Oxidation of cerium and titanium studied by photoelectron spectroscopy

Cerium and titanium are examples of reactive metals that form protective oxide films on their surfaces upon exposure to oxygen. In order to study the building up of these oxide films we have undertaken photoemission measurements with X-ray and ultraviolet radiation (ESCA and UPS). Cerium and titanium levels were studied using ESCA on freshly in situ evaporated metal films. These levels, as well as the O 1s level, were studied after different oxygen exposures. In order to vary the probing depth, spectra have been recorded at two different electron emission angles. All measurements were performed at room temperature. Effects of oxygen exposures upon core levels were quite different in the two metals. In the Ce 3d spectrum a strong peak related to the oxide was observed at an exposure of only 2 L. Such a strong peak was not observed in the Ti 2p spectrum even after an exposure of 3000 L. The valence band spectrum of Ti as observed both by UPS and ESCA measurements, however, changed significantly at much smaller exposures.     

Infrared spectroscopy of solids

For materials like small gap semiconductors or intercalated layered compounds the general form of the complex dielectric function is: ϵ(ω) = ϵ_x + Δϵ_inter + Δϵ_intra + Δϵ_ph, where ϵ_∞is the high frequency dielectric constant due to all interband transitions except the uppermost valence band and the lowest conduction band, Δϵ_inter is the contribution to the dielectric constant due to this two bands in particular, Δϵ_intra is the contribution due to intraband free carrier transitions and Δϵ_ph is the contribution due to lattice vibrations. The contribution from transitions between valence and conduction bands to the imaginary part of the dielectric function Δϵ_inter(ω,T) for a narrow gap material can be readily calculated in the random phase approximation (RPA) formalism. The real part Δϵ_inter is obtained by performing the Kramers-Kronig inversion on the expression Δϵ_inter. Dielectric function of HgTe between 8 and 300 K is discussed. The interband contribution to the complex dielectric function in a layered intercalation compound is also examined. Pure graphite, first and second stage compounds are treated as an example. Reflectivity and magnetoreflectivity spectra simultaneously determining the plasma and the cyclotron frequencies, allow one to measure the free carrier density, hence the Fermi level, and the effective mass of the carriers. The variation of the effective mass as a function of the position of the Fermi level traces the energy bands dispersion relation. An example of such investigations is given for PbSe layered materials like Bi₂Se₃ are also studied by infrared reflectivity spectroscopy. Intercalation of such materials increases the free carrier population which consequently moves the Fermi level up in the conduction band. Analysis of reflectivity spectra allows an accurate determination of the free carrier concentration and gives a useful tool for the investigation of atom insertion in layered materials. Recent experiments on the intercalation of Li in a certain number of layered materials will be presented. In the frame of the classical theory of independent harmonic oscillators, the phonon contribution to the dielectric function is given by the sum of transverse modes for each oscillator with the corresponding damping parameters and oscillator strength. The complex dielectric function can then be written as a set of separate equations for the real and imaginary parts of the wave-number-dependent dielectric function. In the spectral region when phonon and plasmon frequencies may coincide a strong plasmon-phonon coupling will be experienced. In a simple model with one LO and one TO frequency, one expects two singularities at the two maxima of the function 1m −ϵ⁻¹; representing longitudinal modes. The frequencies generally labeled ω₊ and ω_- correspond to longitudinal oscillations with the lattice and electron plasma vibrating, respectively, in phase and 180° out of phase. In small gap materials the situation is more complex. Because of the particular band structure, the contribution Δϵ_inter(ω) must be included. In some cases it also becomes necessary to include additional oscillators with strong polar character corresponding to a particular defect or to additional vibrations. The implications of all these fundamental concepts in the investigation of high Tc materials is discussed and examples given.     

Infrared diode laser spectroscopy

Three types of lasers (double-heterostructure 66 K InAsSb/InAsSbP laser diode, room temperature, multi quantum wells with distributed feedback (MQW with DFB) (GaInAsSb/AlGaAsSb based) diode laser and vertical cavity surface emitting lasers (VCSELs) (GaSb based) have been characterized using Fourier transform emission spectroscopy and compared. The photoacoustic technique was employed to determine the detection limit of formaldehyde (less than 1 ppmV) for the strongest absorption line of the v₃ + v₅ band in the emission region of the GaInAsSb/AlGaAsSb diode laser. The detection limit (less than 10 ppbV) of formaldehyde was achieved in the 2820 cm⁻¹ spectral range in case of InAsSb/InAsSbP laser (fundamental bands of v₁, v₅). Laser sensitive detection (laser absorption together with high resolution Fourier transform infrared technique including direct laser linewidth measurement, infrared photoacoustic detection of neutral molecules (methane, form-aldehyde) is discussed.     

Infrared laser modulation spectroscopy

The lack of sensitivity in far infrared of conventional modulation techniques can be overcome by the use of a laser beam as a powerful high resolution infrared source. As an illustration of these features we describe a thermoreflectance experiment performed on mercury telluride using a frequency stabilised CO₂ laser. In this experiment a thin slab of HgTe was illuminated by the beam of the laser. A continuous shift of the Γ_6v?Γ_8c energy interval was produced by a slow temperature variation while the sample was submitted to a slight temperature modulation obtained by low frequency Joule heating. Synchronous and direct detection of the reflected beam gave the relative variation of reflectivity as a function of the sample temperature. Several spectra obtained at different emission lines enable us to determine the energy difference (E_g) between Γ_6v and Γ_8c inverted states. As a first approach a qualificative fit has been obtained with a simple model of dielectric constant and its temperature derivative. These results give the first direct determination of E_g near room temperature E_g = ? 117.04 meV at T = 286 ± 2 K.     

Novel gamma-phase of titanium metal at megabar pressures

Group IV transition metals titanium, zirconium, and hafnium are expected to transform from an ambient hexagonal close packed (hcp, alpha-phase) to a body centered cubic (bcc, beta-phase) at high pressures. This transition path is usually facilitated by the occurrence of an intermediate hexagonal phase (distorted bcc, omega-phase). The existence of a bcc phase in zirconium and hafnium at high pressures has been known for the past ten years; however, its occurrence in titanium has been theoretically predicted but never observed. We report a novel unexpected transformation in titanium metal from an omega phase to an orthorhombic phase (distorted hcp, gamma-phase) at a pressure of 116+/-4 GPa.     

Infrared spectroscopy of ICAO taggants

The IR absorption spectra of the ICAO taggants, ethylene glycol dinitrate (EGDN), o-mononitrotoluene (2-NT), p-mononitrotoluene (4-NT) and 2,3-dimethyl-2,3-dinitrobutane (DMDNB) in the vapor phase, are studied at room temperature over a wide frequency range (500–4000 cm^–1). The pre-assignment of the observed vibrational bands was performed. Modern quantum-chemical methods are applied to calculate the equilibrium geometries of these molecules and the frequencies of their fundamental vibrations. For the most intense bands of 2-NT and 4-NT, the absorption cross sections are estimated. Based on analysis of current laser technology, it has been concluded that their use in conjunction with the available spectroscopic data makes it possible to reliably perform local and remote detection and identification of ICAO taggants in an open atmosphere in real time.     

Infrared spectroscopy of nano-porous silicon

The first measurements of dielectric-permittivity and conductivity spectra of several samples of nano-porous silicon prepared by anodization of low-resistance monocrystalline silicon are performed at room temperature by means of subterahertz and IR spectroscopy in the frequency range 7–4000 cm^?1. The obtained spectra are analyzed in terms of the effective-medium theory with a size-dependent dielectric-response function of nanoinclusions and average dielectric parameters of the surronding medium. It is found that the dielectric properties of the inclusions are dependent on nano-size effects such as charge-carrier scattering at the boundaries of the nanocrystallites and increase in the band-gap energy due to the quantum size effect. The geometric and dielectric characteristics of silicon nano-size inclusions are determined. We consider the mechanisms of variation in the wide-band dielectric permittivity and conductivity spectra of monocrystalline silicon during transformation of its structure from monocrystalline to nano-porous.     

Infrared and Raman spectroscopy of graphite-ferric chloride

We present the first detailed study of the stage dependence of the IR- and Raman-active optic graphitic modes in a graphite acceptor intercalation compound. The general frequency upshift observed with increasing FeCl₃ concentration for all optic modes is interpreted to indicate an in-plane compression within the graphitic layers. An identification of the IR-active modes with bounding and interior graphite layers is made. A lineshape analysis of the IR spectra implies IR dipole moments corresponding to ～70% of the effective charge in the graphite bounding layers, independent of stage, and ～30% distributed among the graphite interior layers for stage n?3 compounds.     

Structural, optical and scintillation properties of cerium cyclotriphosphates and polyphosphates

The cerium cyclotriphosphate CeP₃O₉·3H₂O and polyphosphate Ce(PO₃)₃ have been optically investigated for the first time. In both materials, excitation and emission spectra under UV and X-ray excitations as well as emission decays of Ce³⁺ were measured at room temperature. The spectroscopic results of anhydrous Ce(PO₃)₃, prepared by progressively heating the corresponding CeP₃O₉. 3H₂O, are discussed and correlated with the structural data.For the Ce(PO₃)₃ polyphosphate material, the Stokes shift of the d-f emission is very small (760 cm⁻¹), inducing an efficient ultraviolet luminescence and a new application as scintillator.     

Infrared spectroscopy with synchrotron radiation

Up to now, storage rings have been used as sources of radiation on the X-ray and the u.v. part of the spectrum. It is shown that, with a specially designed part, a storage ring like ACO at Orsay is a very powerful far-infrared source, whose advantages over classical wide band sources are reviewed.     

Infrared reflectivity spectroscopy of electron-phonon interactions

The crucial role of electron-phonon interactions and their signatures in optical conductivity deduced from the analysis of infrared-visible reflection spectra is reviewed. The usefulness of a general phenomenological model able to describe the couplings of phonons, polarons, plasmon, superconducting condensate, is discussed. Among other examples of applications, the problem of the signature of Cooper pair condensation in the superconducting phase of high-T _c cuprates is discussed in the framework of London and Mattis-Bardeen models.     

Infrared laser stark spectroscopy of ammonia

Refined values for molecular constants of¹⁴NH₃ and less precise values for those of¹⁵NH₃ and¹⁴NH₂D were obtained with laser Stark spectroscopy. Paper was prepared for presentation at FICOLS     

Infrared Fourier transform spectroscopy of PH

The infrared vibration-rotation spectrum of the PH radical was observed in emission using a high-resolution Fourier transform spectrometer. The observation of five bands (1-0, 2-1, 3-2, 4-3, and 5-4) allowed the first six vibrational energy levels of the ground X³Σ⁻ state to be characterized. An RKR potential curve for the ground state was computed.     

Electron-energy-loss spectroscopy and X-ray absorption spectroscopy as complementary probes for complex f-electron metals: cerium and plutonium

In this paper, we demonstrate the power of electron-energy-loss spectroscopy (EELS) in a transmission electron microscope by investigating the electron structure of two f-electron metals: Ce and Pu. It is shown that EELS in a transmission electron microscope may be used to circumvent the difficulty of producing single-phase or single-crystal samples owing to its high spatial resolution, and that diffraction patterns and images can be acquired, providing unambiguous phase determination when acquiring spectra. EELS results are supported by synchrotron-radiation-based X-ray absorption, multielectron atomic spectral simulations, and local density approximation calculations based on density-functional theory with the generalized gradient approximation. For Ce, it is shown that changes in {111} stacking sequences can drive substantial modifications in the electronic structure of close-packed phases of Ce that have similar atomic volumes, contrary to previous assumptions in literature. For Pu, it is shown that Russell–Saunders (L–S) coupling fails for the 5f states and that either a j–j or an intermediate scheme must be used for the actinides because of the considerable spin–orbit interaction in the 5f states. We present a model showing how the 5f states behave along the light actinide series.     

Infrared optical constants of n-type silicon

The infrared optical constants of n-type Si are determined from reflectance and transmittance spectra. The Drude formula with empirically adjusted, concentration dependent, parameters is used. Its low-wavelength limit is in agreement with recent mobility results. A pronounced difference between As-, P-, and Sb-doped Si is found for the free electron concentration above 10¹⁹ cm^–3. Simple empirical formulae are given for the optical constants as functions of both wavenumber and concentration.     

Infrared spectroscopy of Landau levels of graphene

We report infrared studies of the Landau level (LL) transitions in single layer graphene. Our specimens are density tunable and show in situ half-integer quantum Hall plateaus. Infrared transmission is measured in magnetic fields up to B=18 T at selected LL fillings. Resonances between hole LLs and electron LLs, as well as resonances between hole and electron LLs, are resolved. Their transition energies are proportional to sqrt[B], and the deduced band velocity is (-)c approximately equal to 1.1 x 10(6) m/s. The lack of precise scaling between different LL transitions indicates considerable contributions of many-particle effects to the infrared transition energies.     

Infrared spectroscopy on lead silicate glass

The reflectance spectra of some lead silicate glasses of general formula (PbO)_x(SiO₂)_y have been measured in the infrared frequency range from 50 to 4000 cm^–1. The dispersion and absorption spectra in the range 50–2000 cm^–1 have been calculated from the reflectance data using the Kramers-Kronig relations. The band at 135 cm^–1 is assigned to the stretching vibration of lead-oxygen bonds. The shoulder band of the silicon-oxygen stretching mode at 900 cm^–1 shows a weak coupling of those bonds to the Pb²⁺ modifier. The vibration strength of those bands shows that the number of the Pb²⁺ modifier increases first up approximately to 50 Mol% with the increase of PbO content and then decreases rapidly. It indicates that different PbO content causes different structural forms in lead silicate glasses: The addition of small amounts of PbO to vitreous silica serves to modify the continuous three-dimensional silica network: whereas in those glasses with a high lead content, the influence of the cation, Pb²⁺, appears to lie between that of network former and network modifier. This result is in agreement with the structural model of Worrel and Henshall.