Raman characterization of bulk ferromagnetic nanostructured graphite

Raman spectroscopy was used to characterize bulk ferromagnetic graphite samples prepared by controlled oxidation of commercial pristine graphite powder. The G:D band intensity ratio, the shape and position of the 2D band and the presence of a band around 2950 cm⁻¹ showed a high degree of disorder in the modified graphite sample, with a significant presence of exposed edges of graphitic planes as well as a high degree of attached hydrogen atoms.     

Tip-Enhanced Raman Spectroscopy and Mapping of Graphene Sheets

Abstract: Single graphene sheets, a few graphene layers, and bulk graphite, obtained via both micromechanical cleavage of highly oriented pyrolytic graphite and carbon vapor deposition methods, were deposited on a thin glass substrate without the use of any chemical treatment. Micro-Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS), and tip-enhanced Raman spectroscopy mapping (TERM) were used for characterization of the graphene layers. In particular, TERM allows for the investigation of individual graphene sheets with high Raman signal enhancement factors and allows for imaging of local defects with nanometer resolution. Enhancement up to 560% of the graphene Raman band intensity was obtained using TERS. TERM (with resolution better than 100 nm) showed an increase in the number of structural defects (D band) on the edges of both graphene and graphite regions.     

Raman scattering characterization of a carbon coating after low-energy argon ion bombardment

The characteristic of Raman scattering spectra of a carbon coating, which was modified by radio frequency argon plasma, has been investigated. The argon ion bombardment causes changes in the microstructure and amount of stress in the coating. Raman scattering spectra are discussed in terms of intensity, bandwidth and wavenumber. The evolvement of Raman spectra shows the following behavior with increasing bombardment time: the intensity changes of the disordered D band, amorphous D″ band and graphite G band could be separated into several stages; low-energy argon ion bombardment over a short period can reduce the number of defects in the carbon coating, while a larger bombardment period can increase the number of defects; the widths of the D and G bands both increase, while that of the D″ band decreases; the wavenumbers of all the three bands fluctuate according to the changes in electronic configuration and amount of stress in the carbon coating.     

Changes in the vibrational modes of carbon nanotubes induced by electron‐beam irradiation: resonance Raman spectroscopy

Influence of electron‐beam (e‐beam) irradiation on multi‐walled (MW) and single‐walled (SW) carbon nanotube films grown by microwave chemical vapor deposition technique is investigated. These films were subjected to an e‐beam energy of 50 keV from a scanning electron microscope for 2.5, 5.5, 8.0, and 15 h, and to 100 and 200 keV from a transmission electron microscope for a few minutes to ∼2 h continuously. Such conditions resemble an increased temperature and pressure regime enabling a degree of structural fluidity. To assess structural modifications, they were analyzed prior to and after irradiation using resonance Raman spectroscopy (RRS) in addition to in situ monitoring by electron microscopy. The experiments showed that with extended exposures, both types of nanotubes displayed various local structural instabilities including pinching, graphitization/amorphization, and formation of an intramolecular junction (IMJ) within the area of electron beam focus possibly through amorphous carbon aggregates. RRS revealed that irradiation generated defects in the lattice as quantified through (1) variation of the intensity of radial breathing mode (RBM), (2) intensity ratio of D to G band (I_D/I_G), and (3) positions of the D and G bands and their harmonics (D* and G*) and combination bands (D + G). The increase in the defect‐induced D band intensity, quenching of RBM intensity, and only a slight increase in G band intensity are some of the implications. The MW nanotubes tend to reach a state of saturation for prolonged exposures, while the SW ones transform from a semiconducting to a quasi‐metallic character. Softening of the q = 0 selection rule is suggested as a possible reason to explain these results. Furthermore, these studies provide a contrasting comparison between MW and SW nanotubes. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Raman study on electrochemical lithium insertion into multiwalled carbon nanotubes

We have carried out in situ Raman studies during the electrochemical insertion of lithium ions (Li⁺) into pristine and thermally treated multiwalled carbon nanotubes (MWNTs). We found an improved structural integrity as well as the removal of defects in the thermally treated tubes. The different Li⁺ insertion behaviors above 0.5 V in as‐grown and thermally treated tubes could be explained by the presence of defects on the outer surface of the tubes. No change of Raman spectra from 2.8 to 0.8 V is characterized by the coverage of Li⁺ on the outer surface of tubes, whereas the upshift of G band and the absence of a separated G band below 0.75 V indicate the formation of diluted graphite intercalation below the stage‐2 phase (LiC₁₂). Copyright © 2008 John Wiley & Sons, Ltd.     

Invoking forbidden modes in SnO2 nanoparticles using tip enhanced Raman spectroscopy

Raman forbidden modes and surface defect‐related Raman features in SnO₂ nanostructures carry information about disorder and surface defects which strongly influence important technological applications like catalysis and sensing. Because of the weak intensities of these peaks, it is difficult to identify these features by using conventional Raman spectroscopy. Tip enhanced Raman spectroscopy (TERS) studies conducted on SnO₂ nanoparticles (NPs) of size 4 and 25 nm have offered significant insights of prevalent defects and disorders. Along with one order enhancement in symmetry allowed Raman modes, new peaks related to disorder and surface defects of SnO₂ NPs were found with significant intensity. Temperature‐dependent Raman studies were also carried out for these NPs and correlated with the TERS spectra. For quasi‐quantum dot sized 4‐nm NPs, the TERS study was found to be the best technique to probe the finite size‐related Raman forbidden modes. Copyright © 2015 John Wiley & Sons, Ltd.     

The Raman spectra and cross-sections of the ν2 band of H2O, D2O, and HDO

We report the experimental Raman spectra of the ν₂ band of H₂O, D₂O, and HDO in the vapor phase at room temperature. A complete interpretation of the Raman intensities is carried out employing the variational rovibrational wavefunctions obtained from a Hamiltonian in Radau coordinates and an ab initio polarizability surface at 514.5 nm. We show the importance of the rotation-vibration coupling to obtain the correct line intensities. Several tables with the assignments of the individual rotational-vibrational transitions and their Raman scattering strengths are reported. From these tables, the ν₂ Raman spectra can be simulated up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Raman and surface-enhanced Raman spectroscopy evidence for oxidation-induced decomposition of graphite

It has been proposed that reduction of exfoliated graphite oxide could be a potential method for producing large quantities of graphene. Raman and surface-enhanced Raman spectroscopy are used to show that oxidation of graphite and exfoliated graphite significantly increases the defect structure of both materials. This would likely lead to a heavily defected graphene structure when oxygen is removed. To insure the observed decomposition is not due to the laser light, the effect of laser intensity on the materials was investigated. It was found that at the highest laser intensity (1.4 × 10⁸ W/M²) there was a significant increase in defects. However, lower laser intensity was found which did not produce defects and was used in the studies of the effect of oxidation on the spectra.     

湖南砂矿金刚石中石墨包裹体拉曼光谱原位测定：形成条件及成因指示

石墨是天然金刚石中最常见的包裹体之一,按其形成顺序可分为原生、同生、次生,原生/同生与次生石墨包裹体的存在指示了金刚石形成的环境及形成后可能经历的变化。对湖南沅水流域产出的13粒宝石级-半宝石级砂矿金刚石中的原生/同生石墨包裹体及次生石墨包裹体进行显微激光拉曼光谱的原位测试。测试显示,湖南沅水流域金刚石中原生/同生石墨包裹体与次生石墨包裹体的G带与D带拉曼位移均存在漂移,其中原生/同生石墨包裹体G带的漂移范围为1 591～1 600 cm-1,次生石墨的漂移范围为1 575～1 588 cm-1,显示其形成压力较低,结晶压力变化范围大。原生/同生石墨漂移程度估算出该区域压力范围为4.01～5.88 GPa,估算结果与利用橄榄石包裹体拉曼位移估算的源区压力范围基本一致。该区域内金刚石中原生/同生石墨包裹体的D带拉曼位移在1 350～1 368 cm-1之间,D带与G带的强度比(I_D/I_G值)值位于0.36～0.82之间,具有较低有序度结构/结晶程度与橄榄岩型金刚石的高结晶度石墨明显不同指示该区域部分砂矿来源的金刚石的形成深度较浅,成因与榴辉岩关系更为密切,形成过程极可能曾位于石墨-金刚石稳定域附近。研究结果表明,金刚石石墨包裹体拉曼位移的漂移程度可成为探索金刚石原生源区形成环境的有效方法之一。     

Experimental determination of the internal photoemission contribution to KLM Auger spectra of Na,Mg and Al

Photoemission from the 2p levels of the light metals excited by internally generated K_α1,2 X-rays has been observed, and the intensities compared with valence band to 2p intensity ratios obtained from X-ray photoemission spectroscopy. It is found that internal photoemission from the valence band contributes 0.5% of the intensity of the KL_2,3M Auger peak.     

Raman identification of lonsdaleite in Popigai impactites

Micro‐Raman spectroscopy and X‐ray diffraction method (XRD) were used to characterize impact carbonaceous rocks excavated from the Popigai crater (Siberia). The deconvolution of the first‐order Raman spectra of the rocks containing different amounts of carbon phases (diamond, lonsdaleite and graphite) allowed the identification of lonsdaleite spectrum. The most intensive band at 1292–1303 cm⁻¹ was ascribed to A_1g vibration mode of lonsdaleite, whereas the less intense band at 1219–1244 cm⁻¹ was attributed, in agreement with previously reported ab initio calculations, to E_2g vibration mode. The established correlation between the intensities of Raman and XRD peaks permits a rough estimation of lonsdaleite/diamond phase ratio in the impact rocks using micro‐Raman measurements. The second‐order Raman spectra of lonsdaleite–diamond rocks were recorded. Copyright © 2014 John Wiley & Sons, Ltd.     

Observation of the diameter-dependent Raman dispersion effect in chemically oxidized multiwalled carbon nanotubes

Chemical oxidation of multiwalled carbon nanotubes (MWCNTs) using H₂SO₄/HNO₃ solution has been monitored by micro-Raman spectroscopy and X-ray absorption spectroscopy. The diameter distribution variation in MWCNTs due to chemical oxidation has been measured by scanning electron microscopy and transmission electron microscopy. The Raman dispersion behaviors of the intensity ratio and the band positions of the D, G, and G′ bands were found to be correlated with the MWCNT diameter distribution. It was also found that, during the nanotube unzipping process, defect formation complicates the observation of the diameter-dependent Raman dispersion effect. The curvature effect plays an important role in the intensity ratio trend. On the other hand, defect formation dominates the band position trend.     

Multiphonon Raman spectroscopy properties and Raman mapping of 2D van der Waals solids: graphene and beyond

Strong in‐plane bonding (covalent) and weak van der Waals (vdW) interplanar interactions characterize a number of layered solids, as epitomized by graphite. The advent of graphene (Gr), individual atomic two‐dimensional (2D) layers, isolated from mineral graphite via micromechanical exfoliation enabled the ability to pick, place and stack of arbitrary compositions. Moreover, this discovery implicated an access to other 2D vdW solids beyond graphene and artificially stacking atomic layers forming heterostructures/superlattices. Raman spectroscopy (RS) is a fast reliable non‐destructive analytical tool and an integral part for lattice dynamical structural characterization of crystalline solids at nanoscale, revealing not only the collective atomic/molecular motions but also localized vibrations/modes and specifically used to determine the number of graphene layers and of other 2D vdW solids. We present Raman spectroscopy in first‐, second‐ and higher‐order vibrational modes involving 3 and 4 phonons (overtones and combination) and mapping of graphene (mono‐, bi‐, tri‐ and few‐) layers, semiconducting transition metal dichalcogenides (TMDs) [molybdenum disulfide (MoS₂) and tungsten disulfide (WS₂)] and wide bandgap hexagonal boron nitride (h‐BN) dispersed monolayers, revealing various molecular vibrations and structural quality/disorder. First‐ and higher‐order phonon modes are observed and analyzed in terms of Raman intensity (spatial inhomogeneity or thickness variation), band position (intrinsic mechanical strain) and intensity ratio (structural disorder) as a function of graphene layer (n). An empirical relation for G band position with n is corroborated. All of the higher order modes are observed to upshift almost linearly with n, betraying the underlying interlayer vdW interactions. These findings exemplify the evolution of structural parameters in layered materials in changing from 3‐ to 2‐ or low‐dimensional regime. The results are presented in view of applications of graphene by itself and in combination that help better understanding of physical and electronic properties for nano‐/optoelectronics. Copyright © 2015 John Wiley & Sons, Ltd.     

High temperature Raman spectroscopy studies of carbon nanowalls

High temperature Raman experiments were carried out on carbon nanowalls (CNWs). The intensity of the defect‐induced D mode decreased significantly after the sample was heated in air ambient. The Raman intensity ratio of D mode and G mode, I_D/I_G, changed from 2.3 at room temperature to 1.95 after the sample was heated to 600 °C. This change was attributed to the removal of surface amorphous carbon by oxidation. In contrast to I_D/I_G, the intensity ratio of the D′ mode and the G mode, I_D′/I_G, did not change much after heating, indicating that the surface amorphous carbon and surface impurity do not contribute as much to the intensity of the D′ mode. The dominant contributor to the D′ mode could be the intrinsic defects. Copyright © 2007 John Wiley & Sons, Ltd.     

Nonlinearity in Intensity versus Concentration Dependence for the Deep UV Resonance Raman Spectra of Toluene and Heptane

Abstract: The relation between Raman scattering, resonance Raman scattering, and absorption is reviewed to determine to what extent quantitative analysis can be applied in resonance Raman spectroscopy. In addition, it is demonstrated experimentally that normal Raman spectra can be dramatically inhibited by absorption and resonance Raman effects. Raman spectra of toluene and heptane mixtures—with progressively increasing concentrations of heptane—were measured using 229-nm laser excitation. The results show that the characteristic band intensities are not directly proportional to the relative concentrations of the compounds and deviate due to absorption resonance effects. An approximated mathematical model is developed to demonstrate that the intensities of the normal Raman scattering bands are suppressed. An inhibition coefficient K_i is introduced to describe the situation and determine the penetration depth. Most remarkably, it is shown that the intensity of the resonance Raman scattering bands can be constant even when the concentration ratios differ substantially in the sampled mixtures.     

Hydrogen bonding in aqueous solution of NaClO4

The ternary system NaClO₄–H₂O–D₂O has been studied, using the Raman spectroscopy. Analysis of the uncoupled OD band of HDO clearly shows that the contour of the band consists of two components only. A new approach has been developed for the quantitative evaluation of the mole fraction of bonded OD groups as a function of perchlorate concentration. It is practically impossible to measure the absolute intensity of Raman scattering. Nevertheless, it is feasible to obtain the specific coefficients of scattering per bonded OD group from the ratio of integrated intensities of the components. For this purpose, the concept of negative ‘phantom’ concentration was introduced, at which all the OD groups must be bonded. As a result, the concentration dependence of the mole fraction of bonded OD groups has been derived. It was found that the infinite network of hydrogen bonds in bulk water ceases to exist at a mole fraction of NaClO₄ above ～0.03–0.035. At higher concentration of perchlorate only residual finite clusters of water molecules can take place. However, the infinite percolation in the system remains. The important fact resulting from the data treatment is that the average number of hydrogen bonds per water molecule in pure water is 2.6?±?0.2.     

Quality improvement of single-walled carbon nanotubes by doping B in Fe/MgO catalyst

We demonstrate that the quality of the as-grown single-walled carbon nanotubes (SWCNTs) can be effectively improved by the addition of the B ingredient in the Fe/MgO catalyst. The as-grown SWCNTs were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. The SWCNTs prepared by the pure Fe/MgO catalyst have relatively low graphite crystallinity and are coated by much amorphous carbon. The intensity ratio of the D- and G-bands (I_D/I_G) in Raman spectra is relatively high (0.098 for laser 532 nm and 0.075 for laser 785 nm). The SWCNTs grown from the Fe/MgO catalyst doped with 0.1 part of B have more regular graphite structure with little amorphous carbon. The I_D/I_G values reduced remarkably (0.041 for laser 532 nm and 0.040 for laser 785 nm). The effect would be attributed to the inhibitory action of the doped B on the formation of radical hydrocarbon species for the formation of SWCNTs.     

射频反应磁控溅射法制备的氟化类金刚石薄膜摩擦特性研究

以高纯石墨做靶,CHF3和Ar气为源气体,采用射频反应磁控溅射法在不同流量比条件下制备了氟化类金刚石(F-DLC)薄膜.利用原子力显微镜、纳米压痕仪、拉曼光谱和红外光谱、摩擦磨损测试仪对薄膜的表面形貌、硬度、键结构以及摩擦性能做了具体分析.表面形貌测试结果表明,制备的薄膜整体均匀致密,表现出了良好的减摩性能.当CHF3与Ar气流量比r为1:6时,所得薄膜的摩擦系数减小至0.42,而纳米压痕结果显示,此时薄膜的硬度也最高.拉曼和红外光谱显示,随着r的增加,薄膜中的F浓度呈上升趋势,薄膜中的芳香环比例减小.研究表明,F原子的键入方式是影响F-DLC薄膜摩擦系数的一个重要因素,CF2反对称伸缩振动强度的减弱和CC中适量碳氢氟键的形成都能导致薄膜具有相对较低的摩擦系数.     

Raman Spectroscopic Characterization of Graphene

Abstract

The recent progress using Raman spectroscopy and imaging of graphene is reviewed. The intensity of the G band increases with increased graphene layers, and the shape of 2D band evolves into four peaks of bilayer graphene from a single peak of monolayer graphene. The G band will blue shift and become narrow with both electron and hole doping, whereas the 2D band will blue shift with hole doping and red shift with electron doping. Frequencies of the G and 2D band will downshift with increasing temperature. Under compressed strain, the upshift of the G and 2D bands can be found. Moreover, the strong Raman signal of monolayer graphene is explained by interference enhancement effect. As for epitaxial graphene, Raman spectroscopy can be used to identify the superior and inferior carrier mobility. The edge chirality of graphene can be determined by using polarized Raman spectroscopy. All results mentioned here are closely relevant to the basic theory of graphene and application in nanodevices.