Double line stimulated Raman scattering in benzene

Simultaneous stimulated Raman scattering at the 992 cm^–1 and the 3063 cm^–1 line of benzene is observed by mode-locked ruby laser pulse excitation. The double line stimulated Raman scattering is initiated by self-focusing. The influence of small-scale self-focusing, self-phase modulation, and cross-phase modulation on the double line stimulated Raman scattering is discussed. At low pump pulse intensities, before the onset of small-scale self-focusing, the steady-state Raman gain factors of both Raman lines are determined by Raman energy conversion efficiency measurements.     

Nonlinear emission in sodium vapour upon pulsed-laser excitation of the 42 P levels

Parametric four-wave mixing, stimulated electronic Raman scattering and amplified spontaneous emission cascades have been studied experimentally by single-photon resonant and near-resonant excitation of the 4² P levels of dense sodium vapour. The dependence of emission intensities on laser detuning and exciting laser power is discussed.     

碳纳米管的拉曼光谱及其温度效应

在室温下首次观察到碳纳米管的四级拉曼光谱，并且发现碳纳米管的Ｄ峰和Ｄ＊峰的斯托克斯线和反斯托克斯线频率不一致。此外，还发现碳纳米管的拉曼特征峰频率严重依赖样品的温度，随着温度增加，碳纳米管拉曼特征峰频率下移，频移与温度变化成线性关系。     

Diamond-like phase formation in an amorphous carbon films prepared by periodic pulsed laser deposition and laser irradiation method

Diamond-like carbon (DLC) films were fabricated by pulsed laser ablation of a liquid target. During deposition process the growing films were exited by a laser beam irradiation. The films were deposited onto the fused silica using 248 nm KrF eximer laser at room temperature and 10⁻³ mbar pressure. Film irradiation was carried out by the same KrF laser operating periodically between the deposition and excitation regimes. Deposited DLC films were characterized by Raman scattering spectroscopy. The results obtained suggested that laser irradiation intensity has noticeable influence on the structure and hybridization of carbon atoms deposited. For materials deposited at moderate irradiation intensities a very high and sharp peak appeared at 1332 cm⁻¹, characteristic of diamond crystals. At higher irradiation intensities the graphitization of the amorphous films was observed. Thus, at optimal energy density the individual sp³-hybridized carbon phase was deposited inside the amorphous carbon structure. Surface morphology for DLC has been analyzed using atomic force microscopy (AFM) indicating that more regular diamond cluster formation at optimal additional laser illumination conditions (∼20 mJ per impulse) is possible.     

Study of Raman spectrum of uranium using a surface‐enhanced Raman scattering technique

Raman spectroscopic investigation on weak scatterers such as metals is a challenging scientific problem. Technologically important actinide metals such as uranium and plutonium have not been investigated using Raman spectroscopy possibly due to poor signal intensities. We report the first Raman spectrum of uranium metal using a surface‐enhanced Raman scattering‐like geometry where a thin gold overlayer is deposited on uranium. Raman spectra are detected from the pits and scratches on the sample and not from the smooth polished surface. The 514.5‐ and 785‐nm laser excitations resulted in the Raman spectra of uranium metal whereas 325‐nm excitation did not give rise to such spectra. Temperature dependence of the B_3g mode at 126 cm⁻¹ is also investigated. Copyright © 2011 John Wiley & Sons, Ltd.     

低温下单壁碳纳米管拉曼光谱温度效应研究

在单壁碳纳米管的低温拉曼光谱测量过程中,发现径向呼吸模(RBM)和正切拉伸模(GM)的拉曼频移在低温下的温度效应和在高温时的温度效应存在着很大的区别,在低温下拉曼光谱的频移和温度并不呈线性关系。而且,在温度为210K时,单壁碳纳米管内部的振动结构可能发生了变化。在低温下单壁碳纳米管拉曼峰的强度的变化是不可逆的。     

Softening of phonon modes in C60 crystals induced by laser irradiation: Thermal effects

Reversible softening of the intramolecular A _g(2) pentagonal pinch (PP) mode of a C₆₀ single crystal in the face centered cubic phase has been studied as a function of laser power density by means of Raman scattering. The average temperature rise in the laser excitation spot has been determined using the Stokes to anti-Stokes integrated peak intensity ratio for the H _g(1) phonon mode. Softening of the PP-mode was found to be due to heating of the sample resulting from laser irradiation, in good quantitative agreement with experimental results obtained for uniformly heated samples. These findings are in excellent agreement with results obtained by numerical calculations of the local temperature distribution and average temperature in the laser spot based on calculated integrated intensities of the Stokes and anti-Stokes bands of the PP-mode. These calculations were based on experimental data for the temperature dependence of phonon frequency and width, absorbance, and thermal conductivity in solid C₆₀. Zh. éksp. Teor. Fiz. 114, 1785–1794 (November 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor     

Double resonance Raman scattering of second-order Raman modes from an individual graphite whisker

Resonant Raman scattering of second-order Raman modes from an individual graphite whisker synthesized by a high-temperature heat-treatment method at a special pressure was discussed here. The dependence of phonon frequencies on the incoming laser light and the frequency difference between Stokes and anti-Stokes scattering show their origin from double resonance Raman scattering. Our results show that all the experimental results of second-order Raman modes in graphite whiskers, such as the excitation-energy dependence on the mode frequency, the frequency shift between a second-order Raman mode and its fundamentals, and the frequency discrepancy between Stokes and anti-Stokes components of a second-order Raman mode can be well understood by double resonance Raman scattering.     

New features in the anti‐Stokes and Stokes Raman spectra of single‐walled carbon nanotubes that are highly separated into their semiconducting and metallic nanotube components

Surface‐enhanced Raman scattering studies were performed using nonresonant (514.5 nm) and resonant (676.4 nm) optical excitations on single‐walled carbon nanotubes thoroughly separated into semiconducting (pure 99%) and metallic (pure 98%) components. Regardless of the support (Au or Ag), the metallic nanotubes do not present an anomalous anti‐Stokes Raman emission. Regardless of whether an on‐resonant or off‐resonant optical excitation is used, only the semiconducting nanotubes produce an abnormal anti‐Stokes Raman emission that grows when increasing the excitation light intensity or temperature. The Raman studies under light polarized relative to the main nanotube axis demonstrate that only semiconducting nanotubes are sensitive toward changes in the polarization of the excitation light. Copyright © 2014 John Wiley & Sons, Ltd.     

Possible interplay between a two phonon mode and high energy magnetic excitations in BiFeO<Subscript>3</Subscript>

We have performed Raman measurements on high energy excitations in BiFeO₃ single crystals as a function of both temperature and laser excitation lines. A strong feature observed at 1250 cm^-1 in the Raman spectra has been previously assigned to two phonon overtone. This peak exhibits an unusual frequency shift with the laser lines and the temperature dependence of its Fano lineshape shows two singularities at 150 K and 200 K which can be related to magnetic excitations. In the same energy range, we have also identified the two-magnon excitation with a temperature dependence very similar to the one measured for the one-magnon modes.     

不同激发波长下单壁碳纳米管与多壁碳纳米管的拉曼光谱比较

对不同激发波长下单壁和多壁碳纳米管的激光拉曼光谱进行了比较。发现单壁碳纳米管D峰强度和G峰强度的比值(ID/IG)几乎不随激发光子能量的改变而变化,多壁碳纳米管ID/IG值随着激发光子能量的增加以斜率0 3/eV减小。并对此现象进行了初步的分析。此外,还发现在1064nm激发波长下,单壁和多壁碳纳米管2500-3500cm-1之间拉曼峰的相对强度随着入射激光功率的增加而增加。     

Photodissociation effects on pulsed laser deposited silver oxide thin films: surface‐enhanced resonance Raman scattering

Temporal Raman scattering measurements with 488, 532 and 632 nm excitation wavelengths and normal Raman studies by varying the power (from 30 W/cm² to 2 MW/cm²) at 488 nm were performed on silver oxide thin films prepared by pulsed‐laser deposition. Initially, silver oxide Raman spectra were observed with all three excitation wavelengths. With further increase in time and power, silver oxide photodissociated into silver nanostructures. High‐intensity spectral lines were observed at 1336 ± 25 and 1596 ± 10 cm⁻¹ with 488 nm excitation. No spectral features were observed with 633 nm excitation. Surface‐enhanced resonance Raman scattering theory is used to explain the complex behavior in the intensity of the 1336/1596 cm⁻¹ lines with varying power of 488 nm excitation. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman studies of nonlinear phenomena in fullerene crystallites

The resonant Raman scattering of C₆₀ crystallites is monitored as a function of excitation intensity at 514.5 nm. At low intensities, a strong line at 1468 cm^–1 is observed. No feature at 1459 cm^–1 is observable. With increasing intensities, the 1468 cm^–1 line shifts continuously and reversibly to lower frequencies. The mode softening is nonlinearly dependent on the input intensity and is accompanied by a nonlinear increase in the Raman intensity. The spectral changes are discussed in terms of a nonlinear reduction in force constant and increase in bond polarisability as a result of an increased intermolecular delocalisation of the -electron cloud. The nonlinear changes are associated with the nonlinear luminescence and photoconductive response observed in fullerenes and are contrasted to the irreversible phototransformation recently discussed.     

Temperature characterization of Raman scattering in an AlGaN/GaN heterostructure

Raman scattering from an AlGaN/GaN heterostructure was performed in the temperature range from 77 to 773 K. The first- and second-order Raman scattering of the A₁ longitudinal-optical phonon–plasmon coupled mode from an AlGaN/GaN interface as well as the Raman scattering from the GaN layer were observed. All the modes downshift, and their intensities weaken with increasing temperature. The free-carrier concentration estimated by the frequency of the coupled mode from an AlGaN/GaN interface is 7.5 times as high as that of n-AlGaN, indicating mass free-carrier transfer from the AlGaN barrier to the GaN well. Moreover, the temperature dependence of the phonon frequency is well described by an empirical formula. PACS 78.30.Fs; 63.20.Ls; 61.82.Fk; 68.60.Dv; 81.15.Gh     

Surface‐enhanced Raman spectroscopy of 4‐tert‐butylpyridine on a silver electrode

We report the observation of large surface‐enhanced Raman scattering (SERS) (10⁶) for 4‐tert‐butylpyridine molecules adsorbed on a silver electrode surface in an electrochemical cell with electrode potential set at − 0.5 V. A decrease in electrode potential to − 0.3 V was accompanied by a decrease in relative intensities of the vibrational modes. However, there were no changes in vibrational wavenumbers. Comparison of both normal solution Raman and SERS spectra shows very large enhancement of the intensities of a₁, a₂, and b₂ modes at laser excitation of 488 nm. Enhancement of the non‐totally symmetric modes indicates the presence of charge transfer as a contributor to the enhancement. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of the Thermal Expansion Coefficient of Single-Wall Carbon Nanotubes by Raman Spectroscopy

We have examined the effect of high temperature on single-wall carbon nanotubes under air and nitrogen ambient by Raman spectroscopy. We observe the temperature dependence of the radial breathing mode and the G-band modes. The thermal expansion coefficient (β) of the bundled nanotubes is obtained experimentally using the estimated volume from Raman scattering. β behaves linearly with temperature from 0.33 × 10^?5 K^?1 to 0.28 × 10^?5 K^?1 in air and from 0.58 × 10^?5 K^?1 to 0.47 × 10^?5 K^?1 in nitrogen ambient, respectively. The temperature dependence of the radial breathing mode Raman frequencies is consistent with a pure temperature effect.     

How does the substrate affect the Raman and excited state spectra of a carbon nanotube?

We study the optical properties of a single, semiconducting single-walled carbon nanotube (CNT) that is partially suspended across a trench and partially supported by a SiO₂-substrate. By tuning the laser excitation energy across the E ₃₃ excitonic resonance of the suspended CNT segment, the scattering intensities of the principal Raman transitions, the radial breathing mode (RBM), the D mode and the G mode show strong resonance enhancement of up to three orders of magnitude. In the supported part of the CNT, despite a loss of Raman scattering intensity of up to two orders of magnitude, we recover the E ₃₃ excitonic resonance suffering a substrate-induced red shift of 50 meV. The peak intensity ratio between G band and D band is highly sensitive to the presence of the substrate and varies by one order of magnitude, demonstrating the much higher defect density in the supported CNT segments. By comparing the E ₃₃ resonance spectra measured by Raman excitation spectroscopy and photoluminescence (PL) excitation spectroscopy in the suspended CNT segment, we observe that the peak energy in the PL excitation spectrum is red-shifted by 40 meV. This shift is associated with the energy difference between the localized exciton dominating the PL excitation spectrum and the free exciton giving rise to the Raman excitation spectrum. High-resolution Raman spectra reveal substrate-induced symmetry breaking, as evidenced by the appearance of additional peaks in the strongly broadened Raman G band. Laser-induced line shifts of RBM and G band measured on the suspended CNT segment are both linear as a function of the laser excitation power. Stokes/anti-Stokes measurements, however, reveal an increase of the G phonon population while the RBM phonon population is rather independent of the laser excitation power.     

Effect of ZnO as modifier on up and downconversion properties of Ho/Yb doped tellurite glasses

Optical absorption and photoluminescent properties of Ho³⁺/Yb³⁺ co-doped tellurite and zinc tellurite glasses are investigated. The effect of zinc oxide as a modifier on the luminescence properties of above mentioned samples has been explored. Two intense upconversion emission bands centered at 546 (⁵F₄ + ⁵S₂ → ⁵I₈) and 660 nm (⁵F₅ → ⁵I₈) are observed on excitation with 976 nm diode laser. Zinc oxide acts as a quencher for 976 nm excited upconversion emission. The up and downconversion emission spectra are recorded with 532 nm excitation source also. In this case zinc oxide improves the up and downconversion emissions. A large enhancement in upconversion intensity has been observed when Ho³⁺ ion is co-doped with Yb³⁺ ion. The dependence of upconversion intensities on excitation power and on temperature has also been studied. The power dependence study shows a quadratic dependence of the fluorescence intensity on the excitation power while a decrement in emission intensity of all the transitions at different rates with increase in temperature is observed in temperature dependence study. The possible mechanisms are also discussed in order to understand the upconversion and energy transfer processes.     

Rapid shifted excitation Raman difference spectroscopy with a distributed feedback diode laser emitting at 785 nm

A distributed feedback (DFB) laser diode emitting at 785 nm was tested and applied as a light source for shifted excitation Raman difference spectroscopy (SERDS). Due to the physical properties of the laser diode, it was possible to shift the emission wavelength by 8 cm^-1 (0.5 nm) required for our SERDS measurements by simply changing the injection current. The internal grating ensured single mode operation at both wavelength with the frequency stability of ±0.06 cm^-1 (0.004 nm) required for high resolution Raman spectroscopic applications. The shifted spectra were used for calculating enhanced Raman spectra being obscured by a strong scattering background. A 16 dB (≈38 fold) improvement of the signal-to-background noise S̄/σ_B was demonstrated using blackboard chalk as a sample. The tunable DFB laser is a versatile excitation source for SERDS, which could be used in any dispersive Raman system to subtract fluorescence contributions and scattering background. PACS 82.80.Gk; 42.55.-f; 42.64.Fi     

Pulsed optoacoustic detection of multiple photon excitation in molecules

Multiple photon excitation, saturation, and linear absorption of SF₆-argon mixtures when irradiated by a high power CO₂ TEA laser is investigated using a pulsed optoacoustic technique. At low intensities the expected linear dependence of the absorption on laser intensity is observed. At intermediate intensities the absorption exhibits a square root dependence on the incident laser intensity, a dependence which is typical for saturation of an inhomogeneously broadened absorption. At even higher intensities, the absorption shows an intensity dependence typical of multiple photon excitation. The laser intensity was varied between 0.016 kW/cm² and 5 MW/cm², values lower than that needed to produce multiple photon dissociation of SF₆. Increasing the collision frequency of the absorbing molecules with an inert buffer gas is observed to quench the multiple photon excitation.