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.     

Effects of green laser fluence on the characteristics of graphene nanosheets synthesized by laser ablation method in liquid nitrogen medium

We have studied the effects of laser fluence on the characteristics of graphene nanosheets produced by pulsed laser ablation technique. In this work, The second harmonic of a Q-switched Nd:YAG laser at 532 nm wavelength and 5 Hz repetition rate with different laser fluences in the range of 0.5–1.8 J/cm² was used to irradiate the graphite target in liquid nitrogen medium. The products of ablation were characterized using Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray diffraction pattern, UV–Vis absorption spectroscopy, Raman spectrum and transmission electron microscopy. The Raman spectroscopy indicates that the quality of the graphene nanosheets was decreased while their structure defects were increased as the laser fluence was increased from 0.5 to 1.4 J/cm². Our results suggest that the amount of defects and the number of layers in graphene nanosheets can be changed by adjusting the laser fluence. This study could be a useful guidance for producing of high quality of graphene nanosheets by laser ablation method.     

Stress‐dependent correlations for resonant Raman bands in graphite with defects

We have studied the Raman features characteristics of defects generated in graphite under high stress conditions. Defects are generated in pristine highly oriented pyrolytic graphite by squeezing the samples in a high‐pressure anvil cell and monitored in situ by Raman spectroscopy. On the basis of our Raman measurements and existing literature correlations, we conclude that vacancies and grain boundaries are generated during compression–decompression cycles, being the defects mostly generated during the decompression stage. Our results demonstrate that the relative intensities of the D, D′, and (D + D′) bands are strongly correlated. Which is important for practical application of Raman spectroscopy in the characterization of carbon materials is that such correlations are essentially constant over the whole stress range covered in the experiments (~7 GPa). An additional interesting result concerns the relative intensities of the denoted 2D₁ and 2D₂ contributions, which are correlated with the intensity of the G band; the intensity ratio between both features is modified by stress indicating that the stress affects the stacking order of pristine graphite. Finally, we find that the decrease in intensity of the 2D₂ band with decreasing crystallite size found in existing studies on unstrained graphite remains under stress conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman spectroscopic studies of pulsed laser‐induced defect evolution in graphene

Raman spectra were obtained for graphene after irradiating the samples by pulsed laser (λ = 248 nm). Changes in the spectra were observed as the pulse laser energy density (PLED) was varied from 0.1 to 0.25 J/cm². Changes in bilayer graphene were accompanied by the appearance of the D peak and the broadening of the G peak. Changes in multilayer graphene are more profound as the Raman spectra changes from a multilayer to bilayer and subsequently to monolayer graphene in response to a slow increase in the PLED. The threshold PLED was found to be dependent on the number of graphene layers. We also irradiate graphene with very high PLED (much above the threshold), and the Raman spectra were found to be significantly changed. The G‐band became broader, and red shifted, while the intensity of the 2D‐band was drastically reduced and an intense defect‐related D peak appeared at about 1350 cm⁻¹. The laser ablation of graphene, both with low‐ and high‐energy intensity, is consistent with the reported theoretical predictions. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural evolution in CVD graphene chemically oxidized by sulphuric acid

The role of sulphuric acid (H₂SO₄) in fabrication graphene oxide besides as intercalant has not been well addressed. In this work, Raman spectroscopy is used to monitor structural evolution in chemical vapor deposition (CVD) graphene chemically oxidized by dilute H₂SO₄. From the analysis of Raman spectra of oxidized graphene, we propose that oxidation first initiates at preexisting defects, and vacancy‐like defects are formed. Following is the radial growth of the vacancy, and oxidation pits appear in graphene. This assumption is further confirmed by atomic force microscope measurement. It is also found that with increase of amounts of defects, G peak is blue shift, and this is explained by defect and hole doping effect. Hole doping in graphene is much stronger at hexagon regions near the oxidation pits. This work helps in understanding the role of H₂SO₄ in fabrication graphene oxide as oxidizer as well as helps in obtaining structure information of graphene oxide. Copyright © 2015 John Wiley & Sons, Ltd.     

The thermal stability of graphene in air investigated by Raman spectroscopy

The thermal stability in air of graphene synthesized by either chemical vapor deposition or mechanical cleavage is studied. It is found that single layer graphene prepared by both methods starts to show defects at ~500 °C, indicated by the appearance of a disorder‐induced Raman D peak. The defects are initially sp³ type and become vacancy like at higher temperature. On the other hand, bilayer graphene shows better thermal stability, and the D peak appears at ~600 °C. These results are quite different from those annealing in vacuum and controlled atmosphere. Raman images show that the defects in chemical vapor deposition graphene are not homogeneous, whereas those in mechanical cleavage graphene are uniformly distributed across the whole sample. The factors that affect the thermal stability of graphene are discussed. Our results could be important for guiding the future electronics process and chemical decoration of graphene. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface-enhanced Raman spectroscopy of hexabenzobenzene,C24H12, an analogue of a graphene nanostructure

While large scale fabrication of graphene nanoribbons remains a challenge, there exist materials which can be fabricated in quantities such as hexabenzobenzene,HBZB, (C₂₄H₁₂) and which have a two-dimensional (2D) carbon structure similar to graphene nanostructures. Using a 632 nm laser, no Raman spectra could be obtained from the solid material because of a strong luminescence produced by the laser. However, surface-enhanced Raman spectroscopy enabled the measurement of some of the Raman active modes. The G and D modes, which are characteristic fingerprints of a 2D graphene structure, were observed at 1331 and 1600 cm^?1, respectively. Density functional theory at the B3LYP/6-31G^* level was used to calculate the minimum energy structure and the Raman active vibrational frequencies of HBZB. The calculated minimum energy structure was 2D having D_6h symmetry in agreement with the experimental structure in the liquid phase. The calculated frequencies were in good agreement with the measured values.     

Confocal Raman spectromicroscopy for tin-core/carbon-shell nanowire heterostructure

High density heterostructures of carbon nanotubes encapsulated single crystalline tin nanowires have been characterized by Raman spectromicroscopy. The morphology, composition and structure of the synthesized nanoheterostructures were examined by using scanning electron microscopy, transmission electron microscopy. The Raman spectra obviously manifest the crystalline nano-graphite within amorphous carbon walls in the heterostructures. The Raman image reproduces the pristine heterostructures of the CNTs as seen in SEM image, which illustrate the single nanowires oriented uniformly grown on micro-graphitic fibers. It was found that the resultant heterostructures are luminescent which was attributed to crystalline nano-graphite embedded in the amorphous carbon matrix, which is a consequence of excitons localization within an increasing number of sp² rich clusters. The contrast in the Raman image reflects nonuniform distribution of the graphite cluster size which acts as the radiative centers. The luminescent property was reviewed. The enhanced Raman spectra and luminescent property by the well-defined tin nanowires inside the heterostructures was revealed.     

Influence of the buffer layer properties on the intensity of Raman scattering of graphene

Using a model of oscillating dipoles, we simulate the intensity of the G‐band in the Raman signal from structures consisting of graphene, separated by an arbitrary buffer layer from a substrate. It is found that a structure with an optimized buffer layer refractive index and thickness exhibits a Raman signal which is nearly 50 times more intense than that from the same structure with a non‐optimized buffer layer. The theoretical simulations are verified by Raman measurements on structures consisting of a layer of graphene on SiO₂ and Al₂O₃ buffer layers. The optical contrast of the single graphene layer is calculated for an arbitrary buffer layer. It was found that both the Raman intensity and optical contrast can be maximized by varying the buffer layer thickness. Copyright © 2013 John Wiley & Sons, Ltd.     

A novel combinative Raman and SEM mapping method for the detection of exfoliation of graphite in electrodes at very positive potentials

The random exfoliation at very positive potentials (>5 V vs Li/Li⁺) of graphite (used as a conductive component in positive electrodes of lithium‐ion batteries) was investigated with in situ Raman microscopy and post mortem scanning electron microscopy (SEM). A novel semiautomated computational method for the data analysis of both characterization methods was developed to correlate Raman and SEM information with good lateral resolution, in order to locate exfoliated graphite particles. Proof is given that the exfoliating particles detected via the semiautomatic in situ Raman microscopy mappings correctly describes exfoliated areas, as confirmed via post mortem SEM pictures. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of micropipes in 6H-SiC by Raman scattering

The spectra of 6H-SiC crystals including micropipes have been examined for the Si face using Raman scattering. The first-order Raman features reveal that the intensity of the transverse optical phonon band centered at ∼796 cm⁻¹ is sensitive to the micropipes. And the second-order Raman features of the micropipes in bulk 6H-SiC are well-defined using the selection rules for second-order scattering in wurtzite structure. It is found that there are some second-order peaks missing for the micropipe-including sample, which may be induced by the reduction of the incident laser intensity at around the micropipe, especially the uneven surface in the inner wall of the micropipe. These features might also be employed to characterize other structural defects such as screw-dislocations and threading edge dislocations.     

Sonochemical preparation of bismuth oxide nanotiles decorated exfoliated graphite for the electrochemical detection of imipramine

This work described the sonohydrolysis of Bi(NO₃)₃ into Bi₂O₃ and simultaneous sonochemical exfoliation of graphite into graphene sheets in the alkaline environment and its electocatalytic performance towards the detection of anti-depression drug imipramine (IMPR). The ultrasound (37/80 kHz; 60 W) effectively hydrolyzed the Bi(NO₃)₃ into a single crystalline monoclinic phase of Bi₂O₃ nanotiles in the alkaline condition. And also, the sonochemical reaction condition can trigger the lamellar particles on the graphite bulk surface and allowed to exfoliated the graphite (EG) into graphene nanosheets as well. The material characterizations are done by XRD, Raman, FESEM, and HRTEM. It shows the α-Bi₂O₃ nanotiles along with EG nanosheets with high crystallinity and low defects. The (0 0 2) plane in XRD confirms the high crystalline nature of EG. The monoclinic stretching vibrations (90–600 cm⁻¹) confirms the Raman modes of Bi₂O₃. The prepared Bi₂O₃-EG composites are subjected to the electrochemical determination of IMPR which revealed appreciable analytical performances. The results showed that the Bi₂O₃-EG exhibits better results in the 3 h sonication process. Bi₂O₃-EG-3 exhibited a good linear range (0.02–82.3 µM) and an acceptable limit of detection (6 nM). And also Bi₂O₃-EG-3 exhibits the significant tolerance limit when compared to other potential interfering compounds.     

Raman spectroscopy study of twisted tetralayer graphene

We present a systematic Raman study of twisted tetralayer graphene (t(2 + 2)LG), under excitation of two laser lines. In t(2 + 2)LG samples, top Bernal stacked bilayer graphene (2LG stands for Bernal‐stacked bilayer graphene) twists different angle relative to bottom 2LG. It is found that 2D and 2D′ peaks of t(2 + 2)LG show positive wavenumber shift relative to those of 2LG. We propose a simplified electronic band structure for t(2 + 2)LG; interlayer interaction‐induced changing in electronic band structure can be used to understand the aforementioned spectral features. The electronic structures of t(2 + 2)LG samples are then probed from resonant Raman studies of 2D and 2D′ peaks using two laser lines; electronic dispersions in t(2 + 2)LG samples are given. Our study facilitates understanding of twist angle‐dependent electronic properties of tetralayer graphene superlattice. Copyright © 2016 John Wiley & Sons, Ltd.     

Irradiation effects in CaF2 probed by Raman scattering

The formation conditions and dynamics of Ca colloids and point defects that appear in irradiated single crystals of CaF₂ were investigated by Raman spectroscopy. The intensity changes in the Raman spectra because of the presence of different concentrations of point defects and Ca colloids that emerged in CaF₂ after irradiation with 2.2 GeV Au ions were used to study their distribution and stability under illumination with three laser wavelengths (473, 532 and 633 nm) at different output powers (2 to 200 mW). A damage saturation at a fluence of 6 × 10¹¹ ion cm⁻² was observed. The dependence of the spectral changes on the ion fluence can be described by a core/halo damage cross‐section model. A radius of 13–18 nm was obtained for the outer (halo) cylinder, in agreement with previous swelling studies. Illuminations of irradiated samples with blue (473 nm) and green (532 nm) lasers were found to be extremely efficient in bleaching the samples, while illumination with a red (633 nm) laser did not lead to a sample recovery. This indicates that the bleaching process is governed by recombination of point defects that have to overcome an energy barrier. Typical time constants for the processes involved are presented. Copyright © 2016 John Wiley & Sons, Ltd.     

Evidence of laser induced decomposition of triaminotrinitrobenzene from surface enhanced Raman spectroscopy

It is observed that the focused 632 nm laser of the confocal micro-Raman spectrometer decomposes triaminotrinitrobenzene (TATB). The temperature generated in the laser spot determined by measuring the ratio of the intensities of the anti-Stokes to Stokes spectra is too low to cause thermal decomposition. The observed decomposition is suggested to be a result of laser induced electronic excitation. The decomposition is even more severe when measured by surface enhanced Raman spectroscopy (SERS) where it results in a highly defected graphite structure. A gold coated silicon substrate having an array of pyramidal shaped holes is used to obtain surface enhanced Raman spectra of TATB deposited on the substrate as a 10^?3 molar solution of toluene.     

HRTEM and Raman study of onion-like fullerenes encapsulated Fe

Onion-like fullerenes (OLFs) encapsulated Fe have been synthesized by chemical vapor deposition (CVD). The samples have been characterized by HRTEM and Raman methods. The diameters of OLFs encapsulated Fe are in the range from 15 to 40 nm with pure Fe particles. HRTEM and Raman spectra show that OLFs are highly graphite. XRD spectrum shows Fe nanoparticles are protected in OLFs and are not oxidized by air. It is the stain of graphene shells and the uneven size of OLFs encapsulated Fe that causes the Raman spectra to shift downward slightly from 1580 cm⁻¹.     

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.     

Curcumin-assisted ultrasound exfoliation of graphite to graphene in ethanol

In this paper, we demonstrated a simple and cost-effective method to produce graphene from graphite in ethanol using ultrasound assisted with curcumin. The influence of curcumin concentration, starting graphite amount, sonication power, and sonication time on the graphene concentration was studied schematically. The π-π interaction between curcumin and graphene, being confirmed by FTIR spectrum, facilitate the exfoliation of the graphite into graphene. The concentration of the graphene in the ethanol reached up to 1.44 mg mL⁻¹ and the exfoliated suspension was relatively stable. The content of monolayer, bilayer, and multilayer in the exfoliated graphene suspension were 21%, 37%, and 42%, respectively. The as-prepared graphene sheets were free-defect. This novel approach may not only enable to exfoliate the graphite into graphene but also to make the graphene-curcumin hybrid which might find applications in pharmaceutical industry.     

”Eau de graphene” from a KC8 graphite intercalation compound prepared by a simple mixing of graphite and molten potassium

We synthesized KC₈ by simply mixing molten potassium and graphite at 180 °C under inert atmosphere. The KC₈ shows typical shiny bronze color, Raman characteristics and XRD pattern of an efficiently intercalated stage 1 GIC, and is of sufficient quality to produce fully exfoliated graphenide solutions in tetrahydrofuran (THF) and subsequently single layer graphene in water as ”eau de graphene” (EdG). The evolution of absorption and Raman spectroscopic signatures of the EdG as a function of processing conditions give key indications on the number of layers of the graphene flakes dispersed in EdG. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)