Raman Cross Section Research Articles

Measurement of shock velocity and temperature in laser-shocked carbon disulphide using time-resolved Raman spectroscopy

High-resolution time-resolved Raman spectroscopy of laser-shocked liquid carbon disulfide (CS2) is reported. The symmetric stretching mode (ν1) and first overtone of the bending mode (2 ν2) of CS2 at 656 cm−1 and 802 cm−1 wavenumbers respectively are analyzed to monitor the possible phase transitions occurring in the sample during shock wave propagation in the pressure range 0.4 – 4.4 GPa by varying the laser intensity on target from 0.2 GW/cm2 (40 mJ) to 6.4 GW / cm2 (1300 mJ). A liquid to solid phase transition is observed at 1.5 GPa, as compared to 0.8 GPa in static compression. The difference in these measurements is thought to be due to the high temperatures involved in the dynamic compression experiments described. The shock wave velocities in CS2 at 1.5 GPa and 2.6 GPa are calculated by measuring the intensity ratio of Raman modes emerging from the shocked region to that of the whole sample. 1D radiation-hydrodynamic simulations are performed to corroborate the experimental data. Enhancement of the Raman cross-section of carbon disulfide is observed from 2.5 GPa, which is much lower than the previously reported threshold of 8 GPa as reported by Yoo et al., [24]. This discrepancy in results is thought to be due to the significant contribution of temperature along with the pressure in laser-driven nanosecond single shock experiment.

Raman efficiency in the middle ultraviolet band for G‐series nerve agents and sulfur mustard

AbstractRaman spectroscopy has proven useful for chemical agent detection, but the wavelength‐dependent scattering cross section and absorption, as well as induced fluorescence, usually affects the sensitivity. Ultraviolet (UV) wavelength excitation is investigated as a method to increase the efficiency and possibly enhance the applicability for detection of contamination on surfaces from a distance, potentially including an imaging capability. With this aim, we have measured UV Raman spectra and their strength as a function of laser wavelength in a range from 210 to 330 nm using a tunable pulsed laser and a response calibrated spectroscopic system. Results from small droplets of the low volatile chemical warfare agents, GA (tabun), GF (cyclosarin), sulfur mustard (HD), and the agent simulant tributyl phosphate (TBP) applied to silicon wafer surfaces are reported. Particular emphasis is put on the radiative ratio of observed Raman scattering to laser excitation, quantified as the Raman target efficiency. Measured absorption cross sections were used to estimate the effective optical depth and molecular Raman cross sections as a function of wavelength. In addition, a secondary optical probe and spectrometer were used to monitor any induced fluorescence.

Nonenzymatic Hydrogen Peroxide Detection Using Surface-Enhanced Raman Scattering of Gold-Silver Core-Shell-Assembled Silica Nanostructures.

Hydrogen peroxide (H2O2) plays important roles in cellular signaling and in industry. Thus, the accurate detection of H2O2 is critical for its application. Unfortunately, the direct detection of H2O2 by surface-enhanced Raman spectroscopy (SERS) is not possible because of its low Raman cross section. Therefore, the detection of H2O2 via the presence of an intermediary such as 3,3,5,5-tetramethylbenzidine (TMB) has recently been developed. In this study, the peroxidase-mimicking activity of gold–silver core–shell-assembled silica nanostructures (SiO2@Au@Ag alloy NPs) in the presence of TMB was investigated using SERS for detecting H2O2. In the presence of H2O2, the SiO2@Au@Ag alloy catalyzed the conversion of TMB to oxidized TMB, which was absorbed onto the surface of the SiO2@Au@Ag alloy. The SERS characteristics of the alloy in the TMB–H2O2 mixture were investigated. The evaluation of the SERS band to determine the H2O2 level utilized the SERS intensity of oxidized TMB bands. Moreover, the optimal conditions for H2O2 detection using SiO2@Au@Ag alloy included incubating 20 µg/mL SiO2@Au@Ag alloy NPs with 0.8 mM TMB for 15 min and measuring the Raman signal at 400 µg/mL SiO2@Au@Ag alloy NPs.

Synergistic SERS Enhancement in GaN-Ag Hybrid System toward Label-Free and Multiplexed Detection of Antibiotics in Aqueous Solutions.

Noble metal‐based surface‐enhanced Raman spectroscopy (SERS) has enabled the simple and efficient detection of trace‐amount molecules via significant electromagnetic enhancements at hot spots. However, the small Raman cross‐section of various analytes forces the use of a Raman reporter for specific surface functionalization, which is time‐consuming and limited to low‐molecular‐weight analytes. To tackle these issues, a hybrid SERS substrate utilizing Ag as plasmonic structures and GaN as charge transfer enhancement centers is presented. By the conformal printing of Ag nanowires onto GaN nanopillars, a highly sensitive SERS substrate with excellent uniformity can be fabricated. As a result, remarkable SERS performance with a substrate enhancement factor of 1.4 × 1011 at 10 fM for rhodamine 6G molecules with minimal spot variations can be realized. Furthermore, quantification and multiplexing capabilities without surface treatments are demonstrated by detecting harmful antibiotics in aqueous solutions. This work paves the way for the development of a highly sensitive SERS substrate by constructing complex metal‐semiconductor architectures.

Anti-Stokes Raman Scattering of Single Carbyne Chains.

We investigate the anti-Stokes Raman scattering of single carbyne chains confined inside double-walled carbon nanotubes. Individual chains are identified using tip-enhanced Raman scattering (TERS) and heated by resonant excitation with varying laser powers. We study the temperature dependence of carbyne's Raman spectrum and quantify the laser-induced heating based on the anti-Stokes/Stokes ratio. Due to its molecular size and its large Raman cross section, carbyne holds great promise for local temperature monitoring, with potential applications ranging from nanoelectronics to biology.

Graphene edge method for three‐dimensional probing of Raman microscopes focal volumes

AbstractIn this work, a layer of graphene was used as a standard material for the measurement of the dimensions of Raman microscopes focal volumes of different confocal Raman spectrometers equipped with different objectives and excitation laser wavelengths. This method consists in probing the volume near the focal point of the system by using a flat graphene monolayer sheet with a straight edge. Graphene was selected because of its high Raman cross section and mechanically and chemically stability, allowing fast measurements and easy manipulation. In this paper, a method to employ graphene to accurately and precisely measure the three dimensions of the focal volume of a Raman microscope is presented; scanning along the axial and lateral directions, it is possible to reconstruct the three dimensions of the focal volume. Furthermore, these operations can be combined in a single procedure which allows the measurement of projections of the volume on planes parallel to the optical axis. Knowledge of these parameters enable absolute quantification of Raman‐active molecules and support high‐resolution Raman imaging.

Stimulated Raman scattering simulation for imaging optimization

Two simulation programs of a stimulated Raman scattering microscopy (SRS) imaging system with lock-in amplifier (LIA) detection were developed. SRS is an imaging technique based on the vibrational Raman cross-section as the contrast mechanism and enables fast, label-free imaging. Most SRS implementations are based on LIA detection of a modulated signal. However, building and operating such SRS set-ups still poses a challenge when selecting the LIA parameter settings for optimized acquisition speed or image quality. Moreover, the type of sample, e.g. a sparse sample vs. a densely packed sample, the required resolution as well as the Raman cross-section and the laser powers affect the parameter choice.A simulation program was used to find these optimal parameters. The focal spot diameters of the individual lasers (pump and Stokes) were used to estimate the effective SRS signal focal spot and the (optical) spatial resolution. By calibrating the signal and noise propagation through an SRS system for a known molecule, we estimated the signal and noise input to the LIA. We used a low pass filter model to simulate the LIA behavior in order to find the optimal parameters (i.e. filter order and time constant).Optimization was done for either image quality (expressed as contrast to noise ratio) or acquisition time. The targeted object size was first determined as a measure for the required resolution. The simulation output consisted of the LIA parameters, pixel dwell time and contrast to noise ratio.In a second simulation we evaluated SRS imaging based on the same principles as the optimal setting simulation, i.e. the signals were propagated through an imaging system and LIA detection. The simulated images were compared to experimental SRS images of polystyrene beads.Finally, the same software was used to simulate multiplexed SRS imaging. In this study we modeled a six-channel frequency-encoded multiplexed SRS system demodulated with six LIA channels. We evaluated the inter-channel crosstalk as a function of chosen LIA parameters, which in multiplex SRS imaging also needs to be considered.These programs to optimize the contrast to noise ratio, acquisition speed, resolution and crosstalk will be useful for operating stimulated Raman scattering imaging setup, as well as for designing novel setups.

Front Cover

AbstractHepatic stellate cells (HSCs) are the key cell type in the development of liver fibrosis. Despite their importance, the identification of HSCs in bulky tissue has remained challenging. Coherent anti‐ Stokes Raman scattering microscopy (CARS) can be used to identify HSCs in the liver of a living mouse. HSCs are the main target of novel nanomedical strategies in the development of a treatment for liver fibrosis. Their role in the vitamin A metabolism and the exceptionally high Raman cross section of retinyl compounds make CARS the ideal tool for this otherwise challenging task.Further details can be found in the article by Marko Rodewald, Hyeonsoo Bae, Sophie Huschke, Tobias Meyer‐Zedler, Michael Schmitt, Adrian Tibor Press, Stephanie Schubert, Michael Bauer, and Jürgen Popp (e202100040). image

(Invited) Combining Absorption, Wavelength-Dependent Raman and Fluorescence-Excitation Spectroscopy with High-Resolution Transmission Electron Microscopy for Determining the Chiral Purity of Sorted SWCNT Samples

Single-wall carbon nanotubes (SWCNTs) possess unique electronic and optical properties that depend strongly on their exact chiral structure. Recent progress in the structure sorting of specific SWCNT chiralities, with increasing chiral purity[1], demands an effective characterization methodology to be developed to accurately determine the chiral composition of any SWCNT chirality. Very often, optical spectroscopy is used to assess the chiral composition of a sample, but absorption cross-sections, PL quantum efficiencies and Raman cross-sections are all depending on the exact chiral structure,[2] and can be strongly influenced by other factors such as the specific internal and external environment of the SWCNTs.[3] In this work, we systematically compare the chirality distribution obtained from 3 different optical spectroscopic techniques, i.e. absorption, wavelength-dependent Raman and fluorescence-excitation spectroscopy with the chirality distribution obtained from high-resolution transmission electron microscopy for both chirality-sorted and unsorted SWCNT samples. This combined approach demonstrates the importance of using a multi-technique characterization strategy for a reliable determination of SWCNT chirality distribution.[4][1] J.A. Fagan, Nanoscale Adv. 1, 3307 (2019) and references therein[2] V.N. Popov, Nano Lett. 4, 1795 (2004)[3] S. Cambré et al, Angew. Chem. – Int Ed. 50, 2764 (2011); ACS nano 6, 2649 (2012)[4] A. Castan et al, Carbon 171, 968 (2021)

Microsecond fingerprint stimulated Raman spectroscopic imaging by ultrafast tuning and spatial-spectral learning

Label-free vibrational imaging by stimulated Raman scattering (SRS) provides unprecedented insight into real-time chemical distributions. Specifically, SRS in the fingerprint region (400–1800 cm−1) can resolve multiple chemicals in a complex bio-environment. However, due to the intrinsic weak Raman cross-sections and the lack of ultrafast spectral acquisition schemes with high spectral fidelity, SRS in the fingerprint region is not viable for studying living cells or large-scale tissue samples. Here, we report a fingerprint spectroscopic SRS platform that acquires a distortion-free SRS spectrum at 10 cm−1 spectral resolution within 20 µs using a polygon scanner. Meanwhile, we significantly improve the signal-to-noise ratio by employing a spatial-spectral residual learning network, reaching a level comparable to that with 100 times integration. Collectively, our system enables high-speed vibrational spectroscopic imaging of multiple biomolecules in samples ranging from a single live microbe to a tissue slice.

In vivo coherent anti-Stokes Raman scattering microscopy reveals vitamin A distribution in the liver.

Here we present a microscope setup for coherent anti-Stokes Raman scattering (CARS) imaging, devised to specifically address the challenges of in vivo experiments. We exemplify its capabilities by demonstrating how CARS microscopy can be used to identify vitamin A (VA) accumulations in the liver of a living mouse, marking the positions of hepatic stellate cells (HSCs). HSCs are the main source of extracellular matrix protein after hepatic injury and are therefore the main target of novel nanomedical strategies in the development of a treatment for liver fibrosis. Their role in the VA metabolism makes them an ideal target for a CARS-based approach as they store most of the body's VA, a class of compounds sharing a retinyl group as a structural motive, a moiety that is well known for its exceptionally high Raman cross section of the C═C stretching vibration of the conjugated backbone.

Preface to the special issue dedicated to Professor Richard P. Van Duyne (1945–2019)

Preface to the special issue dedicated to Professor Richard P. Van Duyne (1945–2019)

Ultra-precision grinding of Gd3Ga5O12 crystals with graphene oxide coolant: Material deformation mechanism and performance evaluation

• GO lubrication assisted grinding was innovatively applied in crack-free machining of GGG crystals. • Plastic deformation of GGG induced by GO assisted grinding was dominated by polycrystallization nanocrystals and amorphous transformation. • Interlayer slip and filling actions of GO significantly affect the deformation and removal processes of GGG crystals. • Compared with conventional grinding, surface roughness and friction coefficient of GO assisted grinding were effectively reduced. Laser crystals of rare-earth oxide are primary host materials for making solid-state lasers of large power. However, brittle fractures and cracks are easily formed on the crystal’s surface and subsurface during abrasive machining process owing to their high hardness and brittleness, which will seriously reduce output power of the lasers. In this work, a grinding coolant was synthesized through dispersing GO nanosheets in water, and the grinding experiment of GGG laser crystals assisted by GO coolant lubrication was systematically performed. The plastic deformation mechanism of GGG crystals induced by GO assisted grinding was revealed at close-to-atomic scale by Raman spectrum and cross-section TEM detection technologies. The results indicated that the plastic deformation of GGG crystals during GO assisted grinding was affected by the interlayer slip and filling actions of GO, and was dominated by polycrystallization nanocrystals and amorphous transformation caused by the crystal plane slipping. The use of the GO coolant enabled to lower friction at the abrasive-substrate interface significantly owing to their self-lubricating effect, thus resulting in improved ground surface quality, in comparison with conventional grinding. This work will provide a new theoretical basis and technical support for high-efficiency and low-damage ultra-precision grinding of laser crystals.

Electrodeposition of NiSn-rGO Composite Coatings from Deep Eutectic Solvents and Their Physicochemical Characterization

The present work describes, for the first time, the electrodeposition of NiSn alloy/reduced graphene oxide composite coatings (NiSn-rGO) obtained under pulse current electrodeposition conditions from deep eutectic solvents (choline chloride: ethylene glycol eutectic mixtures) containing well-dispersed GO nanosheets. The successful incorporation of the carbon-based material into the metallic matrix has been confirmed by Raman spectroscopy and cross-section scanning electron microscopy (SEM). A decrease in the crystallite size of the coating was evidenced when graphene oxide was added to the electrolyte. Additionally, the topography and the electrical properties of the materials were investigated by atomic force microscopy (AFM). The corrosion behavior in 0.5 M NaCl solution was analyzed through potentiodynamic polarization and electrochemical impedance spectroscopy methods for different immersion periods, up to 336 h, showing a slightly better corrosion performance as compared to pure NiSn alloy.

Resonant Raman Scattering of 4‐Nitrothiophenol

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.

228‐nm quadrupled quasi‐three‐level Nd:GdVO4 laser for ultraviolet resonance Raman spectroscopy of explosives and biological molecules

AbstractWe describe a new compact diode‐pumped solid‐state frequency quadrupled quasi‐three‐level neodymium‐doped gadolinium vanadate (Nd:GdVO4) laser that generates ~50 mW of 228‐nm quasi‐continuous wave light as ns pulses at a tunable kilohertz repetition rate. We developed two generations of this laser. The first generation has a high duty cycle and a tunable repetition rate. The second generation is optimized for maximum output power. We utilize these new lasers to measure ultraviolet resonance Raman (UVRR) spectra of many important chromophores that absorb in deep ultraviolet (UV). We demonstrate the utility of this excitation by measuring the 228‐nm absolute differential Raman cross sections of explosives, peptides, aromatic amino acids, and DNA/RNA nucleotides. Deep UV excitation at 228 nm occurs within the π → π* electronic transitions of these molecules. The 228‐nm resonance excitation enhances the Raman intensities of vibrations of NOx groups, peptide bonds, aromatic amino acid side chains, and DNA/RNA nucleotides. The measured 228‐nm UVRR cross sections of these molecules are 103–104 fold greater than those excited in the visible spectral region. These new lasers should be of great interest for UVRR spectroscopy and for other applications that benefit from compact, high average power deep UV laser light sources with low peak powers.

Theoretical treatment of single‐molecule scanning Raman picoscopy in strongly inhomogeneous near fields

AbstractTip‐enhanced Raman spectroscopy (TERS) of a single molecule is commonly described by considering the change in the polarizability of the molecule with respect to a normal coordinate induced by homogeneous illumination. However, the local fields induced by nanoscale and atomic‐scale features at the surface of metallic clusters and nanogaps show strong inhomogeneities in their spatial distribution, which induces breaking of Raman selection rules. In this context, the spatial extension of the molecular electronic states subjected to strongly varying local fields challenges the validity of the point–dipole approximation as an adequate description of TERS in such configurations. Here, we introduce a general treatment to simulate single‐molecule TERS spectra and their energy‐filtered vibrational fingerprints maps, in which the polarization properties of the single molecule and that of the optical enhancing nanoresonator can be calculated separately and then conveniently combined to obtain the total Raman cross section of the molecule under the strongly inhomogeneous field. We apply the general method to study tip‐enhanced scanning Raman picoscopy of a 4,4′‐bipyridine and biphenyl molecules in the proximity of a silver icosahedral cluster with a few atoms at the tip apex mimicking an enhancing picocavity. The polarization of the molecules is calculated within density functional theory (DFT), and the optical response of the tip is calculated within a classical atomistic discrete–dipole approximation. The Raman spectra are found to be extremely sensitive to the spatial distribution of the local fields and to the orientation of the molecule. Our calculations show that the spatial mapping of molecular vibrational fingerprints, as probed by a tip with atomic protrusions, is capable to reveal intramolecular features of a single molecule in real space and thus establish a robust basis for scanning Raman picoscopy.

Assessing the reliability of the Raman peak counting method for the characterization of SWCNT diameter distributions: a cross characterization with TEM

Resonant Raman spectroscopy is a widely used technique for single-walled carbon nanotube (SWCNT) characterization, in particular in the radial breathing mode (RBM) range which provides direct information on the structure of the nanotube in resonance. The RBM peak counting method, i.e. acquiring Raman spectrum grids on a substrate with a select set of discrete laser lines and counting RBM peaks as single nanotubes, is frequently used to characterize SWCNT growth samples, despite the many factors that can induce errors in the results. In this work, we cross-characterize the diameter distributions obtained through this methodology with diameter distributions obtained by counting SWCNT diameters in transmission electron microscopy (TEM) and discuss the different results and biases between the techniques. This study is performed on a broad diameter distribution sample, and on two chirality-enriched samples whose chirality distributions are determined by photoluminescence excitation spectroscopy (PLE) and statistical analysis of high resolution TEM (HRTEM) images. We show that the largest differences between the Raman peak counting and TEM diameter distributions stem from the chirality-dependence of SWCNT Raman cross-sections and the patchy vision offered by the use of only a few discrete excitation wavelengths. The effect of the substrate and TEM-related biases are also discussed.

Raman Scattering Cross Section of Confined Carbyne

We experimentally quantify the Raman scattering from individual carbyne chains confined in double-walled carbon nanotubes. We find that the resonant differential Raman cross section of confined carbyne is on the order of 10-22 cm2 sr-1 per atom, making it the strongest Raman scatterer ever reported.

Controlling Optically Driven Atomic Migration Using Crystal-Facet Control in Plasmonic Nanocavities.

Plasmonic nanoconstructs are widely exploited to confine light for applications ranging from quantum emitters to medical imaging and biosensing. However, accessing extreme near-field confinement using the surfaces of metallic nanoparticles often induces permanent structural changes from light, even at low intensities. Here, we report a robust and simple technique to exploit crystal facets and their atomic boundaries to prevent the hopping of atoms along and between facet planes. Avoiding X-ray or electron microscopy techniques that perturb these atomic restructurings, we use elastic and inelastic light scattering to resolve the influence of crystal habit. A clear increase in stability is found for {100} facets with steep inter-facet angles, compared to multiple atomic steps and shallow facet curvature on spherical nanoparticles. Avoiding atomic hopping allows Raman scattering on molecules with low Raman cross-section while circumventing effects of charging and adatom binding, even over long measurement times. These nanoconstructs allow the optical probing of dynamic reconstruction in nanoscale surface science, photocatalysis, and molecular electronics.