Near-field Raman Spectroscopy Research Articles

Modification of transition pathways in polarized resonance Raman spectroscopy for carbon nanotubes by highly confined near-field light

We observed a modification of transition pathways in polarized resonance Raman spectroscopy during tip-enhanced Raman spectroscopy (TERS) analysis of metallic carbon nanotubes (CNTs). At a spatial resolution reaching up to the sub-nanometer regime, the signal intensity of the typical D-band is observed to be even higher than the intensity of the G-band all over the probed CNTs in TERS imaging. The measured D-band is attributed to the non-vertical transitions of electrons in k-space that are facilitated by highly confined near-field light at the tip–sample junction of our scanning tunneling microscope based TERS system. The D-band signal was observed even when the CNTs were excited by light polarized perpendicular to the tube axis that corresponds to electronic excitations between different cutting line numbers of a CNT. By combining the electron pathways brought about by both the near-field light and its polarization, we found a unique optical transition of electrons of CNTs in near-field Raman spectroscopy.

Interfacial Chemistry of Thiophene As an Effective Film-Forming Additive on High Voltage Cathode Revealed By Operando Raman Spectroscopy

For decades intense research efforts have been aimed at increasing energy densities with new rechargeable lithium battery (RLB) designs to meet the anticipated increasing energy storage demands. These efforts have yielded much higher capacities with novel materials. However, the theoretical capacity of an RLB cell is seeded in the structure of the electrode, while its practical capacity, performance, cycle life, and safety are deep-rooted in the side reactions at the interphase between electrode and electrolyte (interphase is the phase at the electrode-electrolyte interface) 1,2.Interphases are essential for the operation of the cells and have been widely recognized as the "most important and the least understood" components of RLBs3. While their characteristics determine their performance, they are not part of the design of RLBs, but only form during the cell operation on the anodes and cathodes. They constitute passivation layers with mixed chemistries due to the electrolytes' electrochemical stability window (ESW) being smaller than the operating potential of RLBs. Although interphase formation is of functional importance, its formation imposes a heavy price on the cell's performance. Formation of the interphase consumes the electrolyte and active lithium stored in the cathode and causes a dramatic capacity loss, especially in the initial charge/discharge cycles. Also, the presence of the interphase introduces a high level of impedance to the cell, which interrupts the fast and constant flow of Li-ion between the anode and cathode. Last but not least, interphase is an active and complex medium that changes its chemical composition and transport properties during charge/discharge cycling and storing conditions. This results in a constant evolution of the interphase and capacity fading, which is more prominent in the high cell voltage applications. Achieving high cell voltage by increasing the cut-off voltage of LiNi x Co y Mn1−x−y O2 cathode (NMC) materials to 4.5 V is an effective way to enhance the energy density of RLBs4. However, a high level of parasitic and decomposition reactions result in severe capacity fading of the battery cell5.Many efforts have been made to improve the properties of the cathode interphase at high cut-off voltage by incorporating different strategies. The in vivo approach is one of the more successful attempts to design the cathode interphase by incorporating film-forming additives in electrolytes to suppress parasite reactions at the electrode-electrolyte interface6-8. In an ideal case, this film should be stable with cycling and have excellent conductivity for Li+ ions and low electronic conductivity9.Thiophene-based molecules are investigated as effective film-forming on NMC at high cut-off voltages of 4.5 V vs. Li/Li+. Electrochemical investigations show that thiophene oxidizes before carbonate-based electrolytes and forms a stable interphase with high conductivity for Li-ion. Also, the electrochemical performance of the cell is enhanced significantly in the presence of thiophene additive with capacity retention of 95% after 100 cycles (75% capacity retention of the benchmark system). To reveal the underlying mechanisms of the interphase formation and thiophene working principle on the surface of NMC cathode, we performed operando near-field Raman spectroscopy. The Raman and electrochemistry results indicate that a poly-thiophene film is formed that covers the surface of the cathode active materials uniformly, protecting further oxidation of the electrolyte and preventing transition metal dissolution and decomposition of the active cathode materials. (1) Freunberger SA Nature Chemistry 2019, 11, 761. (2) Yang Y, Yan C, Huang JQ Acta Physico-Chimica Sinica 2021, 37. (3) Winter M Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics 2009, 223, 1395. (4) Fergus JW Journal of Power Sources 2010, 195, 939. (5) Yan GC, Li XH, Wang ZX, Guo HJ, Wang C Journal of Power Sources 2014, 248, 1306. (6) Zhang L, Zhang ZC, Wu HM, Amine K Energy & Environmental Science 2011, 4, 2858. (7) Liu QY, Yang GJ, Li SW, Zhang SM, Chen RJ, Wang ZX, Chen LQ Acs Applied Materials & Interfaces 2021, 13, 21459. (8) Zhu XB, Schulli T, Wang LH Chemical Research in Chinese Universities 2020, 36, 24. (9) Xu K Chemical Reviews 2014, 114, 11503.

Near-field probing of dielectric screening by hexagonal boron nitride in graphene integrated on silicon photonics

Hexagonal boron nitride (hBN) is one of the most suitable 2D materials for supporting graphene in electronic devices, and it plays a fundamental role in screening out the effect of charge impurities in graphene in contrast to inhomogeneous supports such as silicon dioxide (SiO2). Although many interesting surface science techniques such as scanning tunneling microscopy (STM) revealed dielectric screening by hBN and emergent physical phenomena were observed, STM is only appropriate for graphene electronics. In this paper, we demonstrate the dielectric screening by hBN in graphene integrated on a silicon photonic waveguide from the perspective of a near-field scanning optical microscopy (NSOM) and Raman spectroscopy. We found shifts in the Raman spectra and about three times lower slope decrease in the measured electric near-field amplitude for graphene on hBN relative to that for graphene on SiO2. Based on finite-difference time-domain simulations, we confirm lower electric field slope and scattering rate in graphene on hBN, which implies dielectric screening, in agreement with the NSOM signal. Graphene on hBN integrated on silicon photonics can pave the way for high-performance hybrid graphene photonics.

Single-Molecule Resonance Raman Spectroscopy

Near-field Raman spectroscopy has attracted significant attention as a tool for performing chemical analysis with submolecular spatial resolution. The mechanism in atomic and molecular scale Raman spectroscopy, however, is not well understood due to the strong perturbation of the molecule during measurements in previous studies. In particular, the resonance effect that greatly enhances Raman scattering has not been clarified on a single molecule scale. Here we demonstrate single-molecule resonance Raman imaging with a scanning tunneling microscope (STM) at submolecular resolution of copper naphthalocyanine molecules. In our experiment, an ultra-thin insulating NaCl film is used as the substrate to keep the molecule in an undisturbed condition for performing a precise analysis. We have succeeded in resonance Raman spectroscopy by tuning the excitation wavelength to the intrinsic electronic transitions of the molecule. This makes it possible to acquire accurate Raman spectra with a short measurement time at single molecule sensitivities. The resonance Raman maps show three different spatial distribution patterns depending on the symmetry of the vibration modes. These results are explained by considering the interaction between the electromagnetic field of the plasmon in the tip-substrate gap and the intrinsic molecular symmetry, thereby a selection rule for the plasmon-enhanced resonant Raman effect is established.

Theoretical method for near-field Raman spectroscopy with multipolar Hamiltonian and real-time-TDDFT: Application to on- and off-resonance tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy in combination with scanning tunneling microscopy could produce ultrahigh-resolution Raman spectra and images for single-molecule vibrations. Furthermore, a recent experimental study successfully decoupled the interaction between the molecule and the substrate/tip to investigate the intrinsic properties of molecules and their near-field interactions by Raman spectroscopy. In such a circumstance, more explicit treatments of the near field and molecular interactions beyond the dipole approximation would be desirable. Here, we propose a theoretical method based on the multipolar Hamiltonian that considers full spatial distribution of the electric field under the framework of real-time time-dependent density functional theory. This approach allows us to treat the on- and off-resonance Raman phenomena on the same footing. For demonstration, a model for the on- and off-resonance tip-enhanced Raman process in benzene was constructed. The obtained Raman spectra are well understood by considering both the spatial structure of the near field and the molecular vibration in the off-resonance condition. For the on-resonance condition, the Raman spectra are governed by the transition moment, in addition to the selection rule of off-resonance Raman. Interestingly, on-resonance Raman can be activated even when the near field forbids the π-π* transition at equilibrium geometry due to vibronic couplings originating from structural distortions.

Near- and far-field Raman spectroscopic studies of nanodiamond composite films deposited by coaxial arc plasma

Raman spectroscopic studies on nanodiamond composite (NDC) films, comprising nano-sized diamond grains and an amorphous carbon (a-C) matrix, deposited by coaxial arc plasma deposition are challenging because the scattering of the nano-sized diamond grains competes with the strong signal of the a-C matrix. To unravel the nanocomposite structure of NDC films, both far- and near-field Raman spectroscopy were employed. Based on the comparison of visible and ultraviolet far-field Raman data, component spectra based on either nanodiamond or a-C were estimated by a peak-decomposition procedure based on band fitting. Near-field optical resolution achieved via tip-enhanced Raman spectroscopy reveals sharper peaks of both the nanodiamond and the amorphous carbon than the far-field spectra. Consequently, the peak-decomposition procedure is not required, which evidently indicates the effective detection of nanodiamond grains embedded in a-C matrices and is a direct result of the high spatial resolution that limits the number of probed grains. The size of the nanocrystals could additionally be estimated from the profile and position of a diamond peak. This work demonstrates that tip-enhanced Raman spectroscopy is a powerful nondestructive method for nanodiamond composite films, which allows direct access to parameters hitherto only available via average data.

Size-Dependent Localized Phonon Population in Semiconducting Si Nanowires.

The optical phonons in semiconductor nanostructures play an indispensable role in fundamental phenomenon and device applications based on these nanostructures. We study the Raman spectroscopy of optical phonons in Si nanowires (NWs) whose sizes are beyond the phonon confinement regime. The peak shift and unusual asymmetric broadening by one-phonon mode in Si NWs is observed during far-field Raman studies. Using an appropriate thermal anchoring and localized Raman measurements on single NWs by near-field tip-enhanced Raman spectroscopy (TERS), we demonstrate the decoupling of multiple origins responsible for the peak shift accompanied by asymmetric broadening of the one-phonon mode and the appearance of multiple phonon peaks from a single measurement area. A model based on the localized phonon population induced by NW size-dependent charge depletion is proposed to explain the observed dependence of phonon characteristics on NW size. The scanning Kelvin probe force microscopy measurements confirm the size-dependent intrinsic semiconductor surface and interface states-induced charge depletions in single Si NWs. The study clearly suggests the size-dependent phonon characteristics of Si NWs which are crucial for several NW-based photovoltaic and thermoelectric devices.

Near-Field Raman Spectroscopy with Aperture Tips.

In this paper, we review nano-Raman techniques based on aperture scanning near-field optical microscopy (SNOM). Fundamentals of SNOM and aperture-tip-based near-field Raman spectroscopy and their applications in key technical issues, including Raman signal intensity and collection time, are introduced. Recent advances in the tip design are discussed, and applications of the aperture-SNOM-based nano-Raman technique are presented. We attempt to identify the most pressing open questions in this field. We believe that, by improving the power transmission efficiency and combining the local field enhancing technique with the tip-enhanced spectroscopy, the performance of aperture-SNOM can be significantly improved. Its nanometer-scale excitation volume and the consequent low background make the aperture-tip technique feasible for many important samples that cannot be measured by other optical nanospectroscopies.

Near-field Raman spectroscopy of nanocarbon materials.

Nanocarbon materials, including sp(2) hybridized two-dimensional graphene and one-dimensional carbon nanotubes, and sp(1) hybridized one-dimensional carbyne, are being considered for the next generation of integrated optoelectronic devices. The strong electron-phonon coupling present in these nanocarbon materials makes Raman spectroscopy an ideal tool to study and characterize the material and device properties. Near-field Raman spectroscopy combines non-destructive chemical, electrical, and structural specificity with nanoscale spatial resolution, making it an ideal tool for studying nanocarbon systems. Here we use near-field Raman spectroscopy to study strain, defects, and doping in different nanocarbon systems.

Silicon nitride grids are compatible with correlative negative staining electron microscopy and tip-enhanced Raman spectroscopy for use in the detection of micro-organisms

Successive application of negative staining transmission electron microscopy (TEM) and tip-enhanced Raman spectroscopy (TERS) is a new correlative approach that could be used to rapidly and specifically detect and identify single pathogens including bioterrorism-relevant viruses in complex samples. Our objective is to evaluate the TERS-compatibility of commonly used electron microscopy (EM) grids (sample supports), chemicals and negative staining techniques and, if required, to devise appropriate alternatives. While phosphortungstic acid (PTA) is suitable as a heavy metal stain, uranyl acetate, paraformaldehyde in HEPES buffer and alcian blue are unsuitable due to their relatively high Raman scattering. Moreover, the low thermal stability of the carbon-coated pioloform film on copper grids (pioloform grids) negates their utilization. The silicon in the cantilever of the silver-coated atomic force microscope tip used to record TERS spectra suggested that Si-based grids might be employed as alternatives. From all evaluated Si-based TEM grids, the silicon nitride (SiN) grid was found to be best suited, with almost no background Raman signals in the relevant spectral range, a low surface roughness and good particle adhesion properties that could be further improved by glow discharge. Charged SiN grids have excellent particle adhesion properties. The use of these grids in combination with PTA for contrast in the TEM is suitable for subsequent analysis by TERS. The study reports fundamental modifications and optimizations of the negative staining EM method that allows a combination with near-field Raman spectroscopy to acquire a spectroscopic signature from nanoscale biological structures. This should facilitate a more precise diagnosis of single viral particles and other micro-organisms previously localized and visualized in the TEM.

Highly sensitive Raman spectroscopy using a gap mode plasmon under an attenuated total reflection geometry

We investigated a gap mode plasmon under an attenuated total reflection (ATR) configuration toward realization of near-field Raman spectroscopy with a single molecule sensitivity and spatial resolution. Additional enhancement in Raman scattering at a nanogap was obtained by a coupling of a propagating surface plasmon (PSP) of Ag films on a prism, and a gap mode between Ag films and Ag nanoparticles (AgNPs). Immobilization of AgNPs on Ag films through thiol-SAM slightly up-shifted the resonance angle of a PSP, which broadened the reflectivity dip owing to an increased out-coupling of a PSP. Raman enhancement factor at a nanogap increased with decreasing surface coverage of AgNPs, albeit the enhancement factor averaged over illuminated area in Ag films decreased, ensuring the largest enhancement factor in tip-enhanced Raman scattering. This is due to increased efficiency for a PSP excitation at lower coverage of AgNPs in consistent with that in theoretical evaluation using finite difference time domain calculations. A gap mode under an ATR configuration was applied to elucidate a plausible photochemical reaction of p-amino thiophenol (PATP) adsorbed on Ag films on a prism. Spectral changes in Raman scattering under laser illumination were observed for PATP with a deuterated amino group, but suppressed by a dimethyl amino group owing to steric hindrance, supporting the photochemical dimerization.

The controlled fabrication of “Tip-On-Tip” TERS probes

Tip-enhanced near-field Raman spectroscopy has exhibited a great ability to detect in situ chemical and structural information on a sample surface with the highest lateral resolution combined with a high sensitivity at the same time. A key challenge in the TERS field is the development and improvement of the fabrication of reproducible metal tip geometries with a sharper apex. In this study, one novel apertureless “Tip-On-Tip” TERS probe with a special plasmonic nanostructure is designed, and a simple Ar+-ion sputtering route has been developed to fabricate silver nanoneedle arrays on the scanning probe microscopy (SPM) cantilevers for tip-enhanced Raman spectroscopy (TERS) probes. These silver nanoneedles possess a very sharp apex with an apex diameter of 15 nm and an apex angle of 20°. The novel TERS probes exhibit enhanced near-field Raman signals compared to an Ag-coated SPM probe, which are attributed to the intense electromagnetic field around the apexes of the Ag nanoneedles and the periodic structure of the Ag nanoneedles.

Plasmonic optical antenna design for performing tip-enhanced Raman spectroscopy and microscopy

This paper highlights optical plasmonic antennas designed with dc-pulsed low-voltage electrochemical etching of a gold wire for implementing tip-enhanced Raman scattering (TERS) measurements. We demonstrate a versatile electrochemical system that allows one to engineer TERS-active metallic gold tips with diverse shapes and sizes in a highly reproducible fashion. The underlying etching mechanism at a voltage-driven meniscus around a gold wire immersed into an electrolyte is discussed in detail. We show that the developed method is suitable to produce not only the simplest geometries such as cones and spheroids, but more complex designs. Attempts have been made to design plasmonic tapered antennas with quasi-uniformly spaced nano-sized bumps on the mesoscopic zone for the extra surface plasmon-light coupling. The capability of the patterned antenna to enhance and localize optical fields is demonstrated with near-field Raman microscopy and spectroscopy of single-walled carbon nanotubes bundles.

G031094 斜め入射型近接場ラマン分光法によるSiのスペクトル評価([G03-09]材料力学部門,一般セッション : 変形,ひずみ)

In this study, near-field Raman spectroscopy with high special resolution has been developed. This near-field Raman spectroscopy system consists of scanning near-field optical microscopy (SNOM) and polarized micro-Raman spectroscopy with oblique backscattering configuration. By using this system, near-field Raman spectrum of Si was evaluated. However, it was very difficult to detect Raman signal because near-field Raman scattering signal was very weak. To improve the signal, tip-enhanced system was added to developed system. Au coating apertureless SNOM probe has been developed by FIB machining. The curvature radius of this probe tip is less than 50nm. Polarized oblique incident light was irradiated to the probe tip and Raman scattering light was detected. As a result, enhancement of Raman scattering intensity was observed in the transition region from non-contact to contact of probe tip. Therefore, near-field Raman Spectrum of Si was able to be evaluated by near-field Raman spectroscopy with oblique backscattering configuration.

Raman spectroscopy and polarization: Selected case studies

We show, through several selected case studies, the potential benefits that can be obtained by controlling the polarization states of the exciting and scattered radiations in a Raman scattering experiment. When coupled with polarization control, Raman spectroscopy is thus capable of providing extra information on the structural properties of the materials under investigation. The experimental examples presented in this work are taken from the area of both conventional, i.e., far-field, as well as from near-field Raman spectroscopy. They cover topics such as the stress tensor measurement in strained semiconductor structures, the vibration mode assignment in pentacene thin films and the Raman scattering tensor determination from near-field measurements on azobenzene monolayers. The basic theory necessary for modelling the far- and near-field polarized Raman responses is also given and the model efficiency is illustrated on the experimental data.

Near-field Raman spectroscopy of biological nanomaterials by in situ laser-induced synthesis of tip-enhanced Raman spectroscopy tips

We report a new approach in tip-enhanced Raman spectroscopy (TERS) in which TERS-active tips with enhancement factors of ∼10(-5)× can be rapidly (1-3 min) produced in situ by laser-induced synthesis of silver nanoparticles at the tip apex. The technique minimizes the risks of tip contamination and damage during handling and provides in situ feedback control, which allows the prediction of the tip performance. We show that TERS tips produced by this technique enable the measurement of spatially resolved TERS spectra of self-assembled peptide nanotubes with a spatial resolution of ∼20 nm.

Molecular Arrangement in Self-Assembled Azobenzene-Containing Thiol Monolayers at the Individual Domain Level Studied through Polarized Near-Field Raman Spectroscopy

6-[4-(phenylazo)phenoxy]hexane-1-thiol self-assembled monolayers deposited on a gold surface form domain-like structures possessing a high degree of order with virtually all the molecules being identically oriented with respect to the surface plane. We show that, by using polarized near-field Raman spectroscopy, it is possible to derive the Raman scattering tensor of the ordered layer and consequently, the in-plane molecular orientation at the individual domain level. More generally, this study extends the application domain of the near-field Raman scattering selection rules from crystals to ordered organic structures.

Nanometer resolution stress measurement of the Si gate using illumination–collection-typescanning near-field Raman spectroscopy with a completely metal-inside-coated pyramidalprobe

We have proposed an illumination–collection-type scanning near-field Ramanspectroscopy (SNRS) with a completely gold metal-inside-coated (MIC) pyramidalprobe without an optical aperture in order to detect the Raman spectra of fine Sidevices for local stress measurements. The gold MIC pyramidal probe has beenstudied to act as a plasmon resonance near-field optical probe with high powerusing a finite differential time domain (FDTD) simulation and the prototypedSNRS. In the simulation, the propagated optical power can be made available forSNRS. In the experiments, it is clear that the prototyped SNRS enhanced the SiRaman peak signal by plasmon resonance and could measure the Si Raman peakshift by line scanning the Si gate region and the Si active layer. Furthermore,compressive and tensile stresses localized around the Si gate were demonstrated by theSi Raman peak shift with a resolution of about 10 nm. It is clarified that theproposed SNRS has the possibility of detecting the Raman spectra of a local area.

Prototype of Illumination-Collection Mode Scanning Near-Field Optical Microscopy and Raman Spectroscopy with Gold Inner-Coated Aperture-Less Pyramidal Probe

We have prototyped illumination-collection mode scanning near-field optical microscopy (SNOM) and near-field Raman spectroscopy (NFRS) with gold inner-covered aperture-less pyramidal probe in order to study the possibility to detect optical images, and Raman spectrum and Raman peak shift for stress distribution in Si device with high resolution of about 10 nm.

Raman scattered photon transmission through a single nanoslit

We demonstrate excitation and detection of Raman scattering of a silicon substrate through a 15 nm gold nanoslit. Along with the nanoslit, a plasmonic cavity is fabricated to optimize optical transmission through the slit. Using a polarization analysis we prove that the plasmons enhanced transmission is responsible for the detection of the Raman scattered photons of the silicon substrate through the nanoslit. The optical cavity between the nanoslit and the Si substrate further enhances this backward photon transmission. This opens up prospects for new tools for near-field Raman spectroscopy and sub-wavelength measurements.