Raman spectroscopy of advanced materials

Many micro-structural aspects of advanced materials and the incidence on the physical properties have been elucidated by Raman micro-spectroscopy. The potential of this technique is demonstrated with new materials interesting in both academic and industrial developments: new carbons and diamonds, superconductors, semiconductors, superhards.     

Raman spectroscopy of advanced materials

Many micro-structural aspects of advanced materials and the incidence on the physical properties have been elucidated by Raman micro-spectroscopy. The potential of this technique is demonstrated with new materials interesting in both academic and industrial developments: new carbons and diamonds, superconductors, semiconductors, superhards.     

Fourth-order coherent Raman spectroscopy in a time domain: applications to buried interfaces

A Raman-based, nonlinear optical spectroscopy is a promising method for observing vibrational modes localized at buried interfaces. The principles of Raman excitation and interface-selective detection of coherent vibrations are described. Applications to air-liquid, liquid-liquid, air-solid, liquid-solid, and solid-solid interfaces are reviewed.     

拉曼光谱表征石墨烯材料的研究进展

石墨烯独特的二元化电子价键结构使其在纳米电子器件中具有良好的应用发展前景。拉曼光谱作为一种灵敏、便捷的技术,已被成功地用作表征石墨烯的结构和特性。本综述着重对沉积在不同基底以及掺杂的石墨烯拉曼光谱研究做了一个简单的总结。通过对铟锡氧化物、蓝宝石和玻璃基底上的石墨烯拉曼光谱进行观察,发现在不同基底上的石墨烯拉曼G峰与2D峰峰值会有不同程度的偏移,但2D峰峰值可判断石墨烯层数这一结论仍适用。掺杂可改变石墨烯的荷电状态,使石墨烯表现出空穴（p）型或电子（n）型掺杂特性,通过石墨烯拉曼光谱的变化可以定性石墨烯的掺杂类别并定量表征石墨烯的载流子浓度。     

Evaluation of Raman spectroscopy to detect fullerenes in geological materials

Fullerene C(60) was determined repeatedly from a few types of carbonaceous matter from geological environments. Detailed investigation of structural aspects of pure carbonaceous matrices as well as of their experimental mixtures with fullerene C(60) permits better understanding of the occurrence mode of fullerenes inside the network of natural samples. However, it appears that Raman microspectrometry is not competitive in the case of investigated current geological carbonaceous matrices with added fullerenes, when the concentration of fullerene C(60) is 100 ppm or lower. In such a situation, C(60) is highly dispersed and careful interpretation of the results of Raman microspectrometry does not permit us to obtain valuable quantitative structural data. Obtained sensitivity for detecting C(60) in investigated matrices was only 1%. Analytical reasons for these results are discussed.     

Measurement of interdiffusion in polymeric materials by applying Raman spectroscopy

Raman spectroscopy was evaluated regarding its specific value in terms of detection of interdiffusion in two-component injection molded parts. Two-component injection molded parts made of four material combinations chosen from polypropylene, styrene based thermoplastic elastomer, polycarbonate, polystyrene and polymethyl methacrylate produced by varying melt temperatures of the second component T_M2 were investigated.In principle, Raman spectroscopy was found to be a powerful tool to detect interdiffusion. However, some restrictions arise. These include spatial resolution limit and detection limit. Interdiffusion lengths ranging from below 1 μm–3 μm were determined. Either an increase, a decrease or no change of the interdiffusion length for increasing T_M2 was detected. The interdiffusion lengths were compared with the stress and elongation at break obtained by tensile tests. No distinct correlation of interdiffusion length and the mechanical properties was found. However, a high T_M2 provoked an increase in the stress and elongation at break.     

High-temperature Raman spectroscopy of solid oxide fuel cell materials and processes

Chemical and material processes occurring in high temperature environments are difficult to quantify due to a lack of experimental methods that can probe directly the species present. In this letter, Raman spectroscopy is shown to be capable of identifying in-situ and noninvasively changes in material properties as well as the formation and disappearance of molecular species on surfaces at temperatures of 715 degrees C. The material, yttria-stabilized zirconia or YSZ, and the molecular species, Ni/NiO and nanocrystalline graphite, factor prominently in the chemistry of solid oxide fuel cells (SOFCs). Experiments demonstrate the ability of Raman spectroscopy to follow reversible oxidation/reduction kinetics of Ni/NiO as well as the rate of carbon disappearance when graphite, formed in-situ, is exposed to a weakly oxidizing atmosphere. In addition, the Raman active phonon mode of YSZ shows a temperature dependent shift that correlates closely with the expansion of the lattice parameter, thus providing a convenient internal diagnostic for identifying thermal gradients in high temperature systems. These findings provide direct insight into processes likely to occur in operational SOFCs and motivate the use of in-situ Raman spectroscopy to follow chemical processes in these high-temperature, electrochemically active environments.     

On the characterization of disordered and heterogeneous carbonaceous materials by Raman spectroscopy

The applicability of Raman spectroscopy to characterize disordered and heterogeneous carbonaceous materials (CM) is discussed, by considering both natural and synthetic CM. First, different analytical mismatches during the measurement are discussed and technical indications are provided in order to eliminate them. Second, the accuracy and relevance of the different parameters obtained by the decomposition of spectra by conventional fitting procedure, is reviewed. Lastly, a new Raman technique (Raman area mode microspectroscopy) giving an homogeneous repartition of power within a large laser beam is presented, this technique being powerful to study strongly heterogeneous CM and/or photosensitive samples.     

Raman and 29Si MAS NMR spectroscopy of framework materials containing three-membered rings

Raman and ²⁹Si MAS NMR spectroscopies are evaluated for the identification of three-membered rings (3MR) in framework oxide materials. Raman and ²⁹Si MAS NMR spectra from the 3MR-containing materials euclase, phenakite, clinohedrite, willemite, lovdarite, VPI-7, ZSM-18 and dipotassium zinc tetrasilicate are presented. The Raman spectra from these materials do not exhibit common bands representing vibrational modes assignable to individual 3MR. The dense beryllosilicate and zincosilicate minerals exhibit ²⁹Si MAS NMR resonances indicative of silicon positioned in 3MR while the molecular sieves lovdarite and VPI-7 give ²⁹Si MAS NMR resonances that can be assigned to silicons located at the center of “spiro-5” units that are constructed from two 3MR. Silicon atoms located in isolated 3MR in the molecular sieves ZSM-18 and dipotassium zinc tetrasilicate do not exhibit ²⁹Si MAS NMR resonances that can be distinguished from those assigned to silicons residing in 4MR and larger.The ²⁹Si MAS NMR spectra from the new materials VPI-8, VPI-9 and VPI-10 do not exhibit ²⁹Si MAS NMR resonances indicative of “spiro-5” units. The presence of isolated 3MR in these materials cannot be ruled out from the ²⁹Si MAS NMR spectroscopic results.     

Highly sensitive Raman spectroscopy using a gap mode plasmon under an attenuated total reflection geometry

We investigated a gap mode plasmon under an attenuated total reflection (ATR) configuration toward realization of near-field Raman spectroscopy with a single molecule sensitivity and spatial resolution. Additional enhancement in Raman scattering at a nanogap was obtained by a coupling of a propagating surface plasmon (PSP) of Ag films on a prism, and a gap mode between Ag films and Ag nanoparticles (AgNPs). Immobilization of AgNPs on Ag films through thiol-SAM slightly up-shifted the resonance angle of a PSP, which broadened the reflectivity dip owing to an increased out-coupling of a PSP. Raman enhancement factor at a nanogap increased with decreasing surface coverage of AgNPs, albeit the enhancement factor averaged over illuminated area in Ag films decreased, ensuring the largest enhancement factor in tip-enhanced Raman scattering. This is due to increased efficiency for a PSP excitation at lower coverage of AgNPs in consistent with that in theoretical evaluation using finite difference time domain calculations. A gap mode under an ATR configuration was applied to elucidate a plausible photochemical reaction of p-amino thiophenol (PATP) adsorbed on Ag films on a prism. Spectral changes in Raman scattering under laser illumination were observed for PATP with a deuterated amino group, but suppressed by a dimethyl amino group owing to steric hindrance, supporting the photochemical dimerization.     

Raman spectroscopy of thiosulphates

The narrow line-width of Fourier transform Raman spectroscopy has been utilized to produce spectra of various simple thiosulphates. The accuracy of the technique has enabled us to show wide frequency shifts and splitting from counter ion to counter ion, and has thrown doubt on the use of vibrational spectra to indicate ion interactions.     

Raman spectroscopy of diamondoids

A selection of diamondoid hydrocarbons, from adamantane to [121321] heptamantane, have been analysed by multi-wavelength laser Raman spectroscopy. Spectra were assigned using vibrational frequencies and Raman intensities were calculated by employing the B3LYP functional and the split valence basis set of Schafer, Horn and Ahlrichs with polarisation functions on carbon atoms. The variation of the spectra and associated vibrational modes with the structure and symmetry of the molecules are discussed. Each diamondoid was found to produce a unique Raman spectrum, allowing for easy differentiation between molecules. Using the peak assignments derived from the calculations we find that the low frequency region of the spectra, corresponding to CCC-bending/CC-stretching modes, is particularly characteristic of the geometric shape of the diamondoid molecules.     

Structural characterization of thin films formed or changed on materials by micro Raman spectroscopy

Micro Raman spectroscopy is shown as a useful method of high spatial resolution in characterization of thin films on or in materials formed or changed as a result of external influences. Identification of black films in the glaze of porcelain, of impairing deposits on components of an ICP mass spectrometer and of tribologically stressed contacts of ADLC films or (Ti,Mo)(C,N) ceramics, respectively, are examples for application.     

Quantitative surface-enhanced Raman spectroscopy

The purpose of this tutorial review is to show how surface-enhanced Raman (SERS) and resonance Raman (SERRS) spectroscopy have evolved to the stage where they can be used as a quantitative analytical technique. SER(R)S has enormous potential for a range of applications where high sensitivity needs to be combined with good discrimination between molecular targets, particularly since low cost, compact spectrometers can read the high signal levels that SER(R)S typically provides. These advantages over conventional Raman measurements come at the cost of increased complexity and this review discusses the factors that need to be controlled to generate stable and reproducible SER(R)S calibrations.     

Raman spectroscopy in astrobiology

Raman spectroscopy is proposed as a valuable analytical technique for planetary exploration because it is sensitive to organic and inorganic compounds and able to unambiguously identify key spectral markers in a mixture of biological and geological components; furthermore, sample manipulation is not required and any size of sample can be studied without chemical or mechanical pretreatment. NASA and ESA are considering the adoption of miniaturised Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for extinct or extant life signals. In this paper we review the advantages and limitations of Raman spectroscopy for the analysis of complex specimens with relevance to the detection of bio- and geomarkers in extremophilic organisms which are considered to be terrestrial analogues of possible extraterrestial life that could have developed on planetary surfaces.     

Filament-driven impulsive Raman spectroscopy

Vibrational Raman spectroscopy is performed in the gas phase using a femtosecond laser pulse undergoing filamentation as an impulsive excitation source. The molecular coherence induced by the filamentary pulse is subsequently probed using a narrowband, sub-picosecond laser pulse to produce Raman spectra of gas phase species in a few tens of milliseconds (~10 laser shots). Pulse shortening with concomitant spectral broadening during filamentation results in a pulse that is both sufficiently short and of sufficient spectral power density to impulsively excite the highest energy ground state vibrations (up to 4158 cm(-1) corresponding to H(2)). Gas phase detection of chloroform, methylene chloride, cyclohexane, toluene, pentane, triethylamine, ammonia, nitromethane, and gasoline is performed.     

Raman spectroscopy on zeolites

The zeolite Raman literature is reviewed, with an emphasis on zeolite structure and synthesis, adsorption and metal complex formation in zeolites