the TERS signal of the surface, the advantage of TERS over SERS for characterizing the surface species on substrates becomes apparent: TERS readily affords vibrational information about the system without disturbing it by surface enhancement. In this sense, TERS can be considered a truly non-invasive tool which is ideal for characterizing the actual surface species on substrates.

单壁碳纳米管束针尖增强近场拉曼光谱探测实验研究

针尖增强近场拉曼光谱术是最近发展起来的光谱技术。金属探针在获得样品纳米局域表面形貌的同时,受激光激发,在针尖附近产生增强电磁场,得到与形貌位置精确对应的针尖增强局域拉曼光谱,形貌和光谱的结合实现了纳米局域的光谱指认。文章建立了一套针尖增强近场拉曼光谱测量装置,并用此装置对电弧法合成的单壁碳纳米管进行了近场拉曼光谱探测。测量了直径为100nm单壁碳纳米管束的针尖增强拉曼光谱,进一步得到至多3根单壁碳纳米管的近场拉曼光谱,实现了超衍射分辨光谱探测。通过与远场拉曼光谱比较发现,针尖增强近场拉曼光谱的增强因子大于230倍。实验证明,同时具有超衍射空间分辨和拉曼光谱信号增强能力的针尖增强近场拉曼光谱术将是纳米材料和纳米结构表征的一种重要方法。

Review： Tip-based vibrational spectroscopy for nanoscale analysis of emerging energy materials

Vibrational spectroscopy is one of the key instrumentations that provide non-invasive investigation of structural and chemical composition for both organic and inorganic materials. However, diffraction of light funda- mentally limits the spatial resolution of far-field vibrational spectroscopy to roughly half the wavelength. In this article, we thoroughly review the integration of atomic force microscopy （AFM） with vibrational spectroscopy to enable the nanoscale characterization of emerging energy materials, which has not been possible with far-field optical techniques. The discussed methods utilize the AFM tip as a nanoscopic tool to extract spatially resolved electronic or molecular vibrational resonance spectra of a sample illuminated by a visible or infrared （IR） light source. The absorption of light by electrons or individual functional groups within molecules leads to changes in the sample＇s thermal response, optical scattering, and atomic force interactions, all of which can be readily probed by an AFM tip. For example, photothermal induced resonance （PTIR） spectroscopy methods measure a sample＇s local thermal expansion or temperature rise. Therefore, they use the AFM tip as a thermal detector to directly relate absorbed IR light to the thermal response of a sample. Optical scattering methods based on scanning near-field optical microscopy （SNOM） correlate the spectrum of scattered near-field light with molecular vibrational modes. More recently, photo-induced force microscopy （PiFM） has been developed to measure the change of the optical force gradient due to the light absorption by molecular vibrational resonances using AFM＇s superb sensitivity in detecting tip-sample force interactions. Such recent efforts successfully breech the diffraction limit of light to provide nanoscale spatial resolution of vibrational spectroscopy,which will become a critical technique for characterizing novel energy materials.

Transforming bilayer MoS2 into single-layer with strong photoluminescence using UV-ozone oxidation

The use of single-layer MoS2 in light emitting devices requires innovative methods to enhance its low photoluminescence （PL） quantum yield. In this work, we report that single-layer MoS2 with a strong PL can be prepared by oxidizing bilayer MoS2 using W-ozone oxidation. We show that as compared to mechanically-exfoliated single-layer MoS2, the PL intensity of the single-layer MoS2 prepared by W-ozone oxidation is enhanced by 20-30 times. We demonstrate that the PL intensity of both neutral excitons and trions （charged excitons） can be greatly enhanced in the oxidized MoS2 samples. These results provide novel insights into the PL enhancement of single-layer MoS2.