We report a joint study, using Raman micro-spectroscopy and molecular dynamics simulations, on the substrate effect on thermal properties of 2D materials and revisit measurement of thermal expansion coefficient (TEC) of supported 2D film. Graphene is employed as a representative. We find that the out-of-plane coupling between graphene and substrate strongly affects the temperature-dependent vibrational modes and TEC of graphene. Density of states for long-wavelength out-of-plane oscillations is significantly reduced when graphene is supported on an alkane substrate. To account for the contribution of the out-of-plane coupling to TEC, a Raman micro-spectroscopic scheme is developed. The TEC of graphene on octadecyltrichlorosilane substrate is found to be (-0.6+-0.5)*10-6/K at room temperature, which is fundamentally smaller than that of free-standing graphene. Our results shed light on the understanding of the interaction between 2D material and substrate, and offer a general recipe for optical measurement of TEC of a supported 2D film.
We present a detailed in-situ Raman analysis of stage-1 KC8, CaC6, and LiC6 graphite intercalation compounds (GIC) to unravel their intrinsic finger print. Four main components were found between 1200 cm-1 and 1700 cm-1, and each of them were assigned to a corresponding vibrational mode. From a detailed line shape analysis of the intrinsic Fano-lines of the G- and D-line response we precisely determine the position (ωph), line width (Γph) and asymmetry (q) from each component. The comparison to the theoretical calculated line width and position of each component allow us to extract the electro…
Al4SiC4 is a wide band gap semiconductor with numerous potential technological applications. We report here the first thorough experimental Raman and Infrared (IR) investigation of vibrational properties of Al4SiC4 single crystals grown by high temperature solution growth method. The experimental results are compared with the full theoretical analysis of vibrational properties based on Density Functional Theory calculations that are revisited here. We have obtained a good agreement between the experimental and calculated Raman phonon modes and this allowed the symmetry assignment of all the me…
We propose and theoretically analyze a new vibrational spectroscopy, termed electron- and light-induced stimulated Raman (ELISR) scattering, that combines the high spatial resolution of electron microscopy with the molecular sensitivity of surface-enhanced Raman spectroscopy. With ELISR, electron-beam excitation of plasmonic nanoparticles is utilized as a spectrally-broadband but spatially-confined Stokes beam in the presence of a diffraction-limited pump laser. To characterize this technique, we develop a numerical model and conduct full-field electromagnetic simulations to investigate two di…
Cr2Ge2Te6 has been of interest for decades, as it is one of only a few ferromagnetic insulators. Recently, this material has been revisited due to its potential as a substrate for Bi2Te3, a topological insulator. This enables the possibility of studying the anomalous quantum Hall effect in topological insulators, and a route to novel spintronic devices. To probe the compatibility of these two materials, we use polarized variable temperature Raman microscopy to study Bi2Te3-Cr2Ge2Te6 heterostructure as well as the phonon dynamics of Cr2Ge2Te6. We found the temperature dependence of the Cr2Ge2Te…
Confined microexplosions induced in silicon by powerful ultrashort laser pulses can lead to new Si phases. Some of these have not previously been observed via near-equilibrium compression of silicon. In this study, confocal Raman micro-spectroscopy and Raman imaging of arrays of microexplosions have been conducted to search for Raman signatures of these novel allotropes of silicon. A microexplosion is generated at the interface between a thick silicon dioxide confinement layer and underlying silicon. It is characterised by a void at the interface above a region of compressed silicon. Raman dat…
In this note, we report a Raman spectroscopy study of annealing-induced effects on graphene samples prepared by the microexfoliation method. It was shown that randomly located adhesive residues often contaminate nearby graphene sheets during thermal annealing. The contamination on graphene can be as thin as ~1 nm, but gives several new Raman bands of unusually strong intensity. We also find that their intensity is strongly dependent on the excitation wavelength implying that graphene-induced Raman enhancement may be operative. The current study also suggests that graphene can be selectively se…
We have performed for the first time micro-Raman studies of lysozyme crystals for the temperatures lower than the room one (in the range 282-300K). Anomalous temperature dependence of the positions of Raman scattering bands has been detected and discussed, which corresponds to the crystalline lysozyme structure in the vicinity of T=285K.
We have revisited the still unresolved puzzle of the dispersion of the Raman disordered-induced D band as a function of laser excitation photon energy E$_L$ in graphite-like materials. We propose that the D-mode is a combination of an optic phonon at the K-point in the Brillioun zone and an acoustic phonon whose momentum is determined uniquely by the double resonance condition. The fit of the experimental data with the double-resonance model yields the reduced effective mass of 0.025m$_{e}$ for the electron-hole pairs corresponding to the A$_{2}$ transition, in agreement with other experiments…
While producing comparable efficiencies and showing similar properties when probed by conventional techniques, such as Raman, photoluminescence and X-ray diffraction, two thin film solar cell materials with complex structures, such as quaternary compound CZTSe, may in fact differ significantly in their microscopic structures. In this work, laser induced modification Raman spectroscopy, coupled with high spatial resolution and high temperature capability, is demonstrated as an effective tool to obtain important structure information beyond that the conventional characterization techniques can o…
We demonstrate gold coated polymer surface enhanced Raman scattering (SERS) substrates with a pair of complementary structures--positive and inverted pyramids array structures fabricated by multiple-step molding and replication process. The uniform SERS enhancement factors over the entire device surfaces were measured as 7.2 X 10^4 for positive pyramids substrate while 1.6 X 10^6 for inverted pyramids substrate with Rhodamine 6G as the target analyte. Based on the optical reflection measurement and FDTD simulation result, the enhancement factor difference is attributed to plasmon resonance mat…
Raman micro-spectroscopy is well suited for studying a variety of properties and has been applied to wide- ranging areas. Combined with tuneable temperature, Raman spectra can offer even more insights into the properties of materials. However, previous designs of variable temperature Raman microscopes have made it extremely challenging to measure samples with low signal levels due to thermal and positional instability as well as low collection efficiencies. Thus, contemporary Raman microscope has found limited applicability to probing the subtle physics involved in phase transitions and hyster…
Ferroelectric-like hysteresis loops of CaCu3Ti4O12 (CCTO) ceramic have been observed. We found that this unusual feature does not arise from the displacement of the Ti ions in the TiO6 octahedron, but apparently comes from the charges at the grain boundaries which consist of a CuO layer. The relaxation time of 2.9 milliseconds by the charges from the grain boundary, nearly corresponding to the inverse P - V sampling frequency of 1kHz, has been found in the impedance spectrum. According to the micro-Raman mapping, the CuO layer is found in the grain boundary and is perfectly distinguished from …
Single phase nano and micro crystalline silicon films deposited using SiF4/H2 plasma at different H2 dilution levels were studied at initial and terminal stages of film growth with spectroscopic ellipsometry (SE), Raman scattering (RS) and atomic force microscopy (AFM). The analysis of data obtained from SE elucidates the microstructural evolution with film growth in terms of the changes in crystallite sizes and their volume fractions, crystallite conglomeration and film morphology. The effect of H2 dilution on film microstructure and morphology, and the corroborative findings from AFM studies…
The temperature dependence of phonon excitations and the presence of spin phonon coupling in polycrystalline Pr2NiMnO6 samples were studied using micro-Raman spectroscopy and magnetometry. Magnetic properties show a single ferromagnetic-to-paramagnetic transition at 228 K and a saturation magnetization close to 4.95 \muB/f.u.. Three distinct Raman modes at 657, 642, and 511 cm-1 are observed. The phonon excitations show a clear hardening due to anharmonicity from 300 K down to 10 K. Further, temperature dependence of the 657 cm-1 mode shows only a small softening. This reflects the presence of…
Polarization resolved micro-Raman spectroscopy was carried out at the edges of bilayer graphene. We find strong dependence of the intensity of the G band on the incident laser polarization, with its intensity dependence being 90 degrees out of phase for the armchair and zigzag case, in accordance with theoretical predictions. For the case of mixed-state edges we demonstrate that the polarization contrast reflects the fractional composition of armchair and zigzag edges, providing a monitor of edge purity, which is an important parameter for the development of efficient nanoelectronic devices.
The use of micro-Raman spectroscopy, through chemical bond nano-scale probes, allows the changes in conformations (alpha helix -> beta sheet), chain orientation, disconnection of disulfide bonds (-20%) and the increase of intra and inter-chain distances during the strain to be distinguished. The combination of micro-Raman spectroscopy and a allows a quantitative measure of the extension of chemical bonds in the peptidic chain during loading. The nano-structural transformations of keratin during the strain of human hair in a dry environment (40-60 % relative humidity) and saturated with water h…
The paper provides a comprehensive study on Raman spectroscopy versatility as a fast and non destructive tool for the prediction of the mechanical properties of SiC fibers derived from a polymeric precursor (NLM, Hi, Hi-S, SA and Sylramic grades) or produced by CVD (SCS-6 fiber), including in situ analysis in CMCs or MMCs. We show how the results of very simple spectra fitting are correlated with Young's modulus, tensile strength and micro-hardness. The reason why such a correlation exists, the common dependency of Raman signal and mechanical behavior to the micro/nanostructure of ceramics, is…
We present a fast and simple way to determine the erosion rate and absorption coefficient of hydrogenated amorphous carbon films exposed to a hydrogen atomic source based on ex-situ Raman micro-spectroscopy. Results are compared to ellipsometry measurement. The method is applied to films eroded at different temperatures. A maximum of the erosion rate is found at ~ 450 {\degree}C in agreement with previous results. This technique is suitable for future quantitative studies on the erosion of thin carbonaceous films, especially of interest for plasma wall interactions occurring in thermonuclear f…
We report strong variations in the Raman spectra for different single-layer graphene samples obtained by micromechanical cleavage, which reveals the presence of excess charges, even in the absence of intentional doping. Doping concentrations up to ~10^13 cm-2 are estimated from the G peak shift and width, and the variation of both position and relative intensity of the second order 2D peak. Asymmetric G peaks indicate charge inhomogeneity on the scale of less than 1 micron.
Phthalocyanines as organic semiconductors and molecular magnets provide plenty of industrial or high-tech applications from dyes and pigments up to gas sensors, molecular electronics, spintronics and quantum computing. Copper phthalocyanine (CuPc) belongs among the most used phthalocyanines, typically in the form of powder or films but self-grown nanowires are also known. Here we describe an opposite, i.e., top-down approach based on fabrication of ordered arrays of CuPc microstructures (microdisks) using electron beam lithography and other steps. Among critical points of this approach belongs…
Bismuth telluride - Bi(2)Te(3)- and related compounds have recently attracted strong interest owing to the discovery of the topological insulator properties in many members of this family of materials. The few-quintuple films of these materials are particularly interesting from the physics point of view. We report results of the micro-Raman spectroscopy study of the "graphene-like" exfoliated few-quintuple layers of Bi(2)Te(3), Bi(2)Se(3) and Sb(2)Te(3). It is found that crystal symmetry breaking in few-quintuple films results in appearance of A1u-symmetry Raman peaks, which are not active in …
We present the Raman microscopy ability to detect and characterize the way hydrogen is bonded with elements that will be used for ITER's plasma facing components. For this purpose we first use hydrogenated amorphous carbon samples, formed subsequently to plasma-wall interactions (hydrogen implantation, erosion, deposition...) occurring inside tokamaks, to demonstrate how this technique can be used to retrieve useful information. We pay attention in identifying which spectroscopic parameters are sensitive to the local structure (sp 3 /sp 2) and which gives information on the hydrogen content us…
