最近用超音速团簇束沉积法制备了一种具有sp-sp2杂化的新型无定形碳，表明膜中存在多炔和累积碳物种[L. Ravagnan等人，Phys. Rev. Lett. 98，216103（2007）]。在这里，我们提出了在不同温度下的sp-sp2膜的低频振动区域（400-800 cm-1）的原位拉曼表征。我们报告存在两个峰值在450 cm-1和720 cm-1。较低的频率峰显示出随sp含量的变化而演化，并且在密度泛函理论（DFT）模拟的支持下，它可以归因于sp线性结构的弯曲模式。720 cm-1处的峰不随sp含量而变化，并且它可以归因于由sp2相的无序激活的振动态密度中的特征。
英文摘要：
A novel form of amorphous carbon with sp-sp2 hybridization has been recently produced by supersonic cluster beam deposition showing the presence in the film of both polyynic and cumulenic species [L. Ravagnan et al. Phys. Rev. Lett. 98, 216103 (2007)]. Here we present a in situ Raman characterization of the low frequency vibrational region (400-800 cm-1) of sp-sp2 films at different temperatures. We report the presence of two peaks at 450 cm-1 and 720 cm-1. The lower frequency peak shows an evolution with the variation of the sp content and it can be attributed, with the support of density functional theory (DFT) simulations, to bending modes of sp linear structures. The peak at 720 cm-1 does not vary with the sp content and it can be attributed to a feature in the vibrational density of states activated by the disorder of the sp2 phase.
In this work we present a detailed Raman scattering investigation of zinc oxide and aluminum-doped zinc oxide (AZO) films characterized by a variety of nanoscale structure and morphology and synthesized by pulsed laser deposition (PLD) under different oxygen pressure conditions. The comparison of Raman data for pure ZnO and AZO films with similar morphology at the nano/mesoscale allows to investigate the relation between Raman features (peak or band positions, width, relative intensity) and material properties such as local structural order, stoichiometry and doping. Moreover Raman measurement…
In this review, we present our recent computational work on carbon-based nanostructured composites. These materials consist of carbon crystallites embedded in an amorphous carbon matrix and are modeled here through classical and semi-empirical quantum-mechanical simulations. We investigate the energetics, mechano-elastic, and optoelectronic properties of these materials. Once the stability of the composites is discussed, we move on to the calculation of their elastic moduli and constants, their anisotropy and elastic recovery. At a next step, we focus on diamond composites, which were found to…
Porous metal oxides with nano-sized features attracted intensive interest in recent decades due to their high surface area which is essential for many applications, e.g. Li ion batteries, photocatalysts, fuel cells and dye-sensitized solar cells. Various approaches were so far investigated to synthesize porous nanostructured metal oxides, including self-assembly and template-assisted synthesis. For the latter approach, forests of carbon nanotubes are considered as particularly promising templates, with respect to their one dimensional nature and the resulting high surface area. In this work, w…
Recent years witnessed a rapid growth of interest of scientific and engineering communities to thermal properties of materials. Carbon allotropes and derivatives occupy a unique place in terms of their ability to conduct heat. The room-temperature thermal conductivity of carbon materials span an extraordinary large range - of over five orders of magnitude - from the lowest in amorphous carbons to the highest in graphene and carbon nanotubes. I review thermal and thermoelectric properties of carbon materials focusing on recent results for graphene, carbon nanotubes and nanostructured carbon mat…
Raman spectroscopic study of amorphous carbon layers for two different excitation wavelengths at room temperature. The amount of sp3 bondings is estimated to about 10% for both samples, evaluated from the ratio of the D- and G-Raman line intensities. The properties of the bondings in the two samples are discussed. Raman-spektroskopische Untersuchungen von amorphen Kohlenstoffschichten fuer zwei unterschiedliche Anregungswellenlaengen bei Raumtemperatur. Der sp3-Bindungsanteil is zu 10% fuer beide Proben bestimmt worden, ermittelt aus dem Intensitaetsverhaeltnis der D- and G-Raman-Linien. Die E…
Raman spectroscopy has been employed to distinguish between the Raman spectrum of pristine hydrogenated diamond like carbon (PHDLC) and that of electrochemically hydrogenated diamond like carbon (ECHDLC). The enhancement of the background photoluminescence (PL) in the Raman spectrum and broadening of PL spectrum of ECHDLC are identified to be due to increase of sp3 C-H density onto the PHDLC surface, during novel electrochemical process of hydrogenation of sp2 C=C into sp3 C-H.
We present an analysis of deep-UV Raman measurements of graphite, graphene and carbon nanotubes. For excitation energies above the strong optical absorption peak at the $M$ point in the Brillouin zone ($\approx 4.7\,\text{eV}$), we partially suppress double-resonant scattering processes and observe the two-phonon density of states of carbon nanomaterials. The measured peaks are assigned to contributions from LO, TO, and LA phonon branches, supported by calculations of the phonon dispersion. Moreover, we gain access to the infrared-active $E_{1u}$ mode in graphite. By lowering the excitation en…
Coral Pt islands films are deposited via electrochemical reduction on silica coated nanostructured Ag electrodes. From these devices surface enhanced (resonance) Raman [SE(R)R] signals of molecules exclusively attached to Pt are obtained with intensities up to 50% of the value determined for Ag. SE(R)R spectroscopic investigations are carried out with different probe molecules, silica coating thicknesses and excitation lines. Additionally, field enhancement calculations on Ag-SiO2-Pt support geometries are performed to elucidate the influence of the Pt island film nanostructure on the observed…
The resonant Raman scattering in N-IR - UV range from amorphous hydrogenated carbon (a-C:H) reveal inclusions of trans-polyacetylene (trans-(CH)x) chains with approximate length of up to 120 C=C units and inclusions of poly(p-phenylene vinylene) (PPV) polymer chains. The PPV is evidenced by a strong dispersive mode at ca. 1175 cm-1. It was found that the Raman response from core Ag trans-(CH)x modes incorporated into a-C:H to changing excitation energy is identical to of free-standing chains thus facilitating identification of trans-(CH)x in complex carbonaceous materials spectra.
Ratio of the intensity of D- Raman peak and G- Raman peak (ID/IG) is often used for characterization of diamond-like carbon films, for example to estimate number and size of the sp2 clusters. In this paper we investigate how the interference effects in the film influence this ratio. It is shown that for films on silicon substrates the distortion of the real ratio can reach 10 % and for films on metals even 40 %. This should be taken into account if some conclusions are made from the measured ID/IG ratio.
Long linear carbon-chains have been attracting intense interest arising from the remarkable properties predicted and their potential applications in future nanotechnology. Here we comprehensively interrogate the excitonic transitions and the associated relaxation dynamics of nanotube confined long linear carbon-chains by using steady state and time-resolved Raman spectroscopies. The exciton relaxation dynamics on the confined carbon-chains occurs on a hundreds of picoseconds timescale, in strong contrast to the host dynamics that occurs on a few picosecond timescale. A prominent time-resolved …
We present a resonance Raman study of the disorder-induced D mode in a sample highly enriched with semiconducting (9,7) single-walled carbon nanotubes in the excitation energy range of 1.49 - 2.05 eV. The intensity of the D mode shows a resonance behavior near the optical transition of the (9,7) tube. The well-known dispersion of the D-mode frequency, on the other hand, is not observed at the resonance, but only above a certain excitation energy. We explain our results by numerical simulations of the D-mode spectra.
Raman studies of nanocomposite SiCN thin film by sputtering showed that with an increase of substrate temperature from room temperature to 500oC, a transition from mostly sp2 graphitic phase to sp3 carbon took place which was observed from the variation of ID/IG ratio and the peak shifts. This process resulted in the growth of C3N4 and Si3N4 crystallites in the amorphous matrix which led to an increase in hardness and modulus obtained through nanoindentation. However, at a further higher temperature of 600oC, again an increase of sp2 C concentration in the film was observed and the H and E val…
Surface Enhanced Raman Spectroscopy (SERS) is exploited here to investigate the interaction of isolated sp carbon chains (polyynes) in a methanol solution with silver nanoparticles. Hydrogen-terminated polyynes show a strong interaction with silver colloids used as the SERS active medium revealing a chemical SERS effect. SERS spectra after mixing polyynes with silver colloids show a noticeable time evolution. Experimental results, supported by density functional theory (DFT) calculations of the Raman modes, allow us to investigate the behavior and stability of polyynes of different lengths and…
Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR - UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy \hbarωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to \hbarωL probing of trans-(CH)x chain inhomogeneity and the distribution of …
We present a high sensitivity single-monochromator Raman spectrometer which allows operation with a tunable laser source. The instrument is based on the modification of a commercial Raman spectrometer; such instruments operate with holographic Rayleigh filters which also act as a laser mirrors and are usually considered as inherently narrow-band. In our design, the two tasks are separated and the filter can be freely rotated without much effect on the light alignment. Since rotation shifts the filter passband, this modification allows tunable operation with efficient stray light filtering down…
With the advent of new synthesis and large-scale production technologies, nanostructured gas-adsorbent materials (GAM) like carbon nanocomposites and metal-organic frameworks are becoming increasingly more influential in our everyday lives. First-principles methods based on density functional theory (DFT) have been pivotal in establishing the rational design of GAM, a factor which has tremendously boosted their development. However, DFT methods are not perfect and due to the stringent accuracy thresholds demanded in modelling of GAM (i.e., exact binding energies to within ~0.01 eV) these techn…
Since graphene, a single sheet of graphite, has all of its carbon atoms on the surface, its property is very sensitive to materials contacting the surface. Herein, we report novel Raman peaks ob-served in annealed graphene and elucidate their chemical origins by Raman spectroscopy and atomic force microscopy (AFM). Graphene annealed in oxygen-free atmosphere revealed very broad additional Raman peaks overlapping the D, G and 2D peaks of graphene itself. Based on the topographic confirmation by AFM, the new Raman peaks were attributed to amorphous carbon formed on the surface of graphene by car…
The Raman response of new structures grown after filling SWCNTs with ferrocene and transformation at moderate high temperatures is demonstrated to be very strong, even stronger than the response from the tubes. Transmission electron microscopy demonstrates that the new objects are flat and exhibit a structure similar to short fragments of nanoribbons. The growth process is controlled by two different activation energies for low and high transformation temperatures, respectively. Immediately after filling Raman pattern from a precursor molecule are detected. Two different types of nanoribbons w…
The paper presents a cooperative consideration of Raman spectra of $^2$ amorphous carbons as well as the nature and type of their amorphicity. The latter was attributed to the amorphization of a new type named as enforced fragmentation. The fragments are stable graphenous molecules, which are the basic structural units (BSUs) of the solids, determining them as amorphics with molecular structure. Due to weak intermolecular interaction, BSUs, once aggregated, are the main defendants for IR absorption and Raman scattering of the solids, just justifying the consideration of them at molecular level…
The main research efforts are aimed at finding inexpensive materials that can be converted into nanostructured carbon-containing materials, such as activated carbon and graphene. Rice husks are one such material, especially in developing countries, where more than 95% of Rice husks are produced worldwide. Although numerous studies have been conducted on the production of activated carbon and graphene structures from Rice husk, the existing scientific information is still widely scattered in the literature. Therefore, this review article provides extensive information on made by various researc…
Raman spectroscopy has been used in chemistry and physics to investigate the fundamental process involving light and phonons (quantum of lattice vibration). The carbon nanohorn introduces a new subject to Raman spectroscopy, namely topology. We show theoretically that a photo-excited carrier with a non-zero winding number activates a topological $D$ Raman band through the Aharonov-Bohm effect. The topology-induced $D$ Raman band can be distinguished from the ordinary $D$ Raman band for a graphene edge by its peak position.
Disordered carbon often exhibit a complex Raman spectrum, with four to six components. Here, a large variety of disordered carbons, forming a collection of samples with a great variety of structures, are analysed using multi-wavelength Raman microscopy (325.0, 514.5, 785.0 nm). They allow us to extend Raman behaviour known for nano-crystalline graphite to amorphous carbons, (dependence with the excitation wavelength) and other known for amorphous carbons to nano-crystalline graphite, (differentiation of the smallest cluster size probed using different excitation wavelengths). Experimental spec…
Surface enhanced Raman scattering (SERS) effects on tin dioxide in the form of bulk material, nanostructured thin films and colloidal solutions were investigated. Raman spectra are characterized by the three Raman scattering peaks at 478, 633, and 776 \invcm, assigned to the E$_g$, A$_{1g}$ and B$_{2g}$ modes, typical of rutile SnO$_2$. In presence of the silver nanoparticles, in addition to the enhancement intensity of some of the fundamental tin dioxide rutile Raman features, the appearance of a new Raman scattering peak at about 600 cm$^{-1}$ is observed. This spectral features is observed,…
We demonstrate that AC arc discharge under de-ionized water which has been recently used for carbon nanotubes (CNT) production can be modified to increase the quantity and quality of carbon nanotubes by applying a magnetic field. The carbon soot thus obtained was analyzed using SEM, TEM and Raman spectroscopy. The Raman scattering measurements showed interesting results. Radial breathing modes (RBM) were observed in the Raman data in the range 150 - 700 cm-1. The presence of RBM is good enough indication of the presence of the carbon nanotubes in the soot collected by us. The RBM data was anal…
Chirality distribution and transition energies of carbon nanotubes
从孤立的纳米管上的共振拉曼散射，我们得到的光学跃迁能量，径向呼吸模式的频率和拉曼强度的金属和半导体管。我们仅根据第三近邻紧束缚Kataura图明确地指定了大约50个纳米管的手性指数（n_1，n_2），并发现omega_RBM= 214.4 cm ^-1 nm/d+18.7 cm ^-1。与发光实验相反，我们观察到所有的手性，包括锯齿管。拉曼强度有一个系统的手性角依赖性确认最近的从头计算。
Boron carbide, a lightweight, high temperature material, has various applications as a structural material and as a neutron absorber. The large solubility range of carbon in boron, between $\approx$ 9% and 20%, stems from the thermodynamical stability of three icosahedral phases at low temperature, with respective carbon atomic concentrations: 8.7% (B$_{10.5}$C, named OPO$_1$), 13.0 \% (B$_{6.7}$C, named OPO$_2$), whose theoretical Raman spectra are still unknown, and 20% (B$_4$C), from which the nature of some of the Raman peaks are still debated. We report theoretical and experimental result…
We used tip-enhanced Raman spectroscopy to study the diameter-dependent Raman modes in a contacted carbon nanotube rope. We show that with the near-field tip enhancement a large number of nanotubes within a rope can be identified, even if the nanotube modes can not be distinguished in the far-field signal. Several metallic and semiconducting nanotubes can be identified and assigned to nanotube families. Additionally, we provide a tentative chiral index assignment.
We have used resonant Raman scattering spectroscopy to fully analyze the relative abundances of different (n,m) species in single-walled carbon nanotube samples that are metallically enriched by density gradient ultracentrifugation. Strikingly, the data clearly show that our density gradient ultracentrifugation process enriches the metallic fractions in armchair and near-armchair species. We observe that armchair carbon nanotubes constitute more than 50% of each (2n + m) family.
Different peak trends of tiny grains carbon film have been observed under the investigations of Raman spectroscopy and energy loss spectroscopy. Carbon films known in nanocrystalline and ultra-nanocrystalline diamond films are synthesized by employing microwave-based vapor deposition system. Carbon atoms exhibit several state behaviors depending on the incurred positions of their electrons. Different morphology of tiny grains under different chamber pressure is related to different rate of arriving typical energies at/near substrate surface. Those tiny grains of carbon film which evolved in gr…
Two-dimensional (2D) hybrid sp-sp2 carbon systems are an appealing subject for science and technology. For these materials, topology and structure significantly affect electronic and vibrational properties. We investigate here by periodic density-functional theory (DFT) calculations we here investigate the Raman and IR spectra of 2D carbon crystals belonging to the family of graphdiynes (GDYs) and having different structures and topologies. By joining DFT calculations with symmetry analysis, we assign the IR and Raman modes in the spectra of all the investigated systems. On this basis, we disc…
The appearance of a broad peak at $\sim$1550 cm$^{-1}$ (G$^{-}$ peak) in carbon nanotube resonant Raman scattering spectra has been conventionally attributed to the presence of metallic nanotubes. Here, we present resonant Raman measurements on macroscopic nanotube ensembles enriched in armchair species prepared through density gradient ultracentrifugation. Our data clearly demonstrate that the broad G$^{-}$ mode is absent for armchair structures and appears only when the excitation laser is resonant with non-armchair "metals." Due to the large number ($\sim$10$^{10}$) of nanotubes across seve…
We study the kinetics of the H release from plasma-deposited hydrogenated amorphous carbon films under isothermal heating at 450, 500 and 600 {\degree}C for long times up to several days using in situ Raman microscopy. Four Raman parameters are analyzed. They allow the identification of different processes such as the carbon network reorganization and the H release from sp3 or sp2 carbon atoms and the corresponding timescales. Carbon reorganization with aromatization and loss of sp3 hybridization occurs first in 100 minutes at 500 {\degree}C. The final organization is similar at all investigat…
We present a fast and simple way to determine the erosion rate and absorption coefficient of hydrogenated amorphous carbon films exposed to a hydrogen atomic source based on ex-situ Raman micro-spectroscopy. Results are compared to ellipsometry measurement. The method is applied to films eroded at different temperatures. A maximum of the erosion rate is found at ~ 450 {\degree}C in agreement with previous results. This technique is suitable for future quantitative studies on the erosion of thin carbonaceous films, especially of interest for plasma wall interactions occurring in thermonuclear f…
Growing graphene nanoribbons from small organic molecules encapsulated in carbon nanotubes can result in products with uniform width and chirality. We propose a method based on encapsulation of 1,2,4-trichlorobenzene from the liquid phase and subsequent annealing. This procedure results in graphene nanoribbons several tens of nanometers long. The presence of nanoribbons was proven by Raman spectra both on macroscopic samples and on the nanoscale by tip-enhanced Raman scattering and high-resolution transmission electron microscopic images.
