Carbon K-edge Region Research Articles

Effect of Surface Passivation on Nanodiamond Crystallinity

Diamonds approaching the nanoscale have the potential for use as probe materials as their optical properties can be sensitive to optical/electric fields, mechanical stress/pressure, and the configuration of nuclear spins. The surface of nanodiamonds impacts their optical properties and sensing capabilities, and examining the nanodiamond surface through X-ray absorption can give insights into molecular surface structures. Here, quantum dot models with varying amounts of surface carbon passivation are prepared, optimized, and compared. The loss of the diamond sp3 lattice is examined by investigating the bond length and tetrahedral character of the carbons comprising nanodiamonds for the appearance of aromatic sp2 surface domains. Electronic transitions in the carbon K-edge region, using the energy-specific time-dependent density functional theory method, as well as vibrational spectra are computed from the optimized models. The surface reorganization is shown to affect the electronic characteristics of the ...

Hybrid Complex Polarization Propagator/Molecular Mechanics Method for Heterogeneous Environments.

We introduce a hybrid complex polarization propagator/molecular mechanics method for the calculation of near-resonant and resonant response properties of molecules in heterogeneous environments, which consist of a metallic surface, or nanoparticle, and a solvent. The applicability and performance of the method is demonstrated by computations of linear absorption spectra of p-nitroaniline physisorbed at a gold/dimethyl sulfoxide interface in the UV/vis and near-carbon-K-edge regions of the spectrum. It is shown that the shift of absorption cross-section induced by the heterogeneous environment varies significantly depending on the nature of the excited states encountered in the targeted frequency region as well as on the actual size of the resonant frequencies, and that the solvent component of the heterogeneous environment is responsible for the major part of the environmental shift, especially in the higher frequency range of the carbon K-edge region.

In situ removal of carbon contamination from a chromium-coated mirror: ideal optics to suppress higher-order harmonics in the carbon K-edge region.

Carbon-free chromium-coated optics are ideal in the carbon K-edge region (280-330 eV) because the reflectivity of first-order light is larger than that of gold-coated optics while the second-order harmonics (560-660 eV) are significantly suppressed by chromium L-edge and oxygen K-edge absorption. Here, chromium-, gold- and nickel-coated mirrors have been adopted in the vacuum ultraviolet and soft X-ray branch beamline BL-13B at the Photon Factory in Tsukuba, Japan. Carbon contamination on the chromium-coated mirror was almost completely removed by exposure to oxygen at a pressure of 8 × 10(-2) Pa for 1 h under irradiation of non-monochromated synchrotron radiation. The pressure in the chamber recovered to the order of 10(-7) Pa within a few hours. The reflectivity of the chromium-coated mirror of the second-order harmonics in the carbon K-edge region (560-660 eV) was found to be a factor of 0.1-0.48 smaller than that of the gold-coated mirror.

Near edge X-ray absorption mass spectrometry on coronene.

We have investigated the photoionization and photodissociation of free coronene cations C24H12 (+) upon soft X-ray photoabsorption in the carbon K-edge region by means of a time-of-flight mass spectrometry approach. Core excitation into an unoccupied molecular orbital (below threshold) and core ionization into the continuum both leave a C 1s vacancy, that is subsequently filled in an Auger-type process. The resulting coronene dications and trications are internally excited and cool down predominantly by means of hydrogen emission. Density functional theory was employed to determine the dissociation energies for subsequent neutral hydrogen loss. A statistical cascade model incorporating these dissociation energies agrees well with the experimentally observed dehydrogenation. For double ionization, i.e., formation of intermediate C24H12 (3+⋆)trications, the experimental data hint at loss of H(+) ions. This asymmetric fission channel is associated with hot intermediates, whereas colder intermediates predominantly decay via neutral H loss.

In situ soft X-ray absorption spectroscopy of flames

The feasibility of in situ soft X-ray absorption spectroscopy for imaging carbonaceous species in hydrocarbon flames is demonstrated using synchrotron radiation. Soft X-rays are absorbed by core level electrons in all carbon atoms regardless of their molecular structure. Core electron spectroscopy affords distinct advantages over valence spectroscopy, which forms the basis of traditional laser diagnostic techniques for combustion. In core level spectroscopy, the transition linewidths are predominantly determined by the instrument response function and the decay time of the core–hole, which is on the order of a femtosecond. As a result, soft X-ray absorption measurements can be performed in flames with negligible Doppler and collisional broadening. Core level spectroscopy has the further advantage of measuring all carbonaceous species regardless of molecular structure in the far-edge region, whereas near-edge features are molecule specific. Interferences from non-carbon flame species are unstructured and can be subtracted. In the present study, absorption measurements in the carbon K-edge region are demonstrated in low-pressure (P total = 20–30 Torr) methane jet flames. Two-dimensional imaging of the major carbonaceous species, CH4, CO2, and CO, is accomplished by tuning the synchrotron radiation to the respective carbon K-edge, near-edge X-ray absorption fine structure (NEXAFS) transitions and scanning the burner.

Near-Edge X-ray Absorption Fine Structure Spectra and Site-Selective Dissociation of Phenol

A time-of-flight mass spectrometer with orthogonal acceleration and soft X-rays from synchrotron radiation were utilized to measure near-edge X-ray absorption fine structure (NEXAFS) spectra of carbon and oxygen in phenol and the corresponding ionic fragments following core excitation. The photon energies were in the range of 284-298 eV for the carbon K-edge and 529.5-554.5 eV for the oxygen K-edge. The total ion yield, ion intensity for each ionic fragment, and ion intensity ratio, defined as ion intensity divided by total ion yield, were measured as a function of photon energy. Possible mechanisms of dissociation are proposed and enhancements of specific products of dissociation are reported. In general, the enhancement of these specific products is small in the carbon K-edge region but is clear for some products at the oxygen K-edge. In particular, elimination of the H atom from the hydroxyl group was observed only at the oxygen K-edge. One remarkable result is that an excitation of a core-level electron of oxygen greatly enhanced the cleavage of specific C-C bonds.

New route to the fabrication of nanocrystalline diamond films

Nanocrystalline diamond (NCD) thin films offer applications in various fields, but the existing synthetic approaches are cumbersome and destructive. A major breakthrough has been achieved by our group in the direction of a non-destructive, scalable, and economic process of NCD thin-film fabrication. Here, we report a cheap precursor for the growth of nanocrystalline diamond in the form of paraffin wax. We show that NCD thin films can be fabricated on a copper support by using simple, commonplace paraffin wax under reaction conditions of Hot Filament Chemical Vapor Deposition (HFCVD). Surprisingly, even the presence of any catalyst or seeding that has been conventionally used in the state-of-the-art is not required. The structure of the obtained films was analyzed by scanning electron microscopy and transmission electron microscopy. Raman spectroscopy and electron energy-loss spectroscopy recorded at the carbon K-edge region confirm the presence of nanocrystalline diamond. The process is a significant step towards cost-effective and non-cumbersome fabrication of nanocrystalline diamond thin films for commercial production.

Attosecond pulse generation in carbon K-edge region (284 eV) with sub-250 μJ driving laser using generalized double optical gating method

We studied attosecond pulse generation in the carbon K-edge region with generalized double optical gating, which provides a temporal gate for a near-infrared driving laser in high harmonic generation. Since the technique selectively generates the harmonics from the peak of driving laser field, the cutoff component is emphasized in the spectrum. Consequently, the harmonics was achieved up to 284 eV using a driving laser with sub-250 μJ pulse energy. The spectrum supported 20-as duration. The driving laser pulse energy is the lowest value ever reported for high harmonic generation in the carbon K-edge region.

Single-step route to diamond-nanotube composite

Candle wax was used as a precursor for the production of a diamond-nanotube composite in a single step. The composite films were fabricated by sulfur-assisted hot-filament chemical vapor deposition technique. The morphology of the composite films was analyzed by scanning electron microscopy and transmission electron microscopy. Raman spectra of the films show characteristic diamond band at 1,332 cm−1, D-band around 1,342 cm−1, and graphitic G-band around 1,582 cm−1. The electron energy-loss spectroscopy recorded at the carbon K-edge region shows signature features of diamond and carbon nanotube in the fabricated material. The ability to synthesize diamond-nanotube composites at relatively low temperatures by a single-step process opens up new possibilities for the fabrication of nanoelectronic devices.

In situremoval of carbon contamination from optics in a vacuum ultraviolet and soft X-ray undulator beamline using oxygen activated by zeroth-order synchrotron radiation

Carbon contamination of optics is a serious issue in all soft X-ray beamlines because it decreases the quality of experimental data, such as near-edge X-ray absorption fine structure, resonant photoemission and resonant soft X-ray emission spectra in the carbon K-edge region. Here an in situ method involving the use of oxygen activated by zeroth-order synchrotron radiation was used to clean the optics in a vacuum ultraviolet and soft X-ray undulator beamline, BL-13A at the Photon Factory in Tsukuba, Japan. The carbon contamination of the optics was removed by exposing them to oxygen at a pressure of 10(-1)-10(-4) Pa for 17-20 h and simultaneously irradiating them with zeroth-order synchrotron radiation. After the cleaning, the decrease in the photon intensity in the carbon K-edge region reduced to 2-5%. The base pressure of the beamline recovered to 10(-7)-10(-8) Pa in one day without baking. The beamline can be used without additional commissioning.

Free standing graphene-diamond hybrid films and their electron emission properties

Free standing graphene-diamond hybrid films have been fabricated using saturated hydrocarbon polymers as seeding material by hot filament chemical vapor deposition technique. The films are characterized with x-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS). The XRD shows the characteristic diffraction peaks of both diamond and graphene. The Raman spectrum shows the characteristic band of diamond at 1332 cm−1 and D, G, and 2D bands of graphene at 1349, 1592, and 2687 cm−1, respectively. Both SEM and TEM depict the presence of diamond and graphene in the films. The EELS recorded in the carbon K-edge region also shows the signature peaks of diamond and graphene. The free standing hybrid films exhibit a remarkably low turn-on field of about 2.4 V/μm and a high emission current density of 0.1 mA/cm2. Furthermore, emission currents are stable over the period of 7 days. The superior field emission characteristics of the free standing graphene-diamond hybrid films are attributed to the heat sink capability of diamond and high electrical conductivity of graphene.

Site- and geometry-specific CH…O interaction in small acetaldehyde clusters studied with core-electron excitation spectroscopy in the carbon K-edge region

Site-dependent C1s-core excitation spectra of small acetaldehyde (AAL) clusters have been studied under the cluster regime of beam conditions. The excitation spectra of the clusters were generated by monitoring the partial-ion-yields of cluster-origin fragments. Comparison of the cluster bands with the monomer bands revealed that the band intensities of C1s core-to-Rydberg transitions come to be strongly excitation-site dependent upon cluster formation showing significant reduction of C1sHCO→Ryd bands relative to the monomer bands. Computer modeling of X-ray absorption spectra using a density functional theory calculation demonstrated that the intensity reduction is the outcome of the site- and geometry-specific CH…O interaction where hydrogen-bonding association between the aldehyde (HCO) sites of different AAL molecules takes place exclusively within the clusters. As the representatives of small AAL clusters (n≥3), two types of molecular complexes (a planar cyclic trimer and a tetramer with a stack of two dimers) were derived to rationalize the site-dependence of the experimental C1s excitation spectra. Spectral simulation of the above complexes could reproduce the experimental site-dependence of the core-to-Rydberg band-features upon clusterization, indicative of significant contribution of these clusters under the present beam-stagnation condition.

Hydrogen bonding in acetone clusters probed by near-edge x-ray absorption fine structure spectroscopy in the carbon and oxygen K-edge regions

Hydrogen bonding in acetone clusters was investigated using near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of the cluster ions were measured as the NEXAFS spectra of acetone clusters. In the carbon K-edge region, the first resonance peak, which was assigned to the C(CO) 1s-->pi( *)(C=O) resonance transition, showed no substantial change in the PIY curves of the acetone clusters, while the C(CH3) 1s-->3ppi(CH(3)) excitation feature was found to be strongly suppressed. The selective suppression of the C(CH3) 1s-->3ppi(CH(3)) resonance transition can be explained by the change in the character of the 3ppi(CH(3)) orbital due to the C=O...H-C type of hydrogen-bonding interaction. On the other hand, the NEXAFS spectra of the acetone molecule and clusters were almost identical in the oxygen K-edge region, except for a small shift in the pi( *)(C=O) resonance of 0.13 eV, because the character of the pi( *)(C=O) orbital remained, regardless of the C=O...H-C hydrogen bonding interaction.

Hydrogen bonding in methanol clusters probed by inner-shell photoabsorption spectroscopy in the carbon and oxygen K-edge regions

Hydrogen bonding in methanol clusters has been investigated by using inner-shell photoabsorption spectroscopy and density functional theory (DFT) calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of H(CH(3)OH)(n)(+) were measured as the soft x-ray absorption spectra of methanol clusters. The first resonance peak in the PIY curves, which is assigned to the sigma*(O-H) resonance transition, exhibits a 1.20 eV blueshift relative to the total-ion-yield (TIY) curves of molecular methanol in the oxygen K-edge region, while it exhibits a shift of only 0.25 eV in the carbon K-edge region. Decreased intensities of the transitions to higher Rydberg orbitals were observed in the PIY curves of the clusters. The drastic change in the sigma*(O-H) resonance transition is interpreted by the change in the character of the sigma*(O-H) molecular orbital at the H-donating OH site due to the hydrogen-bonding interaction.

Vibrational effect on the fragmentation dynamics of the C K-shell excited CF 2CH 2

Photoabsorption cross-sections of CF 2CH 2 were measured in the carbon K-edge region and linear time-of-flight mass spectra were acquired at some photon energies across the two π * peaks. The kinetic energy distributions of CH 2 + and CF 2 + with two components were deduced from the analysis of the mass spectra. The CH 2 + ion with high kinetic energies increases with the extent of vibrational excitation of the C F 1s → π * state, indicating that molecular vibrations play an important role in the photofragmentation of the inner-shell excited molecule.

Resonance photoemission and near edge X-ray absorption fine structure (NEXAFS) of Ni 3Al(111) covered with CO

The adsorption of carbon monoxide (CO) on the (111) surface of the ordered alloy Ni 3Al has been investigated by photoelectron spectroscopy using synchrotron radiation. The valence region spectrum was analyzed as the photon energy changed in the range between 60 and 75 eV. A resonance enhancement of a CO peak (1π) was observed for energy close to the Ni 3p ionization threshold (67–68 eV). This result suggested that CO molecules adsorbed on the (111) crystal face of Ni 3Al are preferentially bonded to Ni atoms. Near edge X-ray absorption fine structure (NEXAFS) spectra of the carbon K-edge region have been studied. The spectra were dominated by resonances arising from a sharp bound state transition to an unoccupied molecular orbital of π symmetry and by a broader σ shape resonance in the continuum. The dependence of these resonance structures on the polarization of the synchrotron light indicated the perpendicular orientation of CO on the surface of Ni 3Al(111).

Orientation dependence of the carbon K-edge in the electron energy loss spectra of a potassium-benzenegraphite intercalation compound

Electron energy loss spectra of the carbon K-edge region in graphite and the first-stage potassium-benzene-graphite intercalation compound (GIC) have been measured as a function of the crystal orientation defined by the angle between the crystal c-axis and the incident electron beam direction. The intensity of the carbon 1s → π ∗ transition peak strongly depends on the crystal orientation. The dependence for potassium-benzene-GIC differs from that for graphite. By analysing the orientation dependence of the 1 s → π ∗ transition intensity observed in potassium-benzene-GIC, it is found that the molecular plane of benzene intercalating between the graphite layers is tilted relative to the crystal c-axis.