Dynamic measurement of an angular Goos-Hänchen shift at a surface plasmon resonance in liquid.

We developed a surface plasmon resonance (SPR)-enhanced angular Goos-Hänchen (GH) shift measurement system capable of tracking small refractive index changes with high sensitivity in a liquid environment. Our method can be performed in angular interrogation schemes, where we demonstrate a simple zero-finding algorithm to locate the SPR angle instead of the complicated data processing algorithms used in conventional sensors. We also propose a displacement interrogation scheme for dynamic measurement of small refractive index changes in the sample. The main advantage of our method is the controllability of the measured displacement by standard geometrical optics, allowing measurement sensitivity enhancement without the need to modify the sensor material.

Monatomic Iodine Dielectric Layer for Multimodal Optical Spectroscopy of Dye Molecules on Metal Surfaces.

Fluorescence and Raman scattering spectroscopies have been used in various research fields such as chemistry, electrochemistry, and biochemistry because they can easily obtain detailed information about molecules at interfaces with visible light. In particular, multimodal fluorescence and Raman scattering spectroscopy have recently attracted significant attention, which enables us to distinguish chemical species and their electronic states that are important for expressing various functions. However, a special strategy is required to perform simultaneous measurements because the cross sections of fluorescence and Raman scattering differ by as much as ∼1014. In this study, we propose a method for the simultaneous measurement of dye molecules on a metal surface using a monatomic layer of iodine as the dielectric layer. The method is based on adequately quenching the photoexcited state of the molecules near the metal surface to weaken the fluorescence intensity and using the resonance effect to increase the Raman signal. We have validated this concept by experiments with insulating layers of different thicknesses and dye molecules of different chemical structures. The proposed multimodal strategy paves the way for various applications such as catalytic chemistry and electrochemistry, where the adsorption structure and electronic states of molecular species near the metal surface determine functionalities.

Chemical Identification and Bond Control of π-Skeletons in a Coupling Reaction.

Highly unsaturated π-rich carbon skeletons afford versatile tuning of structural and optoelectronic properties of low-dimensional carbon nanostructures. However, methods allowing more precise chemical identification and controllable integration of target sp-/sp2-carbon skeletons during synthesis are required. Here, using the coupling of terminal alkynes as a model system, we demonstrate a methodology to visualize and identify the generated π-skeletons at the single-chemical-bond level on the surface, thus enabling further precise bond control. The characteristic electronic features together with localized vibrational modes of the carbon skeletons are resolved in real space by a combination of scanning tunneling microscopy/spectroscopy (STM/STS) and tip-enhanced Raman spectroscopy (TERS). Our approach allows single-chemical-bond understanding of unsaturated carbon skeletons, which is crucial for generating low-dimensional carbon nanostructures and nanomaterials with atomic precision.

Mid-infrared imaging through up-conversion luminescence in trivalent lanthanide ion-doped self-organizing optical fiber array crystal.

We propose a scheme for imaging mid-infrared (MIR) wavelengths via pre-excitation-assisted up-conversion luminescence in lanthanide ion (Ln3+)-doped Self-organizing Optical FIber Array (SOFIA) crystal. First, near-infrared pre-excitation wavelength excites an electron from the ground state to an excited state of Ln3+. Next, the MIR wavelength to be imaged promotes this excited electron to a higher-lying energy state. Finally, relaxation of the electron from the higher-lying energy state to the ground state emits the up-conversion luminescence in the visible region, completing the MIR-to-visible wavelength conversion. An analysis of the 4f to 4f intra-configurational energy level transitions in Ln3+, together with an appropriate selection of the pre-excitation wavelength and the visible luminescence constrained within the 500-700 nm wavelength range, reveals that trivalent erbium (Er3+), thulium (Tm3+), holmium (Ho3+), and neodymium (Nd3+) can be used to image MIR wavelengths. Our proposed scheme, called MIR imAging through up-Conversion LuminEscence in a SOFIA crystal, will enable the imaging of MIR wavelengths using low-cost optics and readily available silicon-based detectors in the visible spectral region and will open up new possibilities for MIR wavelength detection and imaging.

Angular Goos-Hänchen Shift Sensor Using a Gold Film Enhanced by Surface Plasmon Resonance.

We demonstrate the surface plasmon resonance (SPR)-enhanced angular Goos-Hänchen (GH) shift. Typical SPR-enhanced GH shift measurements make use of loosely collimated beams, which enhances only the spatial GH shift (ΔGH). Unlike this scheme, we focused the incident beam to a small beam waist to induce enhancement in the angular GH shift (ΘGH). Although this makes ΔGH negligible, the enhancement of ΘGH is much larger than the decrease in ΔGH. In order to excite surface plasmons, we employ a Kretschmann configuration using a simple gold (Au) film on a substrate. We show that although the efficiency of surface plasmon excitation is decreased by the focused geometry, a significantly large ΘGH was induced. With the simultaneous measurement of reflectivity for SPR and the beam shift for the GH shift used in this work, we experimentally show the potential of measuring enhanced ΘGH toward sensing application when the Au film is exposed to local environmental changes even in the simplest thin film structure.

Molecular Monolayer Sensing Using Surface Plasmon Resonance and Angular Goos-Hänchen Shift.

We demonstrate potential molecular monolayer detection using measurements of surface plasmon resonance (SPR) and angular Goos-Hänchen (GH) shift. Here, the molecular monolayer of interest is a benzenethiol self-assembled monolayer (BT-SAM) adsorbed on a gold (Au) substrate. Excitation of surface plasmons enhanced the GH shift which was dominated by angular GH shift because we focused the incident beam to a small beam waist making spatial GH shift negligible. For measurements in ambient, the presence of BT-SAM on a Au substrate induces hydrophobicity which decreases the likelihood of contamination on the surface allowing for molecular monolayer sensing. This is in contrast to the hydrophilic nature of a clean Au surface that is highly susceptible to contamination. Since our measurements were made in ambient, larger SPR angle than the expected value was measured due to the contamination in the Au substrate. In contrast, the SPR angle was smaller when BT-SAM coated the Au substrate due to the minimization of contaminants brought about by Au surface modification. Detection of the molecular monolayer acounts for the small change in the SPR angle from the expected value.

Tip-enhanced THz Raman spectroscopy for local temperature determination at the nanoscale.

Local temperature of a nanoscale volume is precisely determined by tip-enhanced terahertz Raman spectroscopy in the low temperature range of several tens of degrees. Heat generated by the tip-enhanced electric field is directly transferred to single-walled carbon nanotubes by heat conduction and radiation at the nanoscale. This heating modulates the intensity ratio of anti-Stokes/Stokes Raman scattering of the radial breathing mode of the carbon nanotube based on the Boltzmann distribution at elevated temperatures. Owing to the low-energy feature of the radial breathing mode, the local temperature of the probing volume has been successfully extracted with high sensitivity. The dependence of the temperature rise underneath the tip apex on the incident power coincides with the analytical results calculated by finite element method based on the tip enhancement effect and the consequent steady-state temperature via Joule heat generation. The results show that the local temperature at the nanoscale can be controlled in the low temperature range simply by the incident laser power while exhibiting a sufficiently high tip enhancement effect as an analytical tool for thermally sensitive materials (e.g., proteins, DNA). Graphical Abstract Tip-enhanced THz Raman spectroscopy detects the low frequency Raman mode both in Stokes and anti-Stokes shifts, which precisely reflects the local temperature of the sample volume.

Direct optical mapping of anisotropic stresses in nanowires using transverse optical phonon splitting.

Strain engineering is ubiquitous in the design and fabrication of innovative, high-performance electronic, optoelectronic, and photovoltaic devices. The increasing importance of strain-engineered nanoscale materials has raised significant challenges at both fabrication and characterization levels. Raman scattering spectroscopy (RSS) is one of the most straightforward techniques that have been broadly utilized to estimate the strain in semiconductors. However, this technique is incapable of measuring the individual components of stress, thus only providing the average values of the in-plane strain. This inherit limitation severely diminishes the importance of RSS analysis and makes it ineffective in the predominant case of nanostructures and devices with a nonuniform distribution of strain. Herein, we circumvent this major limitation and demonstrate for the first time the application of RSS to simultaneously probe the two local stress in-plane components in individual ultrathin silicon nanowires based on the imaging of the splitting of the two forbidden transverse optical phonons.

Plasmonically nanoconfined light probing invisible phonon modes in defect-free graphene.

We present a simple plasmonic method that enables tuning of accessibility to the dipole-forbidden transition states of matter. This technique is realized by well-controlled plasmonic dimers, which can confine optical fields on the order of molecular dimensions. As an example, the approach is applied to activate invisible noncenter phonon modes of defect-free graphene in resonance Raman spectra. The relative intensity of the normally forbidden modes with respect to the dipole allowed modes progressively increases as the degree of field confinement increases. This opens up a novel avenue for both photochemical excitation of molecular systems and nanoscale characterization of materials.

Intermolecular Interaction between Single-Walled Carbon Nanotubes and Encapsulated Molecules Studied by Polarization Resonance Raman Microscopy.

In the present study, we investigated the intermolecular interactions between single-walled carbon nanotubes (SWCNTs) and encapsulated molecules by polarization resonance Raman microscopy. C70 encapsulated in SWCNTs is investigated under incident laser polarization parallel and perpendicular to the tube axis. We employed two excitation laser wavelengths 442 and 532 nm, which are in resonance with different electronic states of C70. Under 532 nm excitation, no distinct polarization dependence is found in the Raman spectral pattern, while under 442 nm excitation, a peak not previously seen for this excitation wavelength was clearly observed for parallel excitation. This result can be explained by the modulation of the resonance Raman process via a charge transfer contribution between C70 and the SWCNTs, which is sensitive to the incident polarization as well as the excitation wavelength. The intensity of the local electronic field inside a SWCNT is higher for the parallel excitation than the perpendicular excitation when the nanotubes are in a bundle. The results can be explained by field localization effects at the nanotube walls, qualitatively supported by finite-difference time-domain simulations.

Mapping the "forbidden" transverse-optical phonon in single strained silicon (100) nanowire.

The accurate manipulation of strain in silicon nanowires can unveil new fundamental properties and enable novel or enhanced functionalities. To exploit these potentialities, it is essential to overcome major challenges at the fabrication and characterization levels. With this perspective, we have investigated the strain behavior in nanowires fabricated by patterning and etching of 15 nm thick tensile strained silicon (100) membranes. To this end, we have developed a method to excite the "forbidden" transverse-optical (TO) phonons in single tensile strained silicon nanowires using high-resolution polarized Raman spectroscopy. Detecting this phonon is critical for precise analysis of strain in nanoscale systems. The intensity of the measured Raman spectra is analyzed based on three-dimensional field distribution of radial, azimuthal, and linear polarizations focused by a high numerical aperture lens. The effects of sample geometry on the sensitivity of TO measurement are addressed. A significantly higher sensitivity is demonstrated for nanowires as compared to thin layers. In-plane and out-of-plane strain profiles in single nanowires are obtained through the simultaneous probe of local TO and longitudinal-optical (LO) phonons. New insights into strained nanowires mechanical properties are inferred from the measured strain profiles.

Generation of broadband longitudinal fields for applications to ultrafast tip-enhanced near-field microscopy.

We report on the generation of broadband longitudinal fields within a tightly focused spot by using a segmented wave plate combined with a phase tailored broadband laser pulse. Their field distribution is characterized by observing the scattered light from a gold-coated glass fiber tip as it is scanned across the focused beam spot. It is observed that efficient coupling to the tip-enhanced field can be achieved over a broad bandwidth of more than 100nm, resulting in a positive contrast at the centre of the focus in the spectrally resolved Rayleigh scattering image. Temporal characteristics of the nonlinear excitation at the tip apex observed by using the fringe resolved autocorrelation technique indicate the possibilities of ultrafast spectroscopy by utilizing the tip-enhanced longitudinal fields.

Localized Graphitization on Diamond Surface as a Manifestation of Dopants.

Doped diamond electrodes have attracted significant attention for decades owing to their excellent physical and electrochemical properties. However, direct experimental observation of dopant effects on the diamond surface has not been available until now. Here, low-temperature scanning tunneling microscopy is utilized to investigate the atomic-scale morphology and electronic structures of (100)- and (111)-oriented boron-doped diamond (BDD) electrodes. Graphitized domains of a few nanometers are shown to manifest the effects of boron dopants on the BDD surface. Confirmed by first-principles calculations, local density of states measurements reveal that the electronic structure of these features is characterized by in-gap states induced by boron-related lattice deformation. The dopant-related graphitization is uniquely observed in BDD (111), which explains its electrochemical superiority over the (100) facet. These experimental observations provide atomic-scale information about the role of dopants in modulating the conductivity of diamond, as well as, possibly, other functional doped materials.

Controlling the Resonance Raman Effect in Tip-Enhanced Raman Spectroscopy Using a Thin Insulating Film.

Both surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS) are widely used for the investigation of nanoscale materials. One of the most critical aspects of both SERS and TERS is the control of both the plasmon and molecular resonance precisely. Here, we demonstrate single-molecule TERS under molecular resonance conditions using a scanning tunneling microscope. This was achieved by placing the molecule on a sodium chloride (NaCl) film in order to directly compare the absorption with Raman excitation spectra. Varying the NaCl film thickness changes the degree of screening effect from the metal surface, which leads to a variation of the molecular resonance phenomena. Although it is generally accepted that the target molecule should be directly attached to the metal surface in SERS, our observation using TERS suggests that this is not always optimal, especially under molecular resonance Raman conditions. Our work demonstrates the possibility of controlling molecular resonance by carefully modifying the local environment. This will be useful for future investigation of isolated single molecules or even two-dimensional molecular assemblies.

Single-molecule resonance Raman effect in a plasmonic nanocavity.

Tip-enhanced Raman spectroscopy (TERS) is a versatile tool for chemical analysis at the nanoscale. In earlier TERS experiments, Raman modes with components parallel to the tip were studied based on the strong electric field enhancement along the tip. Perpendicular modes were usually neglected. Here, we investigate an isolated copper naphthalocyanine molecule adsorbed on a triple-layer NaCl on Ag(111) using scanning tunnelling microscope TERS imaging. For flat-lying molecules on NaCl, the Raman images present different patterns depending on the symmetry of the vibrational mode. Our results reveal that components of the electric field perpendicular to the tip should be considered aside from the parallel components. Moreover, under resonance excitation conditions, the perpendicular components can play a substantial role in the enhancement. This single-molecule study in a well-defined environment provides insights into the Raman process at the plasmonic nanocavity, which may be useful in the nanoscale metrology of various molecular systems.

Controlling the plasmon resonance wavelength in metal-coated probe using refractive index modification.

We present a novel technique to tune the plasmon resonance of metal-coated silicon tips in the whole visible region without altering the tips original sharpness. The technique involves modification of the refractive index of silicon probe by thermal oxidization. Lowering the refractive index of silicon tip coated with metal shift the PRW of the metallic layer to shorter wavelength. Numerical simulation using FDTD agrees well with the empirical results. This novel technique is very useful in tip-enhanced Raman spectroscopy studies of various materials because plasmon resonance can tuned to a specific Raman excitation wavelength.

Tip-enhanced Raman spectroscopy for nanoscale strain characterization.

Tip-enhanced Raman spectroscopy (TERS), which utilizes the strong localized optical field generated at the apex of a metallic tip when illuminated, has been shown to successfully probe the vibrational spectrum of today's and tomorrow's state-of-the-art silicon and next-generation semiconductor devices, such as quantum dots. Collecting and analyzing the vibrational spectrum not only aids in material identification but also provides insight into strain distributions in semiconductors. Here, the potential of TERS for nanoscale characterization of strain in silicon devices is reviewed. Emphasis will be placed on the key challenges of obtaining spectroscopic images of strain in actual strained silicon devices.

Highly efficient tip-enhanced Raman spectroscopy and microscopy of strained silicon.

We present a versatile tip-enhanced Raman spectroscopy (TERS) system that permits efficient illumination and detection of optical properties in the visible range to obtain high signal-to-noise Raman signals from surfaces and interfaces of materials using an edge filter. The cutoff wavelength of the edge filter is tuned by changing the angle of incident beam to deliver high incident power and effectively collect scattered near-field signals for nanoscopic investigation in depolarized TERS configuration. The dynamic design of the instrument provides a unique combination of features that allows us to perform reflection or transmission mode TERS to cover both opaque and transparent samples. A detailed description of improvements of TERS was carried out on a thin strained silicon surface layer. The utilization of an edge filter for shorter collection time, specialized tip for higher field enhancement and for elimination of Raman signal from the tip, shorter wavelength, sample orientation relative to probing polarization, and depolarized configuration for higher contrast Raman signal is discussed.

DFT vibrational calculations of rhodamine 6G adsorbed on silver: analysis of tip-enhanced Raman spectroscopy.

The tip-enhanced near-field Raman (TERS) bands of Rhodamine 6G (R6G), that we reported earlier [Chem. Phys. Lett. 2001, 335, 369.], are assigned on the basis of density-functional theory (DFT) calculations at the 6-311++G(d,p) level. The Raman and infrared intensities as well as frequencies of the vibrational modes are used for band assignments. These vibrational modes, in combination with characterization of resonant electronic transitions using time-dependent DFT calculations, predict spectral changes in resonant Raman and surface-enhanced resonant Raman scatterings of R6G. Moreover, the TERS spectra of R6G are analyzed in detail, where interactions between the tip and R6G molecules and their enhancement mechanisms are discussed. Finally, we propose a novel Raman spectroscopy technique capable of detecting molecular vibrations at sub-nanometer scale.

A 1.7 nm resolution chemical analysis of carbon nanotubes by tip-enhanced Raman imaging in the ambient.

Surface morphology of materials is routinely analysed by an atomic force microscope and scanning tunneling microscope (STM) down to subnanometer precision. However, it is still challenging to investigate the surface chemistry simultaneously, which requires specific capability of force or tunneling spectroscopy in ultrahigh vacuum environment and liquid Helium temperature. Here we demonstrate the simultaneous chemical and structural analysis of individual carbon nanotubes (CNTs) by STM-based tip-enhanced Raman spectroscopy (STM-TERS) with 1.7 nm spatial resolution in the ambient. Raman contrast over different types of CNTs, local defects, diameters and bundling effect are all visualized in real space. Disengaging from ultrahigh vacuum and cryogenic environment, our ambient STM-TERS imaging is powerful in analysing local chemistry for CNTs and also suitable for analysing as-made and soft materials, which cannot be seen with general electron microscopy techniques.