Structural analysis of polycrystalline graphene systems by Raman spectroscopy

A theoretical model supported by experimental results explains the dependence of the Raman scattering signal on the evolution of structural parameters along the amorphization trajectory of polycrystalline graphene systems. Four parameters rule the scattering efficiencies, two structural and two related to the scattering dynamics. With the crystallite sizes previously defined from X-ray diffraction and microscopy experiments, the three other parameters (the average grain boundaries width, the phonon coherence length, and the electron coherence length) are extracted from the Raman data with the geometrical model proposed here. The broadly used intensity ratio between the C–C stretching (G band) and the defect-induced (D band) modes should be used to measure samples with crystallite sizes larger than the phonon coherence length, which is found equal to 32 nm. The Raman linewidth of the G band is more appropriate to characterize the crystallite sizes below the phonon coherence length, down to the average grain boundaries width, which is found to be 2.8 nm. “Ready-to-use” equations to determine the crystallite dimensions based on the Raman spectroscopy data are given.     

Thermal Effects on Electron-Phonon Interactions in Silicon Nanostructures

Raman spectroscopy of silicon nanostructures, recorded using an excitation laser power density of 1.0 kW/cm ² , was employed here to reveal the dominance of thermal effects at temperatures higher than room temperature. The room temperature Raman spectrum showed only phonon confinement and Fano effects. Raman spectra recorded at higher temperatures showed an increase in FWHM and a decrease in asymmetry ratio with respect to its room temperature counterpart. Experimental Raman scattering data were analyzed successfully using theoretical Raman line-shapes generated by incorporating the temperature dependence of a phonon dispersion relation. The experimental and theoretical temperature dependent Raman spectra are in good agreement. Although quantum confinement and Fano effects persist, heating effects start dominating at temperatures higher than room temperature.     

Raman and dielectric spectroscopic analysis of magnetic phase transition in Y(Fe0.5Cr0.5)O3 multiferroic ceramics

Here, we report the Raman and dielectric spectroscopic studies as a function of temperature of orthorhombically distorted Y(Fe_0.5Cr_0.5)O₃ (YFC) ceramics, measured from 80 to 300 K. The dc-magnetization measurements under field cooled (FC)-zero field cooled (ZFC) protocol indicate a small onset of magnetic ordering at T_N∼270 K. The field dependent magnetization plot recorded at 50 K, 150 K and 200 K show a clear opening in hysteresis loops. The linear dependence of magnetization plot at high field without any saturation of magnetization indicates the coexistence of weak ferromagnetic (WFM) component within the canting antiferromagnetic (CAFM) matrix. Temperature evolution of Raman line-shape parameter of B_2g(4) phonon mode clearly exhibits an anomalous behavior of phonon shift near T_N∼270 K, indicating the spin-phonon coupling in the ceramics. From the temperature dependent dielectric permittivity (ε(T)) study, two dielectric relaxation peaks are detected below 200 K and above 250 K. The appearance of former relaxation peak is responsible for polaronic conduction mechanism, while the later one is associated with magnetic phase transition which might be relevant to the presence of magnetoelectric coupling in YFC ceramics. The observed P-E hysteresis loops at room temperature indicate weak ferroelectric nature of the ceramics.     

Vibrational and NMR properties of polyynes

The bond-stretching phonon modes of linear polyynes with hydrogen atom termination at the both ends are calculated as a function of chain length within the density functional theory. The frequency of one of two particular Raman active phonon modes monotonically decreases with the increase of polyyne chain length while that of the other one shows an oscillating behavior, consistent with previous Raman measurements. The relative Raman intensity of the two phonon modes are evaluated by optimized geometries for ground states and excited states. We also present a nuclear magnetic resonance (NMR) calculation for spin–spin coupling constants as a function of distance between hydrogen and carbon-13 nuclei and, within carbon-13 nuclei, up to the polyyne center of symmetry. We compare the calculated results with recent NMR experiments.     

Size-dependent Fano Interaction in the Laser-etched Silicon Nanostructures

Photo-excitation and size-dependent Raman scattering studies on the silicon (Si) nanostructures (NSs) prepared by laser-induced etching are presented here. Asymmetric and red-shifted Raman line-shapes are observed due to photo-excited Fano interaction in the quantum confined nanoparticles. The Fano interaction is observed between photo-excited electronic transitions and discrete phonons in Si NSs. Photo-excited Fano studies on different Si NSs show that the Fano interaction is high for smaller size of Si NSs. Higher Fano interaction for smaller Si NSs is attributed to the enhanced interference between photo-excited electronic Raman scattering and phonon Raman scattering.     

Characterizing intrinsic charges in top gated bilayer graphene device by Raman spectroscopy

In this work we study the behavior of the optical phonon modes in bilayer graphene devices by applying top gate voltage, using Raman scattering. We observe the splitting of the Raman G band as we tune the Fermi level of the sample, which is explained in terms of mixing of the Raman (E_g) and infrared (E_u) phonon modes, due to different doping in the two layers. We theoretically analyze our data in terms of the bilayer graphene phonon self-energy which includes non-homogeneous charge carrier doping between the graphene layers. We show that the comparison between the experiment and theoretical model not only gives information about the total charge concentration in the bilayer graphene device, but also allows to separately quantify the amount of unintentional charge coming from the top and the bottom of the system, and therefore to characterize the intrinsic charges of bilayer graphene with its surrounding environment.     

Fano resonance in Raman scattering of graphene

Fano resonances and their strong doping dependence are observed in Raman scattering of single-layer graphene (SLG). As the Fermi level is varied by a back-gate bias, the Raman G band of SLG exhibits an asymmetric line shape near the charge neutrality point as a manifestation of a Fano resonance, whereas the line shape is symmetric when the graphene sample is electron or hole doped. However, the G band of bilayer graphene (BLG) does not exhibit any Fano resonance regardless of doping. The observed Fano resonance can be interpreted as interferences between the phonon and excitonic many-body spectra in SLG. The absence of a Fano resonance in the Raman G band of BLG can be explained in the same framework since excitonic interactions are not expected in BLG.     

Raman spectroscopic determination of the length, strength, compressibility, Debye temperature, elasticity, and force constant of the C-C bond in graphene

From the perspective of bond relaxation and bond vibration, we have formulated the Raman phonon relaxation of graphene, under the stimuli of the number-of-layers, the uni-axial strain, the pressure, and the temperature, in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of the Raman shifts, which are due to the number-of-layers reduction, of the G-peak shift and arises from the vibration of a pair of atoms, while the D- and the 2D-peak shifts involve the z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C(3v) bond geometry to the C(2v) uni-axial bond elongation; (iii) the thermal softening of the phonons originates from bond expansion and weakening; and (iv) the pressure stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift as well as the length, energy, force constant, Debye temperature, compressibility and elastic modulus of the C-C bond in graphene, which is of instrumental importance in the understanding of the unusual behavior of graphene.     

Physical and Electrical Performance of Vapor–Solid Grown ZnO Straight Nanowires

Physical and electrical properties of wurtzitic ZnO straight nanowires grown via a vapor–solid mechanism were investigated. Raman spectrum shows four first-order phonon frequencies and a second-order Raman frequency of the ZnO nanowires. Electrical and photoconductive performance of individual ZnO straight nanowire devices was studied. The results indicate that the nanowires reported here are n-type semi-conductors and UV light sensitive, and a desirable candidate for fabricating UV light nanosensors and other applications.     

Spectroscopic Investigation of Quantum Confinement Effects in Ion Implanted Silicon-on-Sapphire Films

Crystalline Silicon-on-Sapphire (SOS) films were implanted with boron (B⁺) and phosphorous (P⁺) ions. Different samples, prepared by varying the ion dose in the range 10¹⁴–5 × 10¹⁵ and ion energy in the range 150–350 keV, were investigated by the Raman spectroscopy, photoluminescence (PL) spectroscopy and glancing angle x-ray diffraction (GAXRD). The Raman results from dose dependent B⁺ implanted samples show red-shifted and asymmetrically broadened Raman line-shape for B⁺ dose greater than 10¹⁴ ions cm⁻². The asymmetry and red shift in the Raman line-shape is explained in terms of quantum confinement of phonons in silicon nanostructures formed as a result of ion implantation. PL spectra shows size dependent visible luminescence at ∼1.9 eV at room temperature, which confirms the presence of silicon nanostructures. Raman studies on P⁺ implanted samples were also carried out as a function of ion energy. The Raman results show an amorphous top SOS surface for sample implanted with 150 keV P⁺ ions of dose 5 × 10¹⁵ ions cm⁻². The nanostructures are formed when the P⁺ energy is increased to 350 keV by keeping the ion dose fixed. The GAXRD results show consistency with the Raman results.     

Doublet of D and 2D bands in graphene deposited with Ag nanoparticles by surface enhanced Raman spectroscopy

Surface enhanced Raman spectrum of graphene was obtained by modifying graphene with Ag nano-particles. The doublet of D band and 2D band was observed due to surface enhanced Raman scattering (SERS) enhancement and relaxation of the selection rules originated from the interaction of Ag nano-particles and graphene. The difference in the doublet of D band in which the separation between the two peaks is 11 cm⁻¹ is close to the theoretical value of 9 cm⁻¹ and can be attributed to the disorder and edge effect. The doublet of 2D band can be assigned to the asymmetry of dispersion relation along KM and KГ respectively. The phonon mode at 1510 cm⁻¹ can be associated with the iTO phonon near ГK/4. This confirms the phonon dispersion based on double resonance (DR) theory in iTO branch.     

Theory of Raman Scattering by Phonons in Germanium Nanostructures

Within the linear response theory, a local bond-polarization model based on the displacement–displacement Green’s function and the Born potential including central and non-central interatomic forces is used to investigate the Raman response and the phonon band structure of Ge nanostructures. In particular, a supercell model is employed, in which along the [001] direction empty-column pores and nanowires are constructed preserving the crystalline Ge atomic structure. An advantage of this model is the interconnection between Ge nanocrystals in porous Ge and then, all the phonon states are delocalized. The results of both porous Ge and nanowires show a shift of the highest-energy Raman peak toward lower frequencies with respect to the Raman response of bulk crystalline Ge. This fact could be related to the confinement of phonons and is in good agreement with the experimental data. Finally, a detailed discussion of the dynamical matrix is given in the appendix section.     

Pressure‐dependent Raman modes near the cubic‐tetragonal transition in strontium titanate

The pressure dependence of the Raman frequency shifts of various Raman modes is calculated at room temperature using the volume data from the literature for the cubic‐tetragonal transition in SrTiO₃. The isothermal mode Grüneisen parameters of those Raman modes are obtained, which decrease with increasing pressure for this molecular crystal. Calculated Raman frequencies are then used to predict the damping constant and the inverse relaxation time of those Raman modes as a function of pressure by means of the pseudospin‐phonon (PS) coupled model and the energy fluctuation (EF) model to describe the cubic‐tetragonal transition in SrTiO₃. Also, the values of the activation energy are extracted for the Raman modes studied using both models (PS and EF). Our predicted damping constant and the inverse relaxation time for the Raman modes, can be compared with the experimental measurements close to the cubic‐tetragonal transition in SrTiO₃.     

Polarization dependence of double resonant Raman scattering band in bilayer graphene

The polarization dependence of the double resonant Raman scattering (2D) band in bilayer graphene (BLG) is studied as a function of the excitation laser energy. It has been known that the complex shape of the 2D band of BLG can be decomposed into four Lorentzian peaks with different Raman frequency shifts attributable to four individual scattering paths in the energy–momentum space. From our polarization dependence study, however, we reveal that each of the four different peaks is actually doubly degenerate in its scattering channels, i.e., two different scattering paths with similar Raman frequency shifts for each peak. We find theoretically that one of these two paths, ignored for a long time, has a small contribution to their scattering intensities but are critical in understanding their polarization dependences. Because of this, the maximum-to-minimum intensity ratios of the four peaks show a strong dependence on the excitation energy, unlike the case of single-layer graphene (SLG). Our findings thus reveal another interesting aspect of electron–phonon interactions in graphitic systems.     

High temperature crystallographic and low temperature magnetic phase transitions in Fe doped Sr2RuMnO6

Fe doped Sr₂RuMnO₆ (SRMO) double perovskites (Sr₂RuMn_1-xFe_xO₆, x = 0, 0.1, 0.2 and 0.3) were prepared by solid-state route. Both x-ray diffraction and Raman spectroscopy were performed to investigate the crystal structure of the synthesized double perovskites. Rietveld refinement of the x-ray diffraction patterns confirmed a phase transition from tetragonal to cubic space group as a function of doping concentration of iron. Raman spectroscopy at room temperature and group theory analysis revealed the phonon modes associated with the space group of the samples. The temperature dependent Raman spectroscopy showed an anharmonic behaviour of the phonon modes of the Fe doped SRMO samples. The temperature evolution of the phononic modes in the range of 300 K–620 K is predominantly influenced by the lattice degrees of freedom. The presence of several oxidation states Mn (2⁺, 3⁺ and 4⁺) and Fe (3⁺ and 4⁺) was confirmed by an X-ray photoemission spectroscopy analysis of the highest doped sample (x = 0.3). The magnetic properties measurements showed that the samples were completely paramagnetic at room temperature. The samples exhibit antiferromagnetism at very low temperatures and we conclude that they exhibit ferrimagnetic ground state in the mid temperature region.     

声子态密度对掺稀土玻璃材料上转换发光强度的影响

用熔融法制备了碲酸盐玻璃(PWT)和锗酸盐玻璃(PWG),测试了它们的上转换发光。试验发现声子能量高的锗酸盐玻璃上转换发光强度远强于声子能量低的碲酸盐玻璃上转换荧光的“异常”现象。从物理模型及其物理意义上,并从Raman光谱定性分析得知,当基质材料的声子能量相差不大时,声子态密度对上转换发光强度起决定性作用,从而能对试验现象进行较为圆满的解释。     

Raman scattering by confined optical phonons in Si and Ge nanostructures

A microscopic theory of the Raman scattering based on the local bond-polarizability model is presented and applied to the analysis of phonon confinement in porous silicon and porous germanium, as well as nanowire structures. Within the linear response approximation, the Raman shift intensity is calculated by means of the displacement-displacement Green's function and the Born model, including central and non-central interatomic forces. For the porous case, the supercell method is used and ordered pores are produced by removing columns of Si or Ge atoms from their crystalline structures. This microscopic theory predicts a remarkable shift of the highest-frequency of first-order Raman peaks towards lower energies, in comparison with the crystalline case. This shift is discussed within the quantum confinement framework and quantitatively compared with the experimental results obtained from porous silicon samples, which were produced by anodizing p--type (001)-oriented crystalline Si wafers in a hydrofluoric acid bath.     

Raman spectroscopy on isolated single wall carbon nanotubes

A review is presented on the resonance Raman spectra from one isolated single wall carbon nanotube. The reasons why it is possible to observe the spectrum from only one nanotube are given and the important structural information that is provided by single nanotube spectroscopy is discussed. Emphasis is given to the new physics revealed by the various phonon features found in the single nanotube spectra and their connection to spectra observed for single wall nanotube bundles. The implications of this work on single wall carbon nanotube research generally are also indicated.     

Phonon transport in helically coiled carbon nanotubes

We perform theoretical studies on the phonon thermal transport in helically coiled carbon nanotubes (HCCNTs). The Grüneisen parameter, as a function of the phonon wave vector and phonon branch, is numerically evaluated for each vibrational mode, so that the three-phonon Umklapp scattering rates can be calculated exactly by taking into account all allowed phonon relaxation channels. We considered wide temperature range and heat conductor lengths from nano- to macro-scale. We examine the crossover from ballistic to diffusive transport regime and impact of HCCNT geometrical parameters on their heat conduction. Thermal conductivity in HCCNTs is found to be slightly lower than that in single walled carbon nanotubes (SWCNTs). This is interpreted by the competition among three factors. Firstly, threefold reduction of the Grüneisen parameter for the acoustic branches. Secondly, lower phonon group velocities. Finally, availability of purely acoustic scattering channels. Nevertheless, HCCNTs are predicted to be more suitable (than SWCNTs) for thermal management applications due to their spring-like shape. HCCNTs are extremely elastic, natural NanoVelcro material.     

Temperature-dependent Raman investigation of rolled up InGaAs/GaAs microtubes

Large arrays of multifunctional rolled-up semiconductors can be mass-produced with precisely controlled size and composition, making them of great technological interest for micro- and nano-scale device fabrication. The microtube behavior at different temperatures is a key factor towards further engineering their functionality, as well as for characterizing strain, defects, and temperature-dependent properties of the structures. For this purpose, we probe optical phonons of GaAs/InGaAs rolled-up microtubes using Raman spectroscopy on defect-rich (faulty) and defect-free microtubes. The microtubes are fabricated by selectively etching an AlAs sacrificial layer in order to release the strained InGaAs/GaAs bilayer, all grown by molecular beam epitaxy. Pristine microtubes show homogeneity of the GaAs and InGaAs peak positions and intensities along the tube, which indicates a defect-free rolling up process, while for a cone-like microtube, a downward shift of the GaAs LO phonon peak along the cone is observed. Formation of other type of defects, including partially unfolded microtubes, can also be related to a high Raman intensity of the TO phonon in GaAs. We argue that the appearance of the TO phonon mode is a consequence of further relaxation of the selection rules due to the defects on the tubes, which makes this phonon useful for failure detection/prediction in such rolled up systems. In order to systematically characterize the temperature stability of the rolled up microtubes, Raman spectra were acquired as a function of sample temperature up to 300°C. The reversibility of the changes in the Raman spectra of the tubes within this temperature range is demonstrated.