This article reviews the new developments in Tip-enhanced Raman scattering (TERS). The fundamental mechanisms underlying the Raman enhancement are discussed, including the role of the plasmonic character of the metallic tips, the nature of the optical tip-sample coupling and the resulting local-field confinement responsible for ultrahigh spatial resolution down to just several nanometers. Criteria for the distinction of near-field signature from far-field imaging artifacts are addressed and TERS results of molecules and nanostructures are presented. With enhancement factors as high as 10$^9$, single molecule spectroscopy is demonstrated. Spatially resolved vibrational mapping of crystalline nanostructures and determination of crystallographic orientation and domains is shown making use of the unique symmetry properties of the tip in conjunction with the intrinsic Raman selection rules.
In the present contribution, specifically designed single-stranded DNA (ssDNA) sequences composed of adenine and cytosine were used as nanometric rulers to target the maximum achievable spatial resolution of tip-enhanced Raman spectroscopy (TERS) under ambient conditions. By stepping along a strand with a TERS tip, the obtained spectra allowed for a clear spectral discrimination including conformational information of the nucleobases, and even sharp adenine-cytosine transitions were detected repeatedly with a spatial resolution below 1 nm.
We investigate theoretically the optical properties associated to plasmon resonances of metal nanowires with cross section given by low-order Chebyshev nanoparticles (like rounded-tip nanostars or nanoflowers). The impact of the nanoflower shape is analyzed for varying symmetry and deformation parameter through the spectral dependence of resonances, and their corresponding near field distributions. Large field intensity enhancements are obtained at the gaps between petals, apart from the tips themselves, which make these nanostars/nanoflowers specially suitable to host molecules for SERS sensi…
A quantitative single-molecule tip-enhanced Raman spectroscopy (TERS) study at room temperature remained a challenge due to the rapid structural dynamics of molecules exposed to air. Here, we demonstrate the single-molecule level hyperspectral TERS imaging of brilliant cresyl blue (BCB) at room temperature for the first time, along with quantitative spectral analyses. Freeze-frame approach using a thin Al2O3 capping layer, which suppresses spectral diffusions and inhibits chemical reactions and contaminations in air, enabled reliable and robust chemical imaging. For the molecules resolved spat…
We demonstrate the acquisition of stimulated Raman scattering spectra with the use of a single femtosecond pulse. High resolution vibrational spectra are obtained by shifting the phase of a narrow band of frequencies in the broadband input pulse spectrum, using spectral shaping. The vibrational spectrum is resolved by examining the amplitude features formed in the spectrum after interaction with the sample. Using this technique, low frequency Raman lines (<100cm^-1) are resolved in a straightforward manner.
We extend the technique of multiplex coherent Raman spectroscopy with two femtosecond mode-locked lasers to oscillators of a pulse repetition frequency of 1 GHz. We demonstrate spectra of liquids, which span 1100 cm$^{-1}$ of Raman shifts. At a resolution of 6 cm$^{-1}$, their measurement time may be as short as 5 microseconds for a refresh rate of 2 kHz. The waiting period between acquisitions is improved ten-fold compared to previous experiments with two lasers of 100-MHz repetition frequencies.
We demonstrate a compact and versatile laser system for stimulated Raman spectroscopy (SRS). The system is based on a tunable continuous wave (CW) probe laser combined with a home-built semi-monolithic nanosecond pulsed pump Nd:YVO4 laser at 1064 nm. The CW operation of the probe laser offers narrow linewidth, low noise and the advantage that temporal synchronization with the pump is not required. The laser system enables polarization-sensitive stimulated Raman spectroscopy (PS-SRS) with fast high resolution measurement of the depolarization ratio by simultaneous detection of Raman scattered l…
We demonstrate a novel technique of coherent Raman spectroscopy with a femtosecond laser. We apply to a molecular sample a sequence of pairs of ultrashort excitation and probe pulses, with a linearly increasing time delay between the two pulses from one pair to the next. We measure, as a function of the delay, the intensity modulation in the signal resulting from the differential detection of the Stokes and anti-Stokes radiations generated at the sample. The Fourier transform of such time-domain signal reveals the spectrum of the excited vibrational Raman transitions. The experimental proof-of…
We demonstrate a method to double the collection efficiency in Laser Tweezers Raman Spectroscopy (LTRS) by collecting both the forward and back-scattered light in a single-shot multitrack measurement. Our method can collect signals at different sample volumes, granting both the pinpoint spatial selectivity of confocal Raman and the bulk sensitivity of non-confocal Raman simultaneously. Further, we display that our approach allows for reduced detector integration time and laser power. Thus, our method will enable the monitoring of biological samples sensitive to high intensities for longer time…
Expressions for the two-dimensional Stimulated x-ray Raman Spectroscopy (2D-SXRS) signal obtained using attosecond x-ray pulses are derived. The 1D- and 2D-SXRS signals are calculated for trans-N-methyl acetamide (NMA) with broad bandwidth (FWHM ~14.2eV, 181 as) pulses tuned to the oxygen and nitrogen K-edges. Crosspeaks in 2D signals reveal electronic Franck-Condon overlaps between valence orbitals and relaxed orbitals in the presence of the core hole.
We propose a novel femtosecond stimulated Raman spectroscopy (FSRS) technique that combines entangled photons with interference detection to select matter pathways and enhance the resolution. Following photo excitation by an actinic pump, the measurement uses a pair of broadband entangled photons, one (signal) interacts with the molecule together with a third narrowband pulse induces the Raman process. The other (idler) photon provides a reference for the coincidence measurement. This interferometric photon-coincidence counting detection allows to separately measure Raman gain and loss signals…
Experimental evidence suggests an extremely high, possibly even sub-molecular, spatial resolution of tip-enhanced Raman spectroscopy. While the underlying mechanism is currently still under discussion, two main contributions are considered: The involved plasmonic particles are able to highly confine light to small spatial regions in the near-field, i.e. the electromagnetic effect, and the chemical effect due to altered molecular properties of the sample in close proximity to the plasmonic tip. Significant theoretical effort is put into the modelling of the electromagnetic contribution by vario…
In general, most of the substances in nature exist in mixtures, and the noninvasive identification of mixture composition with high speed and accuracy remains a difficult task. However, the development of Raman spectroscopy, machine learning, and deep learning techniques have paved the way for achieving efficient analytical tools capable of identifying mixture components, making an apparent breakthrough in the identification of mixtures beyond the traditional chemical analysis methods. This article summarizes the work of Raman spectroscopy in identifying the composition of substances as well a…
Raman spectroscopy of crystalline/molecular systems is well backed with quantum chemical calculations and group theory, making it a unique characterization tool. For the "intermediate" case of nanoscale systems, however, the use of Raman spectroscopy is limited by the lack of such theoretical bases. Here, we suggest to couple a scaled quantum-mechanical (SQM) calculation with the phonon confinement model (PCM) to construct a universal and physically consistent basis for nanoscale Raman spectroscopy. Unlike the commonly used one-dimensional dispersion PCM, we take into account the confinement a…
Single-beam spectrally controlled (SBSC) two-dimensional (2D) Raman spectroscopy is a unique 2D vibrational measurement technique utilizing trains of short pulses that are generated from a single broadband pulse by pulse shaping. This approach overcomes the difficulty of 2D Raman spectroscopy in dealing with small-signal extraction and avoids complicated low-order cascading effects, thus providing a new possibility for measuring the intramolecular and intermolecular modes of molecular liquids using fifth-order 2D Raman spectroscopy. Recently, for quantitatively investigating the mode-mode coup…
For nanoscale systems such as nanoparticles and 3D-bonded networks, the range of spatial coherence is well reflected in the Raman spectral pattern. For confined, or localized, phonons, the range of q-points contributing to the spectrum depends on the phonon confinement length, which makes possible to derive the size information from the spectra. In this work, Raman spectrum of vitreous silica is described as localized phonons of SiO2 network. The convergence of the spectral pattern with the confinement size is studied. It is shown that the phonon propagation scale in vitreous silica is within …
Disordered carbon often exhibit a complex Raman spectrum, with four to six components. Here, a large variety of disordered carbons, forming a collection of samples with a great variety of structures, are analysed using multi-wavelength Raman microscopy (325.0, 514.5, 785.0 nm). They allow us to extend Raman behaviour known for nano-crystalline graphite to amorphous carbons, (dependence with the excitation wavelength) and other known for amorphous carbons to nano-crystalline graphite, (differentiation of the smallest cluster size probed using different excitation wavelengths). Experimental spec…
