Characterisation of carbonaceous materials using Raman spectroscopy: a comparison of carbon nanotube filters,single‐ and multi‐walled nanotubes,graphitised porous carbon and graphite

Multi‐walled carbon nanotube (MWCNT) filters have been recently synthesised which have specific molecular filtering capabilities and good mechanical strength. Optical and scanning electron microscopy (SEM) reveals the formation of highly aligned arrays of bundles of carbon nanotubes having lengths up to 500 µm. The Raman spectra of this material along with four other carbonaceous materials, commercially available single‐walled carbon nanotubes (SWCNTs) and MWCNTs, graphitised porous carbon (Carbotrap) and graphite have been recorded using two‐excitation wavelengths, 532 and 785 nm, and analysed for band positions and shape with special emphasis paid to the D‐, G‐ and G′‐bands. A major difference between the different MWCNT varieties analysed is that G‐bands in the MWCNT filters exhibit almost no dispersion, whereas the other MWCNTs show a noticeable dispersive behaviour with a change in the excitation wavelength. Spectral features similar to those of the MWCNT filter varieties were observed for the Carbotrap material. From the line shape analysis, the intensity ratio, I_D/I_G, of the more ordered MWCNT filter material using the integral G‐band turns out to be two times lower than that of the less ordered MWCNT filter product at both excitation wavelengths. This parameter can, therefore, be used as a measure of the degree of MWCNT alignment in filter varieties, which is well supported also by our SEM study. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of gas composition on the growth of multi-walled carbon nanotube

This paper studies the effects of different gas compositions on the growth of multi-walled carbon nanotube (MWCNT) films by using an electron cyclotron resonance chemical vapor deposition (ECR-CVD) method. The Raman spectrum was employed to explore the composition of the MWCNT films grown under different mixtures of C₃H₈ and H₂. The results showed that the optimum relative intensity ratio of the D band to G band (i.e., I_D/I_G) is 2 for the cases considered in this study. In addition, the morphology and microstructure of the MWCNTs were examined by field emission scanning electron microscopy (FE-SEM) and field emission gun transmission electron microscopy (FEG-TEM). Furthermore, atomic force microscopy (AFM) and scanning thermal microscopy (SThM) were used to study the surface topography and thermal properties of the MWCNTs.     

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.     

Multipeak fitting analysis of Raman spectra on DLCH film

The hydrogenated diamond‐like carbon (DLCH) film with 1‐µm thickness is deposited by direct hydrocarbon gas ion beam method on silicon wafer and annealed at 400 °C. Detailed Raman spectra feature are fitted from nine sets of different peak fitting functions, including Gaussian, Lorentzian and Breit‐Wigner‐Fano (BWF) functions. These fitting results obtained from a two‐peak combination show some specific variances on the G peak position, FWHM_G and I_D/I_G ratio for as‐deposited and as‐annealed DLCH films. The most popular two‐peak fitting method with full Gaussian function tends to exhibit a higher ratio of the G peak position shift and higher I_D/I_G ratio than others fitting methods, the drastic difference among the most popular G (G) & G (D) and B (G) & L (D) schemes also have brought out in I_D/I_G ratio. However, for a more complex four‐peak Gaussian function fitting Raman spectra, the I_D/I_G ratio is close to that of a two‐peak fitting function with a mixture functions of BWF (G) and L (D). Furthermore, a series of systematic peak fitting procedures and comparisons of Raman spectra have been discussed in this study. Copyright © 2009 John Wiley & Sons, Ltd.     

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.     

Bias‐driven super‐insulating state in prismane single‐molecule contacts

Quantum transport in a single‐molecule contact made of a prismane cluster C₈ attached to quasi‐one‐dimensional gold (100) electrodes is calculated using the ab initio methodology based on the density‐functional theory and the nonequilibrium Green's functions formalism. Varying the junction length L we calculate the length dependence of the zero‐bias conductance G (L) and, for a set of the interelectrode distances, the current–voltage (I –V) characteristics. It is shown that the G (L) dependence is strongly nonmonotonic with a sharp dip at some value of L. With increase in L, the I –V curves change their shape from monotonic curves to curves with a negative differential resistance area and, for a larger L, the junction exhibits the super‐insulating state, i.e., within some applied bias voltage range the current through the junctions is about two orders of magnitude less than the current outside this bias range. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

退火对B掺杂纳米金刚石薄膜微结构和电化学性能的影响

采用热丝化学气相沉积法制备B掺杂纳米金刚石薄膜,并对薄膜进行真空退火处理,系统研究了不同退火温度对B掺杂纳米金刚石薄膜的微结构和电化学性能的影响.结果表明,当退火温度升高到800 ℃后,薄膜的Raman谱图中由未退火时在1157,1346,1470,1555 cm^-1处的4个峰转变为只有D峰和G峰,说明晶界上的氢大量解吸附量减少,并且D峰和G峰的积分强度比I_D/I_G值变为最小,即sp²相团簇     

Effect of Thermal Treatment on the Structure of Multi-walled Carbon Nanotubes

The effects of vacuum annealing and oxidation in air on the structure of multi-walled carbon nanotubes (MWCNTs) produced by a large-scale catalytic chemical vapor deposition (CCVD) process are studied using Raman spectroscopy and transmission electron microscopy (TEM). A detailed Raman spectroscopic study of as-produced nanotubes has also been conducted. While oxidation in air up to 400°C removes disordered carbon, defects in tube walls are produced at higher temperatures. TEM reveals that MWCNTs annealed at 1,800°C and above become more ordered than as-received tubes, while the tubes annealed at 2,000°C exhibit polygonalization, mass transfer and over growth. The change in structure is observable by the separation of the Raman G and D′ peaks, a lower R-value (I _D/I _G ratio), and an increase in the intensity of the second order peaks. Using wavelengths from the deep ultraviolet (UV) range (5.08 eV) extending into the visible near infrared (IR) (1.59 eV), the Raman spectra of MWCNTs reveal a dependence of the D-band position proportional to the excitation energy of the incident laser energies.     

Solid‐phase epitaxy of InOx Ny alloys via thermal oxidation of InN films on yttria‐stabilized zirconia

The characteristics of InO_x N_y alloy films prepared via thermal oxidation of InN epitaxial films with In‐ or N‐polarities grown on nearly lattice‐matched, yttria‐stabilized zirconia (YSZ) substrates are investigated. The InN films were oxidized to InO_x N_y with a gradual change in O/N composition by annealing in air. Structural analysis revealed that the temperature for phase transition from wurtzite structure depends on the polarity of InN, and N‐polar InO_x N_y films can retain their wurtzite structure even at higher temperatures compared with the case of In‐polar films. Furthermore, changes in the valence band structure and optical characteristics of the InO_x N_y alloys take place via thermal oxidation. These results indicate that InO_x N_y grown via thermal oxidation of N‐polar InN on YSZ can be considered as an alloy semiconductor for optoelectronic devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Invariant states in statistical mechanics

Mathematically we consider aC*-algebra , acted upon by the groupT of space-translations, which has an asymptotic abelian property. We analyse invariant states over . Physically this programme can be considered as a kinematical study of equilibrium states in statistical mechanics. Each invariant state can be uniquely decomposed into elementary invariant states (E-states). These elementary states have, amongst other characteristics, the physical property that space-averages of local observables are constants in the corresponding representations. In anE-state the discrete spectrum S _D of space-translations is additive which gives rise to the classificationE _I,E _II, andE _III corresponding to the three possibilities that S _D contains one point, a lattice of points, or a set with accumulation points. AnE _II-state can be uniquely decomposed into states (L-states) having a symmetry with respect to a closed subgroupT _L of (S _D and T _L are reciprocal lattices).L-states have properties with respect toT _L analogous to the properties ofE _I-states with respect toT. The decomposition intoL-states is the inverse process of homogenizing a lattice state by smearing it over a lattice distance. The mathematical methods which we employ have more general applications.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Standard‐free composition measurements of Alx In1–xN by low‐loss electron energy loss spectroscopy

We demonstrate a standard‐free method to retrieve compositional information in Al_x In_1–xN thin films by measuring the bulk plasmon energy (E_p), employing electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Two series of samples were grown by magnetron sputter epitaxy (MSE) and metal organic vapor phase epitaxy (MOVPE), which together cover the full com‐ positional range 0 ≤ x ≤ 1. Complementary compositional measurements were obtained using Rutherford backscattering spectroscopy (RBS) and the lattice parameters were obtained by X‐ray diffraction (XRD). It is shown that E_p follows a linear relation with respect to composition and lattice parameter between the alloying elements from AlN to InN allowing for straightforward compositional analysis. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Localized states emission in type‐I GaAsSb/AlGaAs multiple quantum wells grown by molecular beam epitaxy

As an important candidate for novel infrared semiconductor lasers, the optical properties of GaAsSb‐based multiple quantum wells (MQWs) are crucial. The temperature‐ and excitation power‐dependent photoluminescence (PL) spectra of the GaAs_0.92Sb_0.08/Al_0.2Ga_0.8As MQWs, which were grown by molecular beam epitaxy, were investigated and are detailed in this work. Two competitive peaks were observed from 40 K to 90 K. The peak located at the low‐energy shoulder was confirmed to be localized states emission (LE) and the high‐energy side peak was confirmed to be free‐carrier emission by its temperature‐dependent emission peak position. It is observed that the LE peak exhibited a blueshift with the increase of laser excitation power, which can be ascribed to the band filling effect of localized states. Our studies have great significance for application of GaAsSb‐based MQWs in infrared semiconductor lasers.

     

How to obtain a reliable structural characterization of polished graphitized carbons by Raman microspectroscopy

A series of graphitized carbon materials, produced by the pyrolysis of an anthracene‐based coke at temperatures ranging from 1600 to 2900 °C, were studied by Raman microspectroscopy to assess the applicability of this technique to the particular case of polished carbon materials. The polishing process was shown to change significantly the first‐order Raman spectra (D band intensity increase) and therefore to induce unacceptable errors in the characterization of the intrinsic structure of these materials. The deconvolution of Raman spectra, related to the unpolished graphitized carbons at varying temperatures, highlighted a linear relationship between the intensity ratio I_D/I_G and the G band width. Thus, as the latter appears to be insensitive to the polishing, we highly recommend using it for a reliable assessment of the intrinsic structural disorder of polished carbon materials. Copyright © 2011 John Wiley & Sons, Ltd.     

Low-temperature time-resolved vacuum ultraviolet luminescent spectroscopy of KH2PO4 crystals with defects

Low-temperature photoluminescence (PL) of unactivated KDP crystals under selective synchrotron excitation is for the first time measured with subnanosecond time resolution. Time-resolved PL (2–6 eV) and PL excitation (4–35 eV) spectra, as well as PL kinetics, are measured at 7 K. From the acquired experimental data, luminescent bands related to intrinsic defects of the KDP lattice are identified; in particular, the long-wave band at 2.6 eV is assigned to L defects, and the band at 3.5–3.6 eV is attributed to D defects. An efficient energy transfer over the hydrogen sublattice is shown to take place in KDP at low temperatures. It results in the efficient excitation of L and D center photoluminescence in the fundamental absorption region, at electron transitions to the bottom levels of the conduction band, corresponding to the states of the hydrogen atom. The band gap E _g is evaluated to be 8.0–8.8 eV.     

Li (i = 1, 2, 3) sub‐shell fluorescence yields for 79Au, 80Hg and 81Tl

The L _i (i = 1, 2, 3) sub‐shell x‐ray fluorescence yields (ω _i ) for ₇₉Au, ₈₀Hg and ₈₁Tl were deduced from the measured cross‐sections for the L _i (i = 1, 2, 3) sub‐shell x‐rays following ionization by 59.54 keV γ‐rays (B < E_inc < B_K) and for the L₃ sub‐shell x‐rays following ionization by Rb K x‐rays (B < E_Kα < B, B < E_Kβ < B_K), where B is the K shell/L _i sub‐shell ionization threshold of the target element. An energy‐dispersive x‐ray fluorescence setup, involving photon sources consisting of a ²⁴¹Am annular source in the direct and secondary excitation modes along with RbCl secondary exciter and an Si(Li) detector, was used for the measurements. The measured ω₂ and ω₃ values exhibit good agreement with those based on the relativistic Dirac–Hartree–Slater (RDHS) calculations, while the ω₁ values are found to be higher by ～25%. The present data indicate that the L₁–L₃ Coster–Kronig yield f₁₃ based on the RDHS calculations are overestimated. Copyright © 2004 John Wiley & Sons, Ltd.     

Enhanced dielectric permittivity of fluorine polyimide matrix with embedded graphene

A polymer nanohybrid material with enhanced dielectric permittivity was prepared using the fluorine‐containing polyimide (PI) 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride/4,4′‐oxydianiline (6FDA/ODA) as matrix and graphene as conductive filler in our present work. Studies on the dielectric properties of the 6FDA/ODA–graphene nanohybrid films show that the dielectric permittivity (ε) can be significantly enhanced by the layer‐by‐layer structure of graphene and the presence of fluorine also has an important influence on the improvement of ε. The percolation theory and microcapacitor model are used to explain the change of dielectric properties and a percolation threshold f_c = 0.0152 (2.45 wt%) was obtained by a linear‐fit calculation.

     

Photoluminescence properties of selectively grown InN microcrystals

We investigated the photoluminescence (PL) properties of regularly arranged N‐polar InN microcrystals with m ‐plane sidewall facets. We observed narrow PL emission at 0.678 eV with a linewidth of ～14 meV at 4 K and a clear band‐filling effect with increasing excitation power. We also observed a normal red shift of the PL peak energy as large as 51 meV (～150 nm) with increasing temperature from 4 to 300 K, similar to that observed for non‐degenerated semiconductors. The integrated PL intensity ratio I_300K/I_4K was measured to be 6.1%. These results indicate that InN microcrystals have a low residual carrier density and excellent optical properties without being adversely affected by surface electron accumulation, despite their relatively high surface area. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Observation of intermediate bands feeding the positive-parity yrast band in 155Gd

High-spin states of ¹⁵⁵Gd were populated by using the ¹⁵⁴Sm(α,3nγ)¹⁵⁵Gd reaction at E _α= 33 MeV. γ-γ coincidence, E _γ singles, excitation function, and the DCO ratios were measured. we have identified three intermediate bands with ΔI= 2 feeding the positive yrast band. The bands are interpreted as such candidate bands that are mixed with the negative-parity ground state band. This observation can provide a plausible explanation for unusually large population of the positive-parity yrast band observed in a recent Coulomb excitation. Received: 2 November 1999