Tip-enhanced Raman Spectroscopy Research Articles

Resonant Tip-Enhanced Raman Spectroscopy of a Single-Molecule Kondo System.

Tip-enhanced Raman spectroscopy (TERS) under ultrahigh vacuum and cryogenic conditions enables exploration of the relations between the adsorption geometry, electronic state, and vibrational fingerprints of individual molecules. TERS capability of reflecting spin states in open-shell molecular configurations is yet unexplored. Here, we use the tip of a scanning probe microscope to lift a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule from a metal surface to bring it into an open-shell spin one-half anionic state. We reveal a correlation between the appearance of a Kondo resonance in differential conductance spectroscopy and concurrent characteristic changes captured by the TERS measurements. Through a detailed investigation of various adsorbed and tip-contacted PTCDA scenarios, we infer that the Raman scattering on suspended PTCDA is resonant with a higher excited state. Theoretical simulation of the vibrational spectra enables a precise assignment of the individual TERS peaks to high-symmetry Ag modes, including the fingerprints of the observed spin state. These findings highlight the potential of TERS in capturing complex interactions between charge, spin, and photophysical properties in nanoscale molecular systems and suggest a pathway for designing single-molecule spin-optical devices.

In situ and ex situ approaches for molecular scale understanding of electrochemical interfaces

Abstract Microscopic studies on electrolyte solution / electrode interfaces provide the most fundamental information not only for understanding the electric double layer formed at the interfaces but also for designing sophisticated electrochemical (EC) devices. In this study, we developed tip-enhanced Raman spectroscopy (TERS), which is based on an electrochemical scanning tunneling microscope (EC-STM), and demonstrated electrochemical TERS (EC-TERS) measurements of benzenethiol monolayers on Au(111). A specially-designed cell enables us to carry out reproducible EC, EC-STM, and EC-TERS measurements, which indicates consistent results among these techniques for the oxidative desorption of the benzenethiol monolayers.

Fabrication of plasmonic probes for reproducible nanospectroscopic investigation of lipid monolayers – The electrochemical etching with DC-pulsed voltage

Tip-enhanced Raman spectroscopy (TERS) is a label-free analytical technique that characterizes molecular systems, potentially even with a nanometric resolution. In principle, the metallic plasmonic probe is illuminated with a laser beam generating the localized surface plasmons, which induce a strong local electric field enhancement in close proximity to the probe. Such field enhancement improves the Raman scattering cross-section from the sample volume localized near the probe apex. TERS provides a high spatial resolution and a great sensitivity, however, it is rather rarely used due to technical limitations causing unstable enhancement and the relative lack of data reproducibility. Despite many scientific efforts for the fabrication of effective TER probes providing robust TER enhancement still requires further investigations. In this work, we explore new possibilities based on preparation of scanning tunnelling microscopy (STM) plasmonic probes, since by nature of the tunnelling effect, they potentially could offer a very high spatial resolution in STM guided TERS experiments. Here we compare two methods of STM-TERS probe preparation for effective spectra acquisition. Our results strongly indicate that an application of square pulse voltage upon the etching procedure significantly improves the quality of the TER data over those obtained with a constant voltage one. To demonstrate the efficiency of our probes we present the results of hyperspectral TER mapping of the 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) monolayer deposited on an ultra-pure and atomically flat gold substrate.

Nano-Raman Spectroscopy of 2D Materials

Abstract The use of nano-Raman spectroscopy to study two-dimensional (2D) systems is presented here. The nano (tip-enhanced) Raman spectroscopy (TERS) technique is briefly introduced, addressing some new theoretical aspects for Raman spectroscopy in the near-field regime, including field coherence, field distribution and the relevance of atomic description and quenching effects. State-of-the-art results in graphene and transition metal dichalcogenides are presented, exploring the connection between micro- and nano-Raman metrology. Various aspects such as defects, homojunctions, twisted-bilayer structures, localized emissions at bubbles, wrinkles, and borders, as well as substrate and coherence effects are addressed in detail. The paper concludes by outlining the perspectives for nano-Raman spectroscopy in 2D systems, highlighting its potential for advancing our understanding of nanoscale phenomena and facilitating further breakthroughs in materials science and characterization.

Strained Silicon Technology: Non-Destructive High-Lateral-Resolution Characterization Through Tip-Enhanced Raman Spectroscopy

Strained Silicon Technology: Non-Destructive High-Lateral-Resolution Characterization Through Tip-Enhanced Raman Spectroscopy

Mechanistic Understanding of Oxygen Activation on Bulk Au(111) Surface Using Tip-Enhanced Raman Spectroscopy.

Gaining mechanistic understanding of oxygen activation on metal surfaces is a topical area of research in surface science. However, direct investigation of on-surface oxidation processes at the nanoscale and the empirical validation of oxygen activation pathways remain challenging for the conventional analytical tools. In this study, we applied tip-enhanced Raman spectroscopy (TERS) to gain mechanistic insights into oxygen activation on bulk Au(111) surface. Specifically, oxidation of 4-aminothiophenol (4-ATP) to 4-nitrothiophenol (4-NTP) on Au(111) surface was investigated using hyperspectral TERS imaging. Nanoscale TERS images revealed a markedly higher oxidation efficiency in disordered 4-ATP adlayers compared to the ordered adlayers signifying that the oxidation of 4-ATP molecules proceeds via interaction with the on-surface oxidative species. These results were further validated via direct oxidation of the 4-ATP adlayers with H2O2 solution. Finally, TERS measurements of oxidized 4-ATP adlayers in the presence of H2O18 provided the first empirical evidence for the generation of oxidative species on bulk Au(111) surface via water-mediated activation of molecular oxygen. This study expands our mechanistic understanding of oxidation chemistry on bulk Au surface by elucidating the oxygen activation pathway.

Spring constant of an AFM cantilever with a thin-film plasmonic waveguide formed at its end

Abstract Atomic-force-microscope (AFM)-based tip-enhanced Raman spectroscopy (TERS) is a promising analytical technique that can identify the physical and chemical properties of a sample’s surface. In the conventional TERS setup, the tip is directly irradiated by an incident light, which causes degradation of the contrast of the TERS signal due to the Raman scattered light from the surface area around the tip. We recently developed an AFM cantilever for indirect illumination AFM-TERS by milling the tip of the conventional cantilever to form a thin-film waveguide. Since the thin-film waveguide is considered as another cantilever attached at the end of the original cantilever, the waveguide cantilever can be treated as cantilevers connected in series. We then analyzed the static spring constant of the waveguide cantilever by both analytical and numerical methods and found that the static spring constant of the waveguide cantilever is lower than that of the original cantilever, which is advantageous in reducing the contact damage during the TERS measurements. We also proposed procedures to experimentally calibrate the static spring constant of the waveguide cantilever.

Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy

Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy

Nanoscale Chemical Analysis of Thin Film Solar Cell Interfaces Using Tip-Enhanced Raman Spectroscopy.

Interfacial regions play a key role in determining the overall power conversion efficiency of thin film solar cells. However, the nanoscale investigation of thin film interfaces using conventional analytical tools is challenging due to a lack of required sensitivity and spatial resolution. Here, we surmount these obstacles using tip-enhanced Raman spectroscopy (TERS) and apply it to investigate the absorber (Sb2Se3) and buffer (CdS) layers interface in a Sb2Se3-based thin film solar cell. Hyperspectral TERS imaging with 10 nm spatial resolution reveals that the investigated interface between the absorber and buffer layers is far from uniform, as TERS analysis detects an intermixing of chemical compounds instead of a sharp demarcation between the CdS and Sb2Se3 layers. Intriguingly, this interface, comprising both Sb2Se3 and CdS compounds, exhibits an unexpectedly large thickness of 295 ± 70 nm attributable to the roughness of the Sb2Se3 layer. Furthermore, TERS measurements provide compelling evidence of CdS penetration into the Sb2Se3 layer, likely resulting from unwanted reactions on the absorber surface during chemical bath deposition. Notably, the coexistence of ZnO, which serves as the uppermost conducting layer, and CdS within the Sb2Se3-rich region has been experimentally confirmed for the first time. This study underscores TERS as a promising nanoscale technique to investigate thin film inorganic solar cell interfaces, offering novel insights into intricate interface structures and compound intermixing.

Mechanistic Understanding of Oxygen Activation on Bulk Au(111) Surface Using Tip‐Enhanced Raman Spectroscopy

AbstractGaining mechanistic understanding of oxygen activation on metal surfaces is a topical area of research in surface science. However, direct investigation of on‐surface oxidation processes at the nanoscale and the empirical validation of oxygen activation pathways remain challenging for the conventional analytical tools. In this study, we applied tip‐enhanced Raman spectroscopy (TERS) to gain mechanistic insights into oxygen activation on bulk Au(111) surface. Specifically, oxidation of 4‐aminothiophenol (4‐ATP) to 4‐nitrothiophenol (4‐NTP) on Au(111) surface was investigated using hyperspectral TERS imaging. Nanoscale TERS images revealed a markedly higher oxidation efficiency in disordered 4‐ATP adlayers compared to the ordered adlayers signifying that the oxidation of 4‐ATP molecules proceeds via interaction with the on‐surface oxidative species. These results were further validated via direct oxidation of the 4‐ATP adlayers with H2O2 solution. Finally, TERS measurements of oxidized 4‐ATP adlayers in the presence of H2O18 provided the first empirical evidence for the generation of oxidative species on bulk Au(111) surface via water‐mediated activation of molecular oxygen. This study expands our mechanistic understanding of oxidation chemistry on bulk Au surface by elucidating the oxygen activation pathway.

Electrochemical Tip-Enhanced Raman Spectroscopy for the Elucidation of Complex Electrochemical Reactions

Electrochemical Tip-Enhanced Raman Spectroscopy for the Elucidation of Complex Electrochemical Reactions

Electro-optical properties of a graphene device on a tip-enhanced Raman spectroscopy system.

This paper investigates the impact of graphene on tip-enhanced Raman spectroscopy (TERS) by developing an electromagnetic characterization of the TERS-graphene device system. The study focuses on the interaction between the tip, the gate voltage, and the sample, specifically examining the electromagnetic effects in the system. Employing a finite element method (FEM)-based simulation model, we meticulously dissect the electric field distribution and the Raman amplification when graphene is introduced into the system. Our findings reveal that including graphene results in a marginal reduction in Raman amplification and a negligible variation in the induced charges within the system. To reinforce our simulations, we employ a simplified capacitor model, which corroborates our results, showcasing negligible induced charges and validating the obtained capacitance values. In this manuscript, we also explore the influence of the setup on the electro-optical properties of graphene, revealing a slight variation in conductivity despite strong changes in chemical potential. Overall, this work contributes to understanding TERS's electromagnetic aspects in the presence of graphene.

Photoluminescence emission and Raman enhancement in TERS: an experimental and analytic revisiting

Abstract An analytic model is used to calculate the Raman and fluorescence enhancement of a molecule in between two closely spaced gold nanospheres. Instead of using the conventional approach that only the dipolar plasmonic mode is considered, we calculate the electric field enhancement in the nanometre sized gap, by taking account of the higher order modes in one gold sphere, which couples to the dipolar mode of the other sphere. The experimental confirmation is performed by gap-dependent tip-enhanced Raman spectroscopy (TERS) measurements. The photoluminescence and Raman enhancement are both observed with different growing trends as the gap width decreases. Red-shift of the background spectra is observed and implies the increasing coupling between the nanospheres. This analytic model is shown to be able to interpret the enhancement mechanisms underlying gap-dependent TERS experimental results.

Probing the multi-disordered nanoscale alloy at the interface of lateral heterostructure of MoS2–WS2

Abstract Transition metal dichalcogenide (TMDs) heterostructure, particularly the lateral heterostructure of two different TMDs, is gaining attention as ultrathin photonic devices based on the charge transfer (CT) excitons generated at the junction. However, the characteristics of the interface of the lateral heterostructure, determining the electronic band structure and alignment at the heterojunction region, have rarely been studied due to the limited spatial resolution of nondestructive analysis systems. In this study, we investigated the confined phonons resulting from the phonon-disorder scattering process involving multiple disorders at the lateral heterostructure interface of MoS2–WS2 to prove the consequences of disorder-mediated deformation in the band structure. Moreover, we directly observed variations in the metal composition of the multi-disordered nanoscale alloy Mo1−x W x S2, consisting of atomic vacancies, crystal edges, and distinct nanocrystallites. Our findings through tip-enhanced Raman spectroscopy (TERS) imply that a tens of nanometer area of continuous TMDs alloy forms the multi-disordered interface of the lateral heterostructure. The results of this study could present the way for the evaluation of the TMDs lateral heterostructure for excitonic applications.

Local heating and Raman thermometry in a single molecule.

Because of the nonequilibrium nature of thermal effects at the nanoscale, the characterization of local thermal effects within a single molecule is highly challenging. Here, we demonstrate a way to characterize the local thermal properties of a single fullerene (C60) molecule during current-induced heating processes through tip-enhanced anti-Stokes Raman spectroscopy. Although the measured vibron populations are far from equilibrium with the environment, we can still define an "effective temperature (Teff)" statistically via a Bose-Einstein distribution, suggesting a local equilibrium within the molecule. With increased current heating, Teff is found to rise up to about 1150 K until the C60 cage is decomposed. Such a decomposition temperature is similar to that reported for ensemble C60 samples, thus justifying the validity of our methodology. Moreover, the possible reaction pathway and product can be identified because of the chemical sensitivity of Raman spectroscopy. Our findings provide a practical method for noninvasively detecting the local heating effect inside a single molecule under nonequilibrium conditions.

Sub-Tip-Radius Near-Field Interactions in Nano-FTIR Vibrational Spectroscopy on Single Proteins.

Tip-enhanced vibrational spectroscopy has advanced to routinely attain nanoscale spatial resolution, with tip-enhanced Raman spectroscopy even achieving atomic-scale and submolecular sensitivity. Tip-enhanced infrared spectroscopy techniques, such as nano-FTIR and AFM-IR spectroscopy, have also enabled the nanoscale chemical analysis of molecular monolayers, inorganic nanoparticles, and protein complexes. However, fundamental limits of infrared nanospectroscopy in terms of spatial resolution and sensitivity have remained elusive, calling for a quantitative understanding of the near-field interactions in infrared nanocavities. Here, we demonstrate the application of nano-FTIR spectroscopy to probe the amide-I vibration of a single protein consisting of ∼500 amino acid residues. Detection with higher tip tapping demodulation harmonics up to the seventh order leads to pronounced enhancement in the peak amplitude of the vibrational resonance, originating from sub-tip-radius geometrical effects beyond dipole approximations. This quantitative characterization of single-nanometer near-field interactions opens the path toward employing infrared vibrational spectroscopy at the subnanoscale and single-molecule levels.

Theoretical and computational methods for tip- and surface-enhanced Raman scattering.

Raman spectroscopy is a versatile tool for acquiring molecular structure information. The incorporation of plasmonic fields has significantly enhanced the sensitivity and resolution of surface-enhanced Raman scattering (SERS) and tip-enhanced Raman spectroscopy (TERS). The strong spatial confinement effect of plasmonic fields has challenged the conventional Raman theory, in which a plane wave approximation for the light has been adopted. In this review, we comprehensively survey the progress of a generalized theory for SERS and TERS in the framework of effective field Hamiltonian (EFH). With this approach, all characteristics of localized plasmonic fields can be well taken into account. By employing EFH, quantitative simulations at the first-principles level for state-of-the-art experimental observations have been achieved, revealing the underlying intrinsic physics in the measurements. The predictive power of EFH is demonstrated by several new phenomena generated from the intrinsic spatial, momentum, time, and energy structures of the localized plasmonic field. The corresponding experimental verifications are also carried out briefly. A comprehensive computational package for modeling of SERS and TERS at the first-principles level is introduced. Finally, we provide an outlook on the future developments of theory and experiments for SERS and TERS.

Toward the nanoscale chemical and physical probing of milk-derived extracellular vesicles using Raman and tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) is an advanced technique to perform local chemical analysis of the surface of a sample through the improvement of the sensitivity and the spatial resolution of Raman spectroscopy by plasmonic enhancement of the electromagnetic signal in correspondence with the nanometer-sized tip of an atomic force microscope (AFM). In this work, TERS is demonstrated to represent an innovative and powerful approach for studying extracellular vesicles, in particular bovine milk-derived extracellular vesicles (mEVs), which are nanostructures with considerable potential in drug delivery and therapeutic applications. Raman spectroscopy has been used to analyze mEVs at the micrometric and sub-micrometric scales to obtain a detailed Raman spectrum in order to identify the 'signature' of mEVs in terms of their characteristic molecular vibrations and, therefore, their chemical compositions. With the ability to improve lateral resolution, TERS has been used to study individual mEVs, demonstrating the possibility of investigating a single mEV selected on the surface of the sample and, moreover, analyzing specific locations on the selected mEV with nanometer lateral resolution. TERS potentially allows one to reveal local differences in the composition of mEVs providing new insights into their structure. Also, thanks to the intrinsic properties of TERS to acquire the signal from only the first few nanometers of the surface, chemical investigation of the lipid membrane in correspondence with the various locations of the selected mEV could be performed by analyzing the peaks of the Raman shift in the relevant range of the spectrum (2800-3000 cm-1). Despite being limited to mEVs, this work demonstrates the potential of TERS in the analysis of extracellular vesicles.

Nanoscale insights into graphene oxide reduction by tip-enhanced Raman spectroscopy.

Graphene oxide (GO) has attracted substantial interest for its tunable properties and as a possible intermediate for the bulk manufacture of graphene. GO and its reduced derivatives display electronic and optical properties that depend strongly on their chemical structure, and with proper functionalization, GO can have a desirable bandgap for semiconductor applications. However, its chemical activity leads to a series of unclear chemical changes under ambient conditions, resulting in changes in color and solubility upon exposure to light. In this paper, we study the properties of fresh and spontaneously reduced GO under ambient conditions using tip-enhanced Raman spectroscopy (TERS) to map its nanometer scale chemical and structural heterogeneity. We observe different types of defect sites on reduced GO (rGO) by spatially mapping the D to G band peak ratio and D and G band spectral positions. The higher spatial resolution and out-of-plane polarization compared to conventional micro-Raman spectroscopy enables us to resolve unusual features, including D-band shifting on rGO. Based on statistical analysis of the spatial variations in modes and theoretical calculations for different functional groups, we conclude the reduction mechanism of GO is a self-photocatalytic reduction with the participation of water and visible light, in which the rate determining step is electron transport through the metal substrate and ion diffusion on the GO surface. These results demonstrate that TERS can reveal structural and chemical details elucidating reduction mechanisms, through the examination of samples at different time points.

Nanoscale Visualization of Phase Separation in Binary Supported Lipid Monolayer using Tip-Enhanced Raman Spectroscopy

Nanoscale Visualization of Phase Separation in Binary Supported Lipid Monolayer using Tip-Enhanced Raman Spectroscopy