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The electromagnetic enhancement theory describes surface-enhanced Raman scattering (SERS) as a Raman effect that takes place in the near-field of a plasmonic nanostructure. The theory has been very successful in explaining the fundamental properties of SERS, modelling the performance of different metals as enhancing materials and optimizing SERS hotspots for strongest possible enhancement. Over the last decade, a number of carefully designed experimental studies have examined predictions of the electromagnetic theory like the size and shape of SERS hotspots, the absolute magnitude of the enhancement and the width of the SERS resonance. Although the overall picture was quite satisfactory, the theory failed to predict key aspects of SERS, for example, the absolute magnitude of the plasmonic enhancement. We scrutinize these experiments and review them focusing on the results that require going beyond the electromagnetic enhancement theory. We argue that the results of these experiments create the need to develop the theory of SERS further, especially the exact role of plasmonic enhancement in inelastic light scattering.

Resonant Raman scattering has been used for decades to study single walled carbon nanotubes (CNTs), but lacks a consistent theory that simultaneously explains all characteristic signatures. We argue that a proper description requires introducing exciton polaritons as couples excitonic and photonic states. We describe the polaritons by waveguided theory for a nanometre thick cylinder with modified dielectric function. During their propagation along the tube, the polaritons scatter with phonons and are re-emitted as photons with smaller energy (Stokes scattering event). This approach consistently explains the energetic positions of the Raman resonances for the radial-breathing mode (RBM), the G and the 2D line as well as the asymmetry in the scattering intensity of the incoming and outgoing resonances without resorting to higher-order scattering events. We measured the Raman effect on chirality-sorted nanotubes over the first and second exciton resonance and excellently predict its behaviour, which has not been achieved before. The formation of polaritonic states will affect other optical processes in CNTs. Furthermore, exciton-polariton effects appear inevitable in all one-dimensional excitonic systems, similar to our observations in single walled carbon nanotubes.

Polariton-based devices require materials where light-matter coupling under ambient conditions exceeds losses, but our current selection of such materials is limited. Here we measured the dispersion of polaritons formed by the $A$ and $B$ excitons in thin ${\mathrm{MoS}}_{2}$ slabs by imaging their optical near fields. We combined fully tunable laser excitation in the visible with a scattering near-field optical microscope to excite polaritons and image their optical near fields. We obtained the properties of bulk ${\mathrm{MoS}}_{2}$ from fits to the slab dispersion. The in-plane excitons are in the strong regime of light-matter coupling with a coupling strength ($40\ensuremath{-}100\phantom{\rule{0.16em}{0ex}}\mathrm{meV}$) that exceeds their losses by at least a factor of two. The coupling becomes comparable to the exciton binding energy, which is known as very strong coupling. ${\mathrm{MoS}}_{2}$ and other transition metal dichalcogenides are excellent materials for future polariton devices.

Surface-enhanced vibrational spectroscopy strongly increases the cross section of Raman scattering and infrared absorption, overcoming the limited sensitivity and resolution of these two powerful analytic tools. While surface-enhanced setups with maximum enhancement have been studied widely in recent years, substrates with reproducible, uniform enhancement have received less attention although they are required in many applications. Here, we show that plasmonic supercrystals are an excellent platform for enhanced spectroscopy because they possess a high density of hotspots in the electric field. We describe the near field inside the supercrystal within the framework of plasmon polaritons that form due to strong light-matter interaction. From the polariton resonances we predict resonances in the far-field enhancement for Raman scattering and infrared absorption. We verify our predictions by measuring the vibrations of polystyrene molecules embedded in supercrystals of gold nanoparticles. The intensity of surface-enhanced Raman scattering is uniform within 10% across the crystal with a peak integrated enhancement of up to 300 and a peak hotspot enhancement of 105. The supercrystal polaritons induce pairs of incoming and outgoing resonances in the enhanced cross section as we demonstrate experimentally by measuring surface-enhanced Raman scattering with multiple laser wavelengths across the polariton resonance. The infrared absorption of polystyrene is likewise enhanced inside the supercrystals with a maximum enhancement of 400%. We show with a coupled oscillator model that the increase originates from the combined effects of hotspot formation and the excitation of standing polariton waves. Our work clearly relates the structural and optical properties of plasmonic supercrystals and shows that such crystals are excellent hosts and substrates for the uniform and predictable enhancement of vibrational spectra.

Thiophenol‐based molecules are commonly used reporter molecules for various experiments, especially within the scope of surface‐ and tip‐enhanced Raman spectroscopy. Due to their molecular structure, they bind covalently to noble metals and have a huge Raman scattering cross section. Herein, the widely uncharted optical properties of the frequently used probe molecule 4‐nitrothiophenol (p‐NTP or 4‐NTP) are analyzed by resonant Raman spectroscopy. Based on the three different types of samples, it is demonstrated that the molecule exhibits two intrinsic resonances at specific wavelengths. For a wide range of experiments, this is an important information since intrinsic resonances may give rise to an enhancement of the Raman intensity at these specific excitation wavelengths. The Raman cross section of p‐NTP in resonance at 1.9 eV (650 nm) to be 6 × 10−26 cm2 per molecule is also measured.

CNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior FINEP - Financiadora de Estudos e Projetos, Financiadora de Estudos e Projetos Tip-enhanced Raman spectroscopy (TERS) has reached nanometer spatial resolution for measurements performed at ambient conditions and subnanometer resolution at ultrahigh vacuum. Super-resolution (beyond the tip apex diameter) TERS has been obtained mostly in the gap mode configuration, where a conductive substrate localizes the electric fields. Here we present experimental and theoretical TERS to explore the field distribution responsible for spectral enhancement. We use gold tips of 40 ± 10 nm apex diameter to measure TERS on graphene, a spatially delocalized two-dimensional sample, sitting on different substrates: (i) glass, (ii) a thin layer of gold and (iii) a surface covered with 12 nm diameter gold spheres, for which 6 nm resolution is achieved at ambient conditions. The super-resolution is due to the field configuration resulting from the coupled tip-sample-substrate system, exhibiting a nontrivial spatial surface distribution. The field distribution and the symmetry selection rules are different for nongap versus gap mode configurations. This influences the overall enhancement which depends on the Raman mode symmetry and substrate structure.

Tip-enhanced Raman spectroscopy (TERS) and scattering-type scanning near-field optical microscopy (s-SNOM) enable optical imaging with a spatial resolution far below the diffraction limit of light. Although s-SNOM records the elastically scattered light (yielding information about the local refractive index and absorption), in TERS, the Raman scattered light is detected, which provides, for example, chemical information. Here, we introduce a combined TERS and s-SNOM setup for correlative studies of tip-enhanced elastically scattered and Raman scattered light. To that end, we equipped a conventional s-SNOM with a grating spectrometer. We validate our setup by characterizing a sample consisting of a self-assembled para-nitrothiophenol monolayer on an Au surface. Comparing s-SNOM and TERS signals, we demonstrate a qualitative correlation between the tip-enhanced elastic and tip-enhanced Raman scattered light. Thus, recording the tip-enhanced elastically scattered light enables a fast and reliable TERS alignm...

While various electronic components based on carbon nanotubes (CNTs) have already been demonstrated, the realization of miniature electromagnetic coils based on CNTs remains a challenge. Coils made of single-wall CNTs with accessible ends for contacting have been recently demonstrated but were found unsuitable to act as electromagnetic coils because of electrical shorting between their turns. Coils made of a few-wall CNT could in principle allow an insulated flow of current and thus be potential candidates for realizing CNT-based electromagnetic coils. However, no such CNT structure has been produced so far. Here, we demonstrate the formation of few-wall CNT coils and characterize their structural, optical, vibrational, and electrical properties using experimental and computational tools. The coils are made of CNTs with 2, 3, or 4 walls. They have accessible ends for electrical contacts and low defect densities. The coil diameters are on the order of one micron, like those of single-wall CNT coils, despite the higher rigidity of few-wall CNTs. Coils with as many as 163 turns were found, with their turns organized in a rippled raft configuration. These coils are promising candidates for a variety of miniature devices based on electromagnetic coils, such as electromagnets, inductors, transformers, and motors. Being chirally and enantiomerically pure few-wall CNT bundles, they are also ideal for fundamental studies of interwall coupling and superconductivity in CNTs.

Carbon nanotubes are one-dimensional nanoscale systems with strongly pronounced chirality-dependent optical properties with multiple excitonic transitions. We investigate the high-energy $G$ mode of semiconducting single-walled nanotubes of different chiralities at first excitonic transition by applying resonant Raman spectroscopy. The $G$ mode intensity dependence on excitation energy yielded asymmetric resonance Raman profiles similar to ones we reported for the second excitonic transition. We find the scattering efficiency to be strongest at the incoming Raman resonance. Still, the degree of asymmetry is different for the first and second transitions and the first transition profiles provide a narrower line shape due to longer exciton lifetimes. The overall scattering efficiency is up to a factor of 25 times more intense at first excitonic transition, compared to the second transition. The fifth-order perturbation theory, with implemented phonon scattering pathways between excitonic states, excellently reproduced experimental data.

Surface-enhanced Raman scattering (SERS) and resonant Raman scattering are widely used techniques to enhance the Raman intensity of molecules and nanomaterials by several orders of magnitude. In SERS, typically, molecules are investigated and their intrinsic resonance is often ignored while discussing the plasmonic enhancement. Here, we study α-sexithiophenes encapsulated in carbon nanotubes placed in the center of a nanodimer. By dielectrophoretic deposition, we place the nanotubes precisely in the center of a plasmonic gold nanodimer and observe SERS enhancement from individual tube bundles. The encapsulated molecules are not subjected to chemical enhancement because of the protective character of the nanotube. Polarization-dependent Raman measurements confirm the alignment of the molecules within the carbon nanotubes (CNTs) and reveal the influence of the plasmonic near field on the molecule’s Raman intensity. We investigate the encapsulated molecules in small CNT bundles with and without plasmonic enhancement and determine the molecular and plasmonic resonance by tuning the excitation wavelength. We observe a strong red shift of the maximum Raman intensity under plasmonic enhancement toward the plasmon resonance., The Journal of Physical Chemistry C, 123 (16), ISSN:1932-7455, ISSN:1932-7447

Light interacting with metallic nanoparticles creates a strongly localized near-field around the particle that enhances inelastic light scattering by several orders of magnitude. Surface-enhanced Raman scattering describes the enhancement of the Raman intensity by plasmonic nanoparticles. We present an extensive Raman characterization of a plasmonic gold nanodimer covered with graphene. Its two-dimensional nature and energy-independent optical properties make graphene an excellent material for investigating local electromagnetic near-fields. We show the localization of the near-field of the plasmonic dimer by spatial Raman measurements. Energy- and polarization-dependent measurements reveal the local near-field resonance of the plasmonic system. To investigate the far-field resonance we perform dark-field spectroscopy and find that near-field and far-field resonance energies differ by 170 meV, much more than expected from the model of a damped oscillator (40 meV).

We demonstrate the excitation of dark plasmon modes with linearly polarized light at normal incidence in self-assembled layers of gold nanoparticles. Because of field retardation, the incident light field induces plasmonic dipoles that are parallel within each layer but antiparallel between the layers, resulting in a vanishing net dipole moment. Using microabsorbance spectroscopy we measured a pronounced absorbance peak and reflectance dip at 1.5 eV for bi- and trilayers of gold nanoparticles with a diameter of 46 nm and 2 nm interparticle gap size. The excitations were identified as dark interlayer plasmons by finite-difference time-domain simulations. The dark plasmon modes are predicted to evolve into standing waves when further increasing the layer number, which leads to 90% transmittance of the incident light through the nanoparticle film. Our approach is easy to implement and paves the way for large-area coatings with tunable plasmon resonance.

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool to investigate chemical composition, for obtaining molecular information and for recording images with a spatial resolution on the nanometer scale. However, it typically has been limited to a fixed excitation wavelength. We demonstrate excitation-dependent hyperspectral imaging by implementing a wavelength-tunable laser to our TERS setup. Varying the excitation wavelength during the TERS experiments is a key to perform spatially resolved resonant Raman scattering with nanometer resolution, which enables mapping of transition centers and to study, for example, the quantum properties of electrons and phonons. To present the application potential and to verify the setup, we recorded excitation-dependent hyperspectral nanoimages of a densely packed film of carbon nanotubes (CNTs) on an Au surface and use the spectral position and intensity of the radial breathing modes for a unique assignment of the CNTs. We succeeded in identifying and imaging at least nine different tube species. The nanoimages revealed the exact position and the distribution of certain CNTs inside the film. e-TERS will have manifold application in nanoimaging, for chemical analysis, and electronic studies on the nanometer scale, making it highly interesting in fields ranging from biomedicine and chemistry to material science.

The dependence of the anti-Stokes Raman intensity on the excitation laser energy in carbon nanotubes is studied by resonant Raman spectroscopy. The complete resonant anti-Stokes and Stokes Raman profiles of the high-energy longitudinal phonon (${G}^{+}$) are obtained for (8,3), (7,5), (6,4), and (6,5) single chirality enriched samples. A high asymmetry between the intensity of the incoming and outgoing resonance is observed in the resonant Raman profiles. In contrast to Stokes scattering, anti-Stokes scattering is more intense at the outgoing resonance then at the incoming resonance. The resonance profiles are explained by a Raman process that includes the phonon-mediated interactions with the dark excitonic state. The chirality dependence of the Raman profiles is due to the variation in the exciton-phonon matrix elements, in agreement with tight-binding calculations. Based on the asymmetric Raman profiles we present the resonance factors for the Stokes/anti-Stokes ratios in carbon nanotubes.

The properties of graphene depend sensitively on strain and doping affecting its behavior in devices and allowing an advanced tailoring of this material. A knowledge of the strain configuration, i.e. the relative magnitude of the components of the strain tensor, is particularly crucial, because it governs effects like band-gap opening, pseudo-magnetic fields, and induced superconductivity. It also enters critically in the analysis of the doping level. We propose a method for evaluating unknown strain configurations and simultaneous doping in graphene using Raman spectroscopy. In our analysis we first extract the bare peak shift of the G and 2D modes by eliminating their splitting due to shear strain. The shifts from hydrostatic strain and doping are separated by a correlation analysis of the 2D and G frequencies, where we find ∆ω2D/∆ωG = 2.21 ± 0.05 for pure hydrostatic strain. We obtain the local hydrostatic strain, shear strain and doping without any assumption on the strain configuration prior to the analysis, as we demonstrate for two model cases: Graphene under uniaxial stress and graphene suspended on nanostructures that induce strain. Raman scattering with circular corotating polarization is ideal for analyzing frequency shifts, especially for weak strain when the peak splitting by shear strain cannot be resolved., 2D Materials, 5 (1), ISSN:2053-1583

We isolated the plasmonic contribution to surface-enhanced Raman scattering (SERS) and found it to be much stronger than expected. Organic dyes encapsulated in single-walled carbon nanotubes are ideal probes for quantifying plasmonic enhancement in a Raman experiment. The molecules are chemically protected through the nanotube wall and spatially isolated from the metal, which prevents enhancement by chemical means and through surface roughness. The tubes carry molecules into SERS hotspots, thereby defining molecular position and making it accessible for structural characterization with atomic-force and electron microscopy. We measured a SERS enhancement factor of 106 on α-sexithiophene (6T) molecules in the gap of a plasmonic nanodimer. This is two orders of magnitude stronger than predicted by the electromagnetic enhancement theory (104). We discuss various phenomena that may explain the discrepancy (including hybridization, static and dynamic charge transfer, surface roughness, uncertainties in molecular position and orientation), but found all of them lacking in enhancement for our probe system. We suggest that plasmonic enhancement in SERS is, in fact, much stronger than currently anticipated. We discuss novel approaches for treating SERS quantum mechanically that appear promising for predicting correct enhancement factors. Our findings have important consequences on the understanding of SERS as well as for designing and optimizing plasmonic substrates.

A novel topological insulator with orthorhombic crystal structure is demonstrated. It is characterized by quasi one-dimensional, conducting atomic chains instead of the layered, two-dimensional sheets known from the established Bi2(Se,Te)3 system. The Sb-doped Bi2Se3 nanowires are grown in a TiO2-catalyzed process by chemical vapor deposition. The binary Bi2Se3 is transformed from rhombohedral to orthorhombic by substituting Sb on ∼38% of the Bi sites. Pure Sb2Se3 is a topologically trivial band insulator with an orthorhombic crystal structure at ambient conditions, and it is known to transform into a topological insulator at high pressure. Angle-resolved photoemission spectroscopy shows a topological surface state, while Sb doping also tunes the Fermi level to reside in the bandgap. (© 2015 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

A controlled alignment of graphite nanoplatelets in a composite matrix will allow developing materials with tailored thermal properties. Achieving a high degree of alignment in a reproducible way, however, remains challenging. Here we demonstrate the alignment of graphite nanoplatelets in copper composites produced via high-energy ball milling and spark plasma sintering. The orientation of the nanoplatelets in the copper matrix is verified by polarized Raman scattering and electron microscopy showing an increasing order with increasing platelet size. The thermal conductivity k along the alignment direction is up to five times higher than perpendicular to it. The composite with the highest degree of alignment has a thermal diffusivity (100 mm(2) s(-1)) comparable to copper (105 mm(2) s(-1)) but is 20% lighter. By modeling the thermal properties of the composites within the effective medium approximation we show that (i) the Kapitza resistance is not a limiting factor for improving the thermal conductivity of a copper-graphite system and (ii) copper-graphite-nanoplatelet composites may be expected to achieve a higher thermal conductivity than copper upon further refinement.

Solar cells with Cu 2 ZnSnS 4 absorber thin films have a potential for high energy conversion efficiencies with earth-abundant and non-toxic elements. In this work the formation of CZTSSe from Cu x SnS y nanoparticles (NPs) deposited on ZnO nanorod (NR) arrays as precursors for zinc is investigated. The NPs are prepared using a chemical route and are dispersed in toluene. The ZnO NRs are grown on fluorine doped SnO 2 coated glass substrates by electro deposition method. A series of samples are annealed at different temperatures between 300 °C and 550 °C in selenium containing argon atmosphere. To investigate the products of the reaction between the precursors the series is analyzed by means of X-ray diffraction (XRD) and Raman spectroscopy. The morphology is recorded by scanning electron microscopy (SEM) images of broken cross sections. The XRD measurements and the SEM images show the disappearing of ZnO NRs with increasing annealing temperature. Simultaneously the XRD and Raman measurements show the formation of CZTSSe. The formation of secondary phases and the optimum conditions for the preparation of CZTSSe is discussed.

We investigated multi-phonon processes in two types of CdSe nanocrystals, spherical quantum dots and nanorods by temperature-dependent Raman spectroscopy. We find the anharmonic constants relating to the two- and three-phonon decay channels to systematically change with changing nanocrystal size. The contributions from two-phonon processes decrease with decreasing diameter, while the contributions from higher-order processes increase. The anharmonicities in the vibrational potential increase due to the phonon confinement, and we did not find a shape dependence.

We report plasmon-enhanced Raman scattering in graphene coupled to a single plasmonic hotspot measured as a function of laser energy. The enhancement profiles of the G peak show strong enhancement (up to $10^5$) and narrow resonances (30 meV) that are induced by the localized surface plasmon of a gold nanodimer. We observe the evolution of defect-mode scattering in a defect-free graphene lattice in resonance with the plasmon. We propose a quantum theory of plasmon-enhanced Raman scattering, where the plasmon forms an integral part of the excitation process. Quantum interferences between scattering channels explain the experimentally observed resonance profiles, in particular, the marked difference in enhancement factors for incoming and outgoing resonance and the appearance of the defect-type modes., Keywords: plasmon-enhanced Raman scattering, SERS, graphene, quantum interferences, microscopic theory of Raman scattering. Content: 22 pages including 5 figures + 11 pages supporting information

We used spatially resolved photoluminescence (PL) and resonant Raman spectroscopy to study the electronic structure of single GaAs nanowires (NWs) consisting of zinc-blende (ZB) and wurtzite (WZ) segments. For narrow ZB segments and stacking faults the energy range of the observed PL peak positions is found to deviate from that of the maxima in resonance Raman profiles. These different energy ranges reflect the fact that the PL recombination is dominated by spatially indirect transitions whereas the resonance enhancement of Raman scattering is caused by direct transitions. Our results provide evidence for the type II band alignment between ZB and WZ GaAs and a coherent picture of all near-band-gap transition energies in GaAs NWs.

High-density growth of single-crystalline Bi2Se2Te nanowires was achieved via the vapour-liquid-solid process. The stoichiometry of samples grown at various substrate temperatures is precisely determined based on energy-dispersive X-ray spectroscopy, X-ray diffraction, and Raman spectroscopy on individual nanowires. We discuss the growth mechanism and present insights into the catalyst-precursor interaction.

We investigate the Raman intensity of E2H phonons in wurtzite GaAs nanowire ensembles as well as single nanowires as a function of excitation wavelength. For nanowires with radii in the range of 25 nm, an almost complete quenching of the E2H phonon line is observed for excitation wavelengths larger than 600 nm. The observed behavior is quantitatively explained by the dielectric polarization contrast for the coupling of light into the GaAs nanowires. Our results define the limits of Raman spectroscopy for the detection of the wurtzite phase in semiconductor nanowires.

We report resonant Raman scattering (RRS) by the TO, LO, and 2 LO modes of single wurtzite and zinc-blende GaAs nanowires. The optical band gap of wurtzite GaAs is $1.460\phantom{\rule{0.16em}{0ex}}\mathrm{eV}\ifmmode\pm\else\textpm\fi{}3\phantom{\rule{0.16em}{0ex}}\mathrm{meV}$ at room temperature, and $35\ifmmode\pm\else\textpm\fi{}3\phantom{\rule{0.16em}{0ex}}\mathrm{meV}$ larger than the GaAs zinc-blende band gap. Raman measurements using incoming light polarized parallel and perpendicular to the wire $c$ axis allowed us to investigate the splitting of heavy ${\ensuremath{\Gamma}}_{9}$ and light-hole ${\ensuremath{\Gamma}}_{7}$ band at the $\ensuremath{\Gamma}$ point of $65\ifmmode\pm\else\textpm\fi{}6\phantom{\rule{0.16em}{0ex}}\mathrm{meV}$.

We present a method to control the length and diameter of Bi 2Se3 nanowires through laser-cutting. Nanowires of the topologically insulating and thermoelectric material Bi2Se 3 were grown using the vapor-liquid-solid method, and cut using a 532-nm-laser operating at a minimum power of 1 μW. The cutting process can be controlled through laser intensity and exposure time, and is based upon evaporation of Se from the nanowires. This method has many applications from pure research to device engineering. © 2014 EDP Sciences.