Structural studies of diamond films and ultrahard materials by Raman and micro-Raman spectroscopies

Correlations between phonon Raman spectra and structure were established and illustrated with natural diamond, graphite, carbon, novel brilliants and novel ultrahard substances. Diamond-like film is characterized by a Raman band at 1540 ± 20 cm⁻¹ which differs from those of graphite and amorphous carbon. A new structure named “bridged graphite” or “diamite”, with interlayer bonds is proposed for diamond-like material. A mechanism for the destruction of ultrahard coatings is also suggested.     

Comparative study of first- and second-order Raman spectra of MWCNT at visible and infrared laser excitation

Comparative studies of first- and second-order Raman spectra of multi-walled carbon nanotubes (MWCNT) and three other graphitic materials - carbon fiber, powdered graphite and highly ordered pyrolytic graphite - are reported. Three laser excitation wavelengths were used: 514.5, 785 and 1064 nm. In first-order Raman spectra, the positions of the bands D, G and D′ (1100-1700 cm⁻¹) presented very similar behavior, however the intensity (I) ratio I_D/I_G ratio showed differed behaviors for each material which may be correlated to differences in their structural ordering. In the second-order spectra, the G′ band varied strongly according to structure with the infrared laser excitation.     

Synthesis of carbon nanosheets by inductively coupled radio-frequency plasma enhanced chemical vapor deposition

An ultrathin sheet-like carbon nanostructure, carbon nanosheet, has been effectively synthesized with CH₄ diluted in H₂ by an inductively coupled radio-frequency plasma enhanced chemical vapor deposition. Nanosheets were obtained without catalyst over a wide range of deposition conditions and on a variety of substrates, including metals, semiconductors and insulators. Scanning electron microscopy shows that the sheet-like structures stand on edge on the substrate and have corrugated surfaces. The sheets are 1 nm or less in thickness and have a defective graphite structure. Raman spectra show typical carbon features with D and G peaks at 1350 and 1580 cm⁻¹, respectively. The intensity ratio of these two peaks, I(D)/I(G), increases with methane concentration or substrate temperature, indicating that the crystallinity of the nanosheets decreases. Infrared and thermal desorption spectroscopies reveal hydrogen incorporation into the carbon nanosheets.     

Ultraviolet and visible Raman spectroscopies of the graphitic BCx phases

Ultraviolet (UV) Raman and visible Raman spectroscopies were applied to study the graphitic BC_x (g-BC_x) phases. The Raman spectra of the g-BC_x phases excited with UV laser at 244 nm have one main peak: a G peak (approximately at 1590 cm^? 1), and do not have the D peak (around 1350 cm^? 1) characteristic for Raman spectra of disordered graphitic phases. The D peak can be detected in all g-BC_x phases when green (534 nm) or near-infrared (785 nm) lasers are used for Raman scattering excitation. The positions of the G and D peaks were found to be independent (within the experimental errors) of the B/C ratio. The pattern of the peaks in UV Raman spectra of g-BC_2.1 phase indicates that the additional peaks centered at 1089 cm^? 1 should be assigned to the E_g mode of B₄C vibration rather than to the T mode characteristic to amorphous graphite. The high signal-to-noise (S/N) ratio and lack of fluorescence of the UV Raman spectra allow an accurate measure of bandwidth and frequency of the G peaks.     

Coherent anti-Stokes Raman scattering enhancement of thymine adsorbed on graphene oxide

Coherent anti-Stokes Raman scattering (CARS) of carbon nanostructures, namely, highly oriented pyrolytic graphite, graphene nanoplatelets, graphene oxide, and multiwall carbon nanotubes as well CARS spectra of thymine (Thy) molecules adsorbed on graphene oxide were studied. The spectra of the samples were compared with spontaneous Raman scattering (RS) spectra. The CARS spectra of Thy adsorbed on graphene oxide are characterized by shifts of the main bands in comparison with RS. The CARS spectra of the initial nanocarbons are definitely different: for all investigated materials, there is a redistribution of D- and G-mode intensities, significant shift of their frequencies (more than 20 cm^-1), and appearance of new modes about 1,400 and 1,500 cm^-1. The D band in CARS spectra is less changed than the G band; there is an absence of 2D-mode at 2,600 cm^-1 for graphene and appearance of intensive modes of the second order between 2,400 and 3,000 cm^-1. Multiphonon processes in graphene under many photon excitations seem to be responsible for the features of the CARS spectra. We found an enhancement of the CARS signal from thymine adsorbed on graphene oxide with maximum enhancement factor about 10⁵. The probable mechanism of CARS enhancement is discussed.     

Raman and surface-enhanced Raman scattering of a series of size-separated polyynes

Solutions of hydrogen-capped polyynes were prepared by laser ablation of graphite powder in n-hexane and subjected to size separation by high-performance liquid chromatography. Solutions of size-selected polyynes C_nH₂ (n = 8–16) were investigated by normal Raman (NR) and surface-enhanced Raman scattering (SERS) spectroscopy. A main band appearing in the 2000–2200 cm⁻¹ region of the NR spectra showed a systematic downward shift as the chain length increased. The observed NR bands were assigned to Raman-active CC stretching vibrational modes by comparison with calculations based on density functional theory. Raman bands observed in SERS spectra were very broad and located at frequencies lower than the NR bands. A systematic band shift with increasing chain length was also observed for one of the bands. This band was thus assigned to a counterpart of the strong band in the NR spectra. These results made it possible to assign the origins of previously reported SERS bands of mixed polyyne solutions.     

Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-Co^IITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-Co^IITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-Co^IITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to Co^III/Co^II and Co^IIIPc⁻¹/Co^IIIPc⁻². The surface coverage (Γ) value, calculated by integrating the charge under Co^II oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-Co^IITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-Co^IITAPc on GC electrode has reached the saturation coverage (Γ_s) within 3 h. The Γ_s value for the SAM of 4α-Co^IITAPc on GC electrode was found to be 2.37 × 10⁻¹⁰ mol cm⁻². Gibbs free energy (ΔG_ads) and adsorption rate constant (k_ad) for the adsorption of 4α-Co^IITAPc on GC surface were found to be −16.76 kJ mol⁻¹ and 7.1 M⁻¹ s⁻¹, respectively. The possible mechanism for the self-assembly of 4α-Co^IITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-Co^IITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-Co^IITAPc is adopting nearly a flat orientation or little bit tilted orientation.     

Proton diffusion in γ-manganese dioxide

Deconvolution of the electrolytic manganese dioxide (EMD) discharge curve has indicated the presence of a number of energetically different reduction processes. This has been used to determine the contribution of each reduction process to the total discharge. Using step potential electrochemical spectroscopy (SPECS), the i-t data were modelled as the sum of the discharge of the individual reduction processes. From this, A√ D for each reduction process as a function of degree of discharge was determined. The maximum A√ D values for each process ranged from 2.3×10⁻² to 4.0×10⁻⁴ cm³ s^−1/2 g⁻¹ values are consistent with previously reported values for A√ D, although in this case we have determined values for the entire compositional range.     

Preparation, structure, and electrical conductivity of vanadium fluoridegraphite intercalation compound

Graphite intercalation compounds (GIC) of vanadium fluoride have been prepared in a fluorine atmosphere. The GICs prepared from highly oriented pyrolytic graphite (HOPG) were stage 1–8 compounds with composition, C_8.4–79.5VF_5.8–6.0. The apparent size of intercalated VF₆⁻(d_i) decreased from 5.33 Å to 4.15 Å along the c axis with increasing x in C_xVF₆. Various intercalated structures of VF₆⁻ between the carbon layers have been proposed for this change in d_i values. The compounds with small d_i around 4.2 Å show high stability in the air, which is due to the nestling of the VF₆⁻ anion between the carbon layers. Electron diffraction measurements have indicated that a well-nestled stage 2 GIC has high regularity in orientation of intercalated VF₆⁻ anions, which make two large unit cells of the hexagonal system ( ) with the different vectors by ±14° from that of graphite lattice. The ¹⁹F-NMR spectra and X-ray diffraction data in the low temperature region suggest a reversible phase transition. The highest electrical conductivity was 1.97 × 10⁵Scm⁻¹, which is 12 times that of pristine HOPG.     

Graphitic mesoporous carbons synthesised through mesostructured silica templates

In this paper the fabrication and characterization of graphitizable and graphitized porous carbons with a well-developed mesoporosity is described. The synthetic route used to prepare the graphitizable carbons was: (a) the infiltration of the porosity of mesoporous silica with a solution containing the carbon precursor (i.e. poly-vinyl chloride, PVC), (b) the carbonisation of the silica–PVC composite and (c) the removal of the silica skeletal. Carbons obtained in this way have a certain graphitic order and a good electrical conductivity (0.3 S cm⁻¹), which is two orders larger than that of a non-graphitizable carbon. In addition, these materials have a high BET surface area (>900 m² g⁻¹), a large pore volume (>1 cm³ g⁻¹) and a bimodal porosity made up of mesopores. The pore structure of these carbons can be tailored as a function of the type of silica selected as template. Thus, whereas a graphitizable carbon with a well-ordered porosity is obtained from SBA-15 silica, a carbon with a wormhole pore structure results when MSU-1 silica is used as template. The heat treatment of a graphitizable carbon at a high temperature (2300 °C) allows it to be converted into a graphitized porous carbon with a relatively high BET surface area (260 m² g⁻¹) and a porosity made up of mesopores in the 2–15 nm range.     

Molecular orbital study of pyrolytic carbons based on small cluster models

Molecular orbital calculations are applied to the Raman scattering and ESR of pyrolytic carbons on the basis of small cluster models. The E_2g and A_1g modes of C-C stretching vibrations of coronene, hexabenzocoronene, and circumcoronene, which belong to D_6h carbon clusters, are shown to appear around the 1550 cm⁻¹ and 1360 cm⁻¹ bands, respectively. The unpaired electrons observed in pyrolytic carbons are attributed to the bond-alternation defects on odd-numbered carbon clusters that are more easily mobile than those of trans-polyacetylene.     

High-Mobility Naphthalene Diimide Derivatives Revealed by Raman-Based In Silico Screening

Charge transport in crystalline organic semiconductors (OSCs) is considerably hindered by low-frequency vibrations introducing dynamic disorder in the charge transfer integrals. Recently, we have shown that the contributions of various vibrational modes to the dynamic disorder correlate with their Raman intensities and suggested a Raman-based approach for estimation of the dynamic disorder and search for potentially high-mobility OSCs. In the present paper, we showcase this approach by revealing the highest-mobility OSC(s) in two series of crystalline naphthalene diimide derivatives bearing alkyl or cycloalkyl substituents. In contrast to our previous studies, Raman spectra are not measured, but are instead calculated using periodic DFT. As a result, an OSC with a potentially high charge mobility is revealed in each of the two series, and further mobility calculations corroborate this choice. Namely, for the naphthalene diimide derivatives with butyl and cyclopentyl substituents, the estimated room-temperature isotropic electron mobilities are as high as 6 and 15 cm² V^–1 s^–1, respectively, in the latter case even exceeding 20 cm² V^–1 s^–1 in a two-dimensional plane. Thus, our results highlight the potential of using the calculated Raman spectra to search for high-mobility crystalline OSCs and reveal two promising OSCs, which were previously overlooked.     

Axial dispersion in flow porous electrodes

The coefficient of axial dispersionD _L in a porous electrode, composed of rolled 80-mesh platinum screen, was determined using the process of the flow electrolysis of 2.0×10^–3 M K₃Fe(CN)₆ in 1 MKCl in water. The results were analysed in the light of an earlier model for flow electrodes.List of symbols a Electrode cross-sectional area (cm²) - b Empirical constant - c ₀ Initial concentration of substrate (mol ml^–1) - D _L Axial dispersion coefficient (cm² s^–1) - D ^* Effective dispersion coefficient (cm² s^–1) - F Faraday constant (C mol^–1) - I ₁ Limiting current (A) - L Electrode height (cm) - R Limiting degree of conversion of substance - v Volume flow rate (ml s^–1) - Empirical constant - Electrode porosity     

Diamond-like carbon thin films by microwave surface-wave plasma CVD aimed for the application of photovoltaic solar cells

The nitrogen doped diamond-like carbon (DLC) thin films were deposited on quartz and silicon substrates by a newly developed microwave surface-wave plasma chemical vapor deposition, aiming the application of the films for photovoltaic solar cells. For film deposition, we used argon as carrier gas, nitrogen as dopant and hydrocarbon source gases, such as camphor (C₁₀H₁₆O) dissolved with ethyl alcohol (C₂H₅OH), methane (CH₄), ethylene (C₂H₄) and acetylene (C₂H₂). The optical and electrical properties of the films were studied using X-ray photoelectron spectroscopy, Nanopics 2100/NPX200 surface profiler, UV/VIS/NIR spectroscopy, atomic force microscope, electrical conductivity and solar simulator measurements. The optical band gap of the films has been lowered from 3.1 to 2.4 eV by nitrogen doping, and from 2.65 to 1.9 eV by experimenting with different hydrocarbon source gases. The nitrogen doped (flow rate: 5 sccm; atomic fraction: 5.16%) film shows semiconducting properties in dark (i.e. 8.1 × 10^{− 4} Ω^{− 1} cm^{− 1}) and under the light illumination (i.e. 9.9 × 10^{− 4} Ω^{− 1} cm^{− 1}). The surface morphology of the both undoped and nitrogen doped films are found to be very smooth (RMS roughness ≤ 0.5 nm). The preliminary investigation on photovoltaic properties of DLC (nitrogen doped)/p-Si structure show that open-circuit voltage of 223 mV and short-circuit current density of 8.3 × 10^{− 3} mA/cm². The power conversion efficiency and fill factor of this structure were found to be 3.6 × 10^{− 4}% and 17.9%, respectively. The use of DLC in photovoltaic solar cells is still in its infancy due to the complicated microstructure of carbon bondings, high defect density, low photoconductivity and difficulties in controlling conduction type. Our research work is in progress to realize cheap, reasonably high efficiency and environmental friendly DLC-based photovoltaic solar cells in the future.     

Raman and Si NMR spectroscopic characterization of lanthanum silicate electrolytes: Emphasis on sintering temperature to enhance the oxide-ion conductivity

Enhancement of oxide-ion conductivity has been investigated with emphasis on the high sintering temperature of apatite-type structure lanthanum silicate (La₁₀Si₆O₂₇) as a potential electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The influence of the sintering temperatures 1500, 1550, 1600 and 1650 °C as a function of ionic conductivity of the La₁₀Si₆O₂₇ electrolyte synthesized via a diethylamine (DEA) precipitation process has been characterized using impedance spectroscopy. The ionic conductivity of the La₁₀Si₆O₂₇ electrolyte sintered at 1650 °C revealed a higher value (1.22 × 10⁻² S cm⁻¹ at 700 °C) of one order of magnitude than the pellets sintered at lower temperatures. The sintered La₁₀Si₆O₂₇ pellets have been characterized by ²⁹Si NMR and Raman spectroscopy. The ²⁹Si NMR data showed the characteristic secondary peak at 81.2 ppm, which confirmed the interstitial oxygen content contributing to high oxide-ion conduction. The Raman spectra revealed the appearance of a new resolved band centered at 861 cm⁻¹ for the pellet sintered at 1650 °C compared with lower temperatures sintered pellets. The results confirmed the possibility of local structural distortion to create additional pathways for interstitial oxide-ion conduction between channels leading to higher conductivity for the pellets sintered above 1600 °C. Thus, the conduction pathway may be determined by the co-operative displacements of the SiO₄ substructure units formed at elevated sintering temperatures for high oxide-ion conductivity.     

Investigation of specific contact resistance of ohmic contacts to B-doped homoepitaxial diamond using transmission line model

In this study, metal (Ti/Pt/Au) contacts to mesa of boron-doped (boron concentration: 10¹⁸ cm⁻³) homoepitaxial diamond were fabricated by metal deposition followed by thermal annealing at 450 °C. Specific contact resistance was determined by characterizing the current–voltage (I–V) relations from transmission line model (TLM) measurement. The specific contact resistances determined from linear TLM corresponding to different lengths of rectangular contacts were in the order of 10⁻⁴ Ω cm². The results suggest that it is possible to reduce the specific contact resistance to 10⁻⁵–10⁻⁶ Ω cm², which would satisfy the operational requirements of diamond electronic devices, provided the dopant concentration in diamond can be increased to 10¹⁹–10²⁰ cm⁻³.     

An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et₄N⁺) and tetrafluoroborate (BF₄⁻) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et₄N⁺ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li⁺. For the positive electrode, BF₄⁻ was shown to intercalate above +4.3 V versus Li/Li⁺. The characteristic G-band doublet peak (E_2g2(i) (1578 cm⁻¹) and E_2g2(b) (1600 cm⁻¹)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm⁻¹) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm⁻¹) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).     

The phosphorous level fine structure in homoepitaxial and polycrystalline n-type CVD diamond

The application of very sensitive photocurrent-based spectroscopic techniques have led to the detection of new levels for the electronic structure of the phosphorous donor in n-type CVD diamond. By combining quasi-steady-state photocurrent measurements (PC), photothermal ionisation spectroscopy (PTIS) and the highly sensitive Fourier transform photocurrent spectroscopy (FTPS) technique at different temperatures, ranging from liquid nitrogen temperature to 170 K, the resulting spectra point to a richer structure than assumed up to now. This is the consequence of the improved sample quality over the last years, opening up to a much larger attainable doping window. By using doping levels, ranging from 10¹⁹ cm⁻³ down to 10¹⁶ cm⁻³ on 111 -oriented Ib HPHT substrates, still giving rise to measurable n-type conductivity, spectra showed less line broadening and more fine structure. Finally, the results will be compared with spectra measured on active P-doped polycrystalline n-type films.     

The synthesis and spectroscopic investigation of dichromophoric hemicyanine dyes

Alkane α,γ-bis[4-methylpyridinium] diiodide and alkane α,γ-bis[4-methylquinolinium] diiodide were prepared and used as starting materials in the synthesis of dichromophoric cyanine dyes. Structural confirmation of the synthesized dyes was carried out by ¹H NMR, MS spectroscopy and elemental analysis. The electronic absorption and the emission spectra for all the hemicyanines were measured in four organic solvents of varying polarity. All derivatives absorb in the region of about 500 nm and have molar absorptivity of about 10⁴ M⁻¹ cm⁻¹. The absorption spectra of tested compounds are affected by their structure i.e. the structure of dialkyl(aryl)amino group, the electron acceptor part of the dye and the linker between two identical hemicyanine chromophores. The fluorescence bands' positions, in contrast to the absorption, are strongly affected by the solvent polarity.     

A mechano- and electrochemically controlled SnSb/C nanocomposite for rechargeable Li-ion batteries

At present, graphite (LiC₆: 372 mAh g⁻¹, 840 mAh cm⁻³) is used as the anode material for lithium-ion batteries. However, methods to enhance the energy density, cyclability, initial Coulombic efficiency, and rate capability of lithium-ion batteries are still actively being researched. Here, we report a simple, fast, and novel method for transforming micron-sized Sn and Sb powders into ca. 10 nm- and 2–3 nm-sized SnSb crystallites by mechanochemical synthesis and electrochemical reactions, respectively. These nanocrystallites are uniformly distributed in an amorphous carbon matrix, resulting in a SnSb/C nanocomposite structure. The fabricated SnSb/C nanocomposite showed excellent electrochemical properties, such as a high energy density (1st charge: 706 mAh g⁻¹), long cyclability (ca. 550 mAh g⁻¹ over 300 cycles), good initial Coulombic efficiency (ca. 81%), and a fast rate capability (1C: 590 mAh g⁻¹, 2C: 550 mAh g⁻¹).