X-ray photoelectron spectroscopic study on initial oxidation of hafnium hydride fractured in an ultra-high vacuum

The initial oxidation of hafnium hydride was studied by X-ray photoelectron spectroscopy (XPS). The clean surface of hafnium hydride was obtained by fracturing the specimen in an XPS measurement chamber under a background pressure of 2.7 × 10⁻⁶ Pa. The fractured surface was oxidized in situ with the exposure to high-purity oxygen and the residual gases in an ultra-high vacuum chamber. The XPS spectra for the oxidized surfaces had the shoulder due to the oxidation, and the shoulder grew up with increase in exposure time even in the ultra-high vacuum. The factor analysis for the XPS spectra of the oxidized surface showed that the oxide formed in the chamber consists of only the hafnium dioxide, and no suboxide states are contained. The result corresponded to the oxide observed on hafnium hydride fractured in air.     

Monoclinic-tetragonal phase transition in zirconium and hafnium dioxides: A high-temperature raman scattering investigation

Zirconium dioxide ZrO₂ and hafnium dioxide HfO₂ are investigated using high-temperature Raman spectroscopy in the temperature range 300–2080 K, including the regions of the monoclinic-tetragonal phase transitions revealed in these materials. An analysis is made of the specific features observed in the evolution of the high-temperature Raman spectra of both the monoclinic (m) and tetragonal (t) modifications of ZrO₂ and HfO₂ with variations in the temperature. The polarized Raman spectra of the metastable tetragonal phases in solid solutions based on zirconia and hafnia are used to identify the symmetry of vibrations in the spectra of the tetragonal modifications of pure zirconium and hafnium dioxides, which exist at high temperatures.     

PAC study of nuclear relaxation in solids:181Ta in hafnium hydrides

The electric quadrupole interaction (QI) at the site of¹⁸¹Ta in different hafnium hydrides HfH_x has been investigated as a function of temperature by TDPAC measurements. Below 300 K the QI is static within a 300 nsec time window. Above 300 K a dynamic QI related to the diffusion of hydrogen atoms leads to relaxation effects in the TDPAC spectra. The average residence time between hydrogen jumps, evaluated on the basis of the theory of stochastic perturbations, ranges from 100 nsec at 400 K in the ɛ-phase to 1 nsec at 700 K in the α-phase of the hafnium-hydrogen system. The activation energy for hydrogen jumps was found to be independent of the hydrogen concentration: E_a=0.53(12) eV.     

Auger parameter of hafnium in elemental hafnium and in hafnium oxide

X-ray photoelectron spectroscopy has been used to determine the Auger parameters in elemental hafnium and in hafnium oxide (HfO₂). The zirconium L_α line has been used as a source of excitation to study the 3d core levels of hafnium, the 1s core level of oxygen, and the X-ray excited MNN Auger region of hafnium and KVV Auger region of oxygen. The Auger parameters for hafnium and oxygen have been determined from these spectral data. In case of oxygen, the Auger parameter has been compared with the corresponding value in water. The change in the Auger parameter is observed to be negative for hafnium and positive for oxygen. We have shown that the opposite signs of the Auger parameters in binary systems can be utilized to determine the direction of charge transfer between the constituents. This is consistent with the chemical shift due to charge transfer. This chemical shift in the core level has been evaluated by subtracting the relaxation shift from the experimentally observed core level shift. It is found to be positive for the 3d_5/2 core level of hafnium in the oxide indicating a charge transfer from hafnium to oxygen in the oxide. The observations are consistent with Pauling’s electronegativity criterion.     

The synthesis of hafnium nanomaterials by alkali metal reduction of hafnium tetrachloride

Hafnium tetrachloride was reduced in organic solvents with lithium powder, sodium–potassium alloy, or lithium hydride/Et₃B. All reductions required sonochemical agitation to proceed at an appreciable rate, with the notable exception of the reaction of HfCl₄ with Li in diethyl ether. Activation of C–H bonds occurred in all reactions, which resulted in carbon-containing products. HfCl₄ was reduced on a 50-g scale with LiH/Et₃B, and a 10-g scale with Li powder in pentane. All the solid products from the reductions were converted to nanomaterials by annealing under vacuum from 500 to 1,000 °C, which also resulted in the sublimation of the alkali metal salts. The nanomaterials contain a mixture of products with the α-Hf (hexagonal) structure (crystallite size 8–250 nm) and the HfC (FCC) structure (crystallite size 3–80 nm), with the amount of hafnium in the bulk annealed product varying from 88 to 99 wt%. When toluene, pentane, or triethylamine solvents were used, the presence of amorphous graphitic or carbonaceous material was also detected by solid state ¹³C NMR. Thermally annealed products were additionally characterized by electron microscopy and thermal analysis under Ar/O₂, and have BET surface areas ranging from 2.7 to 155 m²/g.     

Electronic structure of hafnium: A compton profile study

In this paper, we report the first-ever isotropic Compton profile of hafnium measured at an intermediate resolution, with 661.65 keV γ-radiation. To compare our experimental data, the theoretical computations have also been carried out within the framework of pseudopotential using CRYSTAL03 code and the renormalized-free-atom (RFA) model. It is found that the present experimental profile is in better agreement with the RFA calculations if the outer electronic configuration is chosen as 5d^3.26s^0.8. The cohesive energy of Hf is also deduced from the experimental data and is compared with the available data. On leave from Hindu College, Sonepat 131 001, India     

Optical characterization of sol gel TiO<Subscript>2</Subscript> monoliths doped with Brilliant Green

Amorphous titanium dioxide monoliths doped with brilliant green (BG) were synthesized by the sol-gel process. The optical properties of the monoliths were characterized by Photoacoustic Spectroscopy and Photoluminescence Spectroscopy. The absorption spectra for the BG-doped TiO₂ monoliths exhibited two well defined absorption regions: a band below 400 nm corresponding to TiO₂ absorption and three absorption bands centered at 424 nm, 588 nm, and 632 nm due to brilliant green. While the undoped TiO₂ monoliths showed no luminescence, the doped samples showed a strong luminescence band at 673 nm, which increased its intensity for increasing organic dye doping.     

Dependence of optical properties on specific surface area and grain sizes in TiO2 powders

The diffuse reflectance (DR) spectra and the cathodoluminescence (CL) spectra in the range 0.34–2.10 μm and changes in the spectra after bombardment by accelerated electrons have been studied as a function of the specific surface area and the grain sizes of titanium dioxide (rutile) powders of different grades (P1, P2, P02, R10). It has been established that the diffuse reflection coefficient and the luminescence band intensity increase as the specific surface area decreases and the grain size of the powder increases. A smaller specific surface area of the powders means lesser initial flareup and subsequent “quenching” of the CL bands as a function of electron fluence. It has been shown that history-related differences between powders of different grades is a less significant factor than the specific surface area in determining the diffuse reflectance and luminescence and also the radiation resistance of the powders. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 73–77, January–February, 2006.     

An XPS study of hafnium nitride films

XPS spectra are presented from films of different stoichiometry: HfN_1.0 made by CVD and reactive sputtering and HfN_1.09 made by ion plating. They support the existing theoretical calculations where the valence band comprises a strong Hf 5d band immediately below E_F and a band of mainly N 2p character some 6 eV below E_F. The core levels are shifted to larger binding energies by about 1.5 eV indicating electron transfer from hafnium to nitrogen. The effect of substoichiometry on the spectra is very small.     

Energy stimulation of autowave synthesis of hafnium aluminides

The production of hafnium aluminides from mixtures of hafnium or its oxide with aluminum in the combustion mode is impossible because of a near-zero thermal effect. The present study is aimed at stimulating autowave chemical transformation with the help of energetic formulations and producing cast hafnium aluminides by means of combustion methods. The characteristics of the autowave synthesis and the conditions for producing cast hafnium aluminides are determined, and their composition and structure are investigated.     

ISOL beams of hafnium isotopes and isomers

The production of ISOL beams of hafnium is described. Radioactive Hf isotopes were produced at ISOLDE by 1.4 GeV proton-induced spallation in Ta and W foils. Chemical evaporation in form of HfF₄ and mass separation in the molecular sideband HfF₃⁺ after electron impact ionization provided intense and pure beams. Beams of ^158-185Hf and short-lived isomers down to 1.1 s ^177mHf were observed, but the method could be extended to reach even more exotic isotopes: down to about ¹⁵⁴Hf (N=82) on the neutron-deficient side and up to neutron-rich ¹⁸⁸Hf.     

Spectral-luminescent parameters of the amniotic fluid

Absorption and luminescence excitation and emission spectra of the amniotic fluid from females with a normal course of pregnancy and with fetation anomalies are investigated. It is shown that the amniotic fluid manifests, in addition to an intense UV luminescence, a luminescence in the range of 380–650 nm. The first luminescence peak with λ_max = 430–450 nm is most likely due to the presence of NADH₂ and hormones in the amniotic fluid, whereas the peak located at longer wavelengths with λ_max = 520–540 nm is due to pigments (bilirubin, etc.). Differences in absorption spectra of the amniotic fluid in the case of the normal course of pregnancy and upon its pathologies are established. Luminescence emission and excitation spectra of the amniotic fluid in cases of intrauterine fetation pathologies are shifted toward the longwave region compared to normal pregnancy cases. It is concluded that the spectral-luminescent analysis of the amniotic fluid can be used as an additional rapid test for monitoring of intrauterine fetal pathologies. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 939–942, November–December, 1998.     

Luminescence centers in α-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics

Luminescence photoexcitation spectra of α-Bi₂O₃ ceramics are investigated. Luminescence spectra were deconvoluted into fundamental components using the Alentsev-Fok method. It is established that the luminescence spectra of α-Bi₂O₃ ceramics consist of three fundamental bands with maxima at 2.75, 2.40, and 1.97 eV. A comparison of the results with those from an investigation of luminescence of various modifications of bismuth oxide and bismuth germanates suggests that luminescence of these compounds is caused by radiation processes that occur in structural complexes that contain the bismuth ion in a nearest oxygen environment. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 672–676, September–October, 2008.     

Trivalent zirconium and hafnium ions in yttrium oxide ceramics

An analysis of the electron spin resonance (ESR) spectrum of transparent ceramics composed of yttrium oxide with zirconium and hafnium additives has revealed the presence of signals (with similar parameters) from Zr³⁺ and Hf³⁺ ions, which have a similar electron configurations of the ground states: [Kr]4d ¹ and [Xe]5d ¹, respectively. It is shown that the pulsed cathodoluminescence spectra of these ions consist of two bands peaking at λ ≈ 818 and 900 nm.     

Luminescence centers in Sc2O3

Sc₂O₃ luminescence spectra are studied. The spectra are separated into elementary bands by the Alentsev–Fock method. It is established that the luminescence spectra consist of a number of overlapping bands with maxima at 3.5; 3.05; 2.65; 2.35, and 2.05 eV. The band at 3.5 eV is interpreted as emission of self-localized excitons, and the other bands, as defect-center recombination. L’vov State University, 50, Dragomanov St., L’vov, 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 776–778, November–December, 1997.     

Luminescence of thulium-activated cubic boron nitride

Under high pressure and temperature conditions, we have obtained samples of thulium-activated cubic boron nitride in the form of micropowders, ceramics, and polycrystals activated by thulium in the presence of aluminum. We studied the cathodoluminescence (CL), photoluminescence (PL), and photoluminescence excitation spectra of the samples. In the luminescence spectra we observe structured bands with maxima at ∼370, ∼475, ∼660, and ∼ 800 nm, assigned to electronic transitions in the triply charged thulium ions. We have established that the most efficient method for excitation of “blue” luminescence at ∼475 nm for thulium ions in cBN is excitation by an electron beam. The cBN samples synthesized in the presence of Al have photoluminescence spectra with a more complex structure compared with samples not containing Al, with the band of dominant intensity at about 660 nm. Hypothetically, this is a consequence of incorporation of thulium ions into the crystalline phases cBN and AlN, which are equally likely to be formed during synthesis. The observed photoluminescence spectrum of the indicated samples is the superposition of the photoluminescence spectra of the Tm³⁺ ions located in the crystal fields of cBN and AlN of different symmetries. The presence in the photoluminescence excitation spectra (at 450, 490, and 660 nm) of structure, with features at wavelengths shorter than the excited photoluminescence, suggests a nonresonant mechanism for its excitation. We have established that luminescence of Tm³⁺ ions is less intense than for other rare earth elements incorporated into cubic boron nitride. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 547–555, July–August, 2008.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

Atomic-vacancy ordering and magnetic susceptibility of nonstoichiometric hafnium carbide

Experimental data on the magnetic susceptibility of nonstoichiometric hafnium carbide HfC_y(0.6< y<1.0) are presented. Anomalies are found in the temperature dependences of the magnetic susceptibility of the carbides HfC_0.71, HfC_0.78, and HfC_0.83 in the temperature range 870–930 K. These anomalies are due to the formation of a superstructural short-range order in their nonmetallic sublattice. It is shown that the short-range order in the carbides HfC_0.71 and HfC_0.78 corresponds to the ordered phase Hf₃C₂, while in the carbide HfC_0.83 it corresponds to the ordered phase Hf₆C₅. It is found that the magnetic susceptibility of the carbide HfC_0.78 in the temperature interval 910–980 K is zero. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 4, 296–301 (25 February 1999)     

Temperature dependence of the electric field gradient at Ta nuclei in hafnium pyrovanadate

The electric field gradient EFG in hafnium pyrovanadate has been measured at Hf sites at different temperatures with the time-differential perturbed angular correlation method. The results obtained show the existence of a phase transition around 110°C.     

Excitation of3 G 0-states of titanium, zirconium, and hafnium atoms by electron impact

Detailed information about excitation cross-selections of spectral lines of titanium, zirconium, and hafnium atoms obtained using extended crossed beams are used for calculation of the excitation cross-sections of the³G⁰-levels of these atoms. Results are compared with cross-sections calculated in Born’s approximation. For titanium: it is found that theoretical predictions agree well with experimental data. Differences found for zirconium are explained by the single-configuration approximation used in the calculation. Moscow Power Institute, Russia, 14 Krasnokazarmennaya St., 111250, Moscow E-250, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 707–710, November–December, 1997.