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.     

Casimir effect demonstrated by Raman spectroscopy on trilayer graphene intercalated into stiff layered structures of surfactant

Polarized Raman scattering studies on stiff layered structure of surfactant intercalated with trilayer graphene were performed at different intensities and excitation wavelengths. The D and 2D Raman bands reach the highest and lowest intensity when the polarization of laser excitation light is oriented along and perpendicular on the edges. The 2D band discloses two lorentzian components, separated by ∼40 cm⁻¹, which result from the action of interplanar forces, of Casimir nature. The value of ∼40 cm⁻¹ is close to the energy value associated with E_2g interplanar layer shear mode evidenced so far only by neutron spectrometry. A new result regards the opposite variation of the intensities of D and 2D bands with the increase of the wavelength of the excitation light. This originates in the different origin of the D and 2D bands; the former is dependent on disorder including also the graphene edges while the latter, results from in a double resonant mechanism combined with a Casimir effect. One demonstrates that the magnitude of Casimir force, which activates interlayer vibration modes, depends on the carrier density on the graphene sheets which can be varied both by the intensity and the wavelength of the excitation laser light.     

Direct formation of graphene layers on diamond by high-temperature annealing with a Cu catalyst

The formation of high-quality graphene layers on diamond was achieved based on a high-temperature annealing method using a Cu catalyst. Typical features of monolayer graphene were observed in the Raman spectra of layers formed by annealing of Cu/diamond heterostructures at 950 °C for 90 min. The coverage ratio of these graphene layers on diamond was estimated to be on the order of 85% by Raman mapping of the 2D peak. The sheet hole concentration and mobility values of the layers were estimated to be ~ 10¹³ cm^− 2 and ~ 670 cm²/Vs, respectively. These values are comparable to those previously observed for high-quality graphene layers on SiC.     

Graphene synthesis by C implantation into Cu foils

Cu foils of 2 × 2 cm² have been implanted with 70 keV C⁻ ions to nominal fluences of (2–10) × 10¹⁵ cm⁻² at room temperature (RT) and subsequently annealed at 900–1100 °C for 15 min, before being cooled to RT to form graphene layers on the Cu surfaces. Analyses with Raman spectroscopy and atomic force microscopy demonstrate that a continuous film of bi-layer graphene (BG) is produced for implant fluences as low as 2 × 10¹⁵ cm⁻², much less than the carbon content of the BG films. This suggests that the implanted carbon facilitates the nucleation and growth of graphene, with additional carbon supplied by the Cu substrate (0.515 ppm carbon content). No graphene was observed on unimplanted Cu foils subjected to the same thermal treatment. This implantation method provides a novel technique for the selective growth of graphene on Cu surfaces.     

High quality graphene sheets from graphene oxide by hot-pressing

We report a simple and effective route to convert graphene oxide sheets to good quality graphene sheets using hot pressing. The reduced graphene oxide sheets obtained from graphene oxide by low temperature thermal exfoliation are annealed at 1500 °C and 40 MPa uniaxial pressures for 5 min in vacuum. No appreciable oxygen content was observed from X-ray photoelectron spectroscopy and no D peak was detected in the Raman spectrum. The graphene sheets produced had a much higher electron mobility (1000 cm² V⁻¹ S⁻¹) than other chemically modified graphenes.     

Bomb calorimetry as a bulk characterization tool for carbon nanostructures

Multiwalled carbon nanotubes (MWCNTs) consisting of coaxial graphene cylinders (cylindrical MWCNTs), cones (herringbone MWCNTs) or carbon fibers were combusted in an isothermal bomb calorimeter. Their standard enthalpies of formation were determined to be 16.56 ± 2.76 kJ mol⁻¹(C – per carbon mol) for carbon fibers, 21.70 ± 1.32 kJ mol⁻¹(C) for herringbone MWCNTs and 8.60 ± 0.52 kJ mol⁻¹(C) for cylindrical ones. All materials were characterized by transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, thermogravimetry, and elemental analysis. A linear correlation between the standard enthalpies of formation and D/G and G′/G Raman bands ratio (D – band is centered at 1350 cm⁻¹, G – 1585 cm⁻¹, G′ – 2700 cm⁻¹) demonstrates the applicability of bomb calorimetry for characterization of the “defectiveness” of the bulk carbon material in the sense Raman spectroscopy is widely used nowadays. Also, we show that the calorimetry may be used to estimate the oxygen content in the bulk carbon nanomaterials, as there is a linear correlation between the oxygen content (both total content and in carboxyl groups separately) and the standard enthalpies of formation for herringbone nanotubes oxidized by nitric acid.     

Densification and properties of transition metal borides-based cermets via spark plasma sintering

Engineering borides like TiB₂ and ZrB₂ are difficult to sinter materials due to strong covalent bonding, low self-diffusion coefficient and the presence of oxide layer on the powder particles. The present investigation reports the processing of hard, tough and electrically conductive transition metal borides (TiB₂ and ZrB₂) based cermets sintered with 6 wt.% Cu using spark plasma sintering (SPS) route. SPS experiments were carried out with a heating rate of 500 K/min in the temperature range of 1200–1500 °C for a varying holding time of 10–15 min and the optimization of the SPS conditions is established. A maximum density of ∼95% ρ_th in ZrB₂/Cu and ∼99% ρ_th in TiB₂/Cu is obtained after SPS processing at 1500 °C for 15 min. While the optimized TiB₂/Cu cermet exhibits hardness and fracture toughness of ∼17 GPa and ∼11 MPa m^1/2, respectively, the optimized ZrB₂/Cu cermet has higher hardness of ∼19 GPa and fracture toughness of ∼7.5 MPa m^1/2, respectively. High electrical conductivity of ∼0.20 MΩ⁻¹ cm⁻¹ (TiB₂/Cu) and ∼0.15 MΩ⁻¹ cm⁻¹ (ZrB₂/Cu) are also measured with the optimally sintered cermets.     

Carbon nanofibres produced from electrospun cellulose nanofibres

Cellulose nanofibres have been fabricated by electrospinning of a cellulose acetate solution followed by deacetylation. The cellulose nanofibres were then carbonized using temperatures in the range 800–2200 °C and the resulting carbon nanofibres (CNFs) were characterized using transmission electron microscopy, X-ray diffraction and Raman spectroscopy. A graphitic structure was observed for CNFs treated at a relatively low temperature of 1500 °C, with no obvious skin-core heterogeneity observed for fibres treated up to 2200 °C, suggesting a possible advantage of using nano-scale precursors. The effective Young’s modulus of the CNFs was assessed using an in situ Raman spectroscopic technique following the shift in the position of the G′ (2D) band located at ∼2660 cm⁻¹ and relating this to a calibration established for a range of other carbon fibres. Using this approach the moduli of the CNFs were found to be ∼60 and ∼100 GPa for samples carbonized at 1500 and 2200 °C, respectively.     

Characterization of free-standing single-crystal diamond prepared by hot-filament chemical vapor deposition

Hot filament chemical vapor deposition (HFCVD) possesses a large potential to scale-up for the growth of single-crystal diamond (SCD). This study investigates the crystalline qualities of SCD fabricated by HFCVD. A tungsten impurity level of 10¹⁸ cm^− 3 was detected with secondary ion mass spectroscopy. The full-width at half maximum (FWHM) of the rocking curve (004) was 39.5 arcsec, where that of seed substrates was 42.8 arcsec. A clear free-exciton recombination radiation was observed in cathodoluminescence spectra. The Raman spectra presented a single peak centered at 1333.2 cm^− 1 with a FWHM value of 1.9 cm^− 1. These results indicate that the HFCVD-grown SCD has good crystalline quality comparable to the seed substrates.     

Nano- and micro-crystalline diamond growth by MPCVD in extremely poor hydrogen uniform plasmas

It is well established that argon rich plasmas (> 90% Ar) in Ar/CH₄/H₂ gas mixtures lead to (ultra)nanodiamond nucleation and growth by microwave plasma chemical vapour deposition (MPCVD). Nonetheless, in the present work, both microcrystalline and nanocrystalline diamond deposits developed under typical conditions for ultrananocrystalline (UNCD) growth by MPCVD. Silicon substrates were pretreated by abrasion using two different diamond powder types, one micrometric (< 0.5 μm) and the other nanometric (∼ 4 nm), the latter obtained by detonation methods. Samples characterization was performed by SEM (morphology), AFM (roughness and morphology) and micro-Raman (structure).For all samples, Raman analysis revealed good crystalline diamond quality with an evident ∼ 1332 cm^− 1 peak. The Raman feature observed at ∼ 1210 cm^− 1 is reported to correlate with two other common bands at ∼ 1140 cm^− 1 and ∼ 1490 cm^− 1 characteristic of nano- and ultra-nanocrystalline diamond.A new growth process is proposed to explain the observed morphology evolution from nano- to microcrystalline diamond. Based on this, the microcrystalline morphology is in fact a crystallographically aligned construction of nanoparticles.     

Investigation of the crystallinity of suspension plasma sprayed hydroxyapatite coatings

Hydroxyapatite coatings were deposited on stainless steel substrates. The arc current was varied to study its effect on the coating crystallinity. The crystallinity was calculated according to the XRD patterns via Jade 6.0 software and the full width at half maximum (FWHM) of Raman peak at 962 cm⁻¹. The FE-SEM images showed that HA coatings had rod-like nanostructures and agglomerated into microspheres. The XRD patterns indicated that the as-sprayed coatings were composed of HA and some decomposition phases. Micro-Raman spectroscopies demonstrated that the main phase in the coatings was HA. The results showed that the crystallinity was increased from 68.68% to 76.84% while the FWHM varied from 9.74 to 6.38 cm⁻¹, when the arc current increased from 400 A to 600 A. The selected area electron diffraction (SEAD) patterns were used to analyze the crystallinity qualitatively, and the results agreed with the conclusions of XRD and FWHM of Raman peak.     

Hydrogen-assisted pulsed KrF-laser irradiation for the in situ photoreduction of graphene oxide films

We report on the use of pulsed KrF-laser irradiation for the in situ reduction of graphene oxide (GO) films under both vacuum and partial hydrogen pressure. By exposing GO films to 500 pulses of a KrF-laser, at a fluence of 10 mJ/cm², their sheet resistance (R_s) is dramatically reduced from highly insulating (∼10¹⁰ Ω/sq) to conductive values of ∼3 kΩ/sq. By increasing the laser fluence, from 10 to 75 mJ/cm², we were able to identify an optimal fluence around 35 mJ/cm² that leads to highly conductive films with R_s values as low as 250 Ω/sq and 190 Ω/sq, under vacuum (10⁻⁵ Torr) and 50 mTorr of H₂, respectively. Raman spectroscopy analyses confirmed the effective reduction of the KrF-laser irradiated GO films through the progressive recovery of the characteristic 2D band of graphene. Furthermore, systematic Fourier-transform infrared spectroscopy analysis has revealed that KrF-laser induced reduction of GO preferentially occurs through photodissociation and removal of carboxyl (COOH) and alcohol (OH) groups. A direct correlation is established between the electrical resistance of photoreduced GO films and their COOH and OH bond densities. The KrF-laser induced reduction of GO films is found to be more efficient under H₂ background than under vacuum. It is concluded that our KrF-laser reduced GO films mainly consist of turbostratic graphite built from randomly organized few-layers-graphene building blocks, which contains some residual oxygen atoms and defects. Finally, by monitoring the KrF-laser fluence, it is shown that reduced GO films combining optical transmission as high as ∼80% along with sheet resistance as low as ∼500 Ω/sq can be achieved with this room-temperature and on-substrate process. This makes the laser-based reduction process developed here particularly attractive for photovoltaic hybrid devices using silicon substrates.     

Large-area reduced graphene oxide thin film with excellent thermal conductivity and electromagnetic interference shielding effectiveness

In this work, we fabricated reduced large-area graphene oxide (rLGO) with maximum surface area of 1592 μm² through a cost-effective chemical reduction process at low temperature. The product revealed large electrical conductivity of 243 ± 12 S cm⁻¹ and thermal conductivity of 1390 ± 65 W m⁻¹ K⁻¹, values much superior to those of a conventional reduced small-area graphene oxide (with electrical conductivity of 152 ± 7.5 S cm⁻¹ and thermal conductivity of 900 ± 45 W m⁻¹ K⁻¹). The rLGO thin film also exhibited not only excellent stiffness and flexibility with Young’s modulus of 6.3 GPa and tensile strength of 77.7 MPa, but also an efficient electromagnetic interference (EMI) shielding effectiveness of ∼20 dB at 1 GHz. The excellent performance of rLGO is attributed to the fact that the larger area LGO sheets include much fewer defects that are mostly caused by the damage of graphene sp² structure around edge boundaries, resulting in large electrical conductivity. The manufacturing process of rLGO is an economical and facile approach for the large scale production of highly thermally conducting graphene thin films with efficient EMI shielding properties, greatly desirable for future portable electronic devices.     

Sp3/sp2 character of the carbon and hydrogen configuration in micro- and nanocrystalline diamond

Hot filament and microwave plasma CVD micro- nanocrystalline diamond films are analysed by visible and ultra-violet excitation source Raman spectroscopy. The sample grain size varies from 20 nm to 2 μm. The hydrogen concentration in samples is measured by SIMS and compared to the grain size, and to the ratio of sp² carbon bonds determined by Raman spectroscopy from the 1332 cm^− 1 diamond peak and the sp² 1550 cm^− 1 G band. Hydrogen concentration appears to be proportional to the sp² bonds ratio. The 3000 cm^− 1 CH_x stretching mode band intensity observed on the Raman spectra is decreasing with the G band intensity. Thermal annealing modifies the sp² phase structure and concentration, as hydrogen outdiffuses.     

Tetracyanoethylene oxide-functionalized graphene and graphite characterized by Raman and Auger spectroscopy

The tetracyanoethylene oxide (TCNEO) functionalization of chemical vapor deposition grown large area graphene and graphite was performed using reaction of TCNEO with carbon surface in chlorobenzene. The successful functionalization has been confirmed by Raman and Auger spectroscopy, and by numerical modeling of the structure and vibrational modes of TCNEO-functionalized graphene. Raman spectra of TCNEO-functionalized graphene and graphite show several groups of lines corresponding to vibrations of attached carbonyl ylide. One of key signatures of TCNEO attachment is the high intensity Raman band at ∼1450 cm⁻¹, which represents the C–CC in plane vibrations in functionalization-distorted graphene. Raman spectra indicate the existence of central (pristine) attachment of TCNEO to graphene surface.     

Effective synthesis of well graphitized high yield bamboo-like multi-walled carbon nanotubes on copper loaded α-alumina nanoparticles

A high-yield bamboo like multiwalled carbon nanotubes (CNTs) were successfully synthesized on copper substituted alumina nanoparticles by thermal chemical vapor deposition (CVD) technique under atmospheric pressure. The obtained products were characterized by various techniques like FESEM with EDX, HRTEM and Raman spectroscopy, which reveals the formation of CNTs and are of bamboo shaped (stacking arrangement) multiwalled type with graphene layers having a diameter between 4 and 9 nm. The appearance of two peaks at 1597 cm^− 1 and 1302 cm^− 1 in Raman spectra are noticed as G-band and D-band for graphitic nature and defects due to bending & curvature of bamboo like carbon nanotubes (b-CNTs), respectively. The influence of reaction parameters such as time, temperature and flow rate was also studied to increase the carbon yield.     

Tuning doping and strain in graphene by microwave-induced annealing

We propose microwave-induced annealing as a rapid, simple, and effective method of controlling surface doping and strain in graphene. Raman spectroscopy was used to confirm that heavy and uniform p-type (1.2 × 10¹³ cm⁻²) doping can be achieved within only 5 min without unintended defects by placing graphene onto a substrate with a sufficiently high dielectric constant and exposing graphene and its substrate to microwave irradiation. Further, we showed that ripples are formed in suspended graphene when it is exposed to microwave irradiation. Silicon has a sufficiently high dielectric constant (11.9) and graphene is commonly deposited on silicon-based substrates, so our proposed microwave-induced annealing technique can be used for the rapid manipulation of the properties of graphene at low cost.     

A review on integrating nano-carbons into polyanion phosphates and silicates for rechargeable lithium batteries

Lithium metal phosphate (Li₂MPO₄) and silicates (Li₂MSiO₄) (where M = Fe, Mn, and Co) are promising polyanion cathodes for rechargeable lithium batteries, owing to the inherent merits such as low cost, decent electrochemical property, and high stability. However, these merits have often been undermined by insufficient energy and power delivery due to poor Li extraction/insertion kinetics. It is generally believed that the extremely low conductivity, i.e. ∼10⁻⁹ s cm⁻¹ for phosphates and 10⁻¹²–10⁻¹⁶ s cm⁻¹ for silicates at room temperature, in combination with slow Li ion diffusion could account for such sluggish Li cycling kinetics. To address this critical issue, it is essential to integrate well-defined nano-carbons such as one-dimensional (1D) carbon nanotube (CNT), two-dimensional (2D) graphene, and their three-dimensional (3D) assembly into polyanion materials. By constructing hybrid architectures, integrated composites could afford much improved activity towards Li storage versus the bare ones. In this short review, we summarize recent advance in integrating CNT, graphene, and their 3D assemblies into LiMPO₄ and Li₂MSiO₄ cathodes, with particular emphasis on how the cathodes interact with carbon materials and their mechanism. We also conclude some general rules to engineer such integration structures to maximize their utilization towards Li storage.     

Single step preparation of meso-porous and reduced graphene oxide by gamma-ray irradiation in gaseous phase

A facile and highly efficient route to produce simultaneously porous and reduced graphene oxide by gamma ray irradiation in hydrogen is here demonstrated. Narrowly distributed nano-scale pores (average size of ∼3 nm and surface density >44,900 pore μm⁻²) were generated across 10 μm thick graphene oxide bucky-papers at a total irradiation dose of 500 kGy. The graphene oxide sheet reduction was confirmed to occur homogeneously across the structures by Fourier transform infrared spectroscopy and Raman analysis. This one-step, catalyst-free, high penetration and through-put technique, offers great promises potential for the mass production of reduced graphene oxide from cheap graphene oxide.     

Synthesis and properties of an atomically thin carbon nanosheet similar to graphene and its promising use as an organic thin film transistor

We synthesize an atomically thin carbon nanosheet (CNS) analogous to graphene with properties suitable for an organic thin film transistor (OTFT). The synthesis of graphene by chemical vapor deposition has serious drawbacks such as wrinkles, grain boundaries, and defects due to catalyst removal and transfer process. Here the CNS is directly synthesized on a silicon wafer by heat-treatment of spin-coated polyacrylonitrile and shows a higher electrical conductivity (>1600 S cm⁻¹) than that of chemically converted graphene. The CNS on glass, transferred from a silicon wafer, exhibits approximately 92% optical transmittance. We have used our CNS as the electrodes of OTFTs, and recorded a mobility (0.25–0.35 cm² V⁻¹ s⁻¹) that exceeds that of gold electrodes (0.2–0.25 cm² V⁻¹ s⁻¹).