Paramagnetische Wasserstoffzentren in Kaliumjodid

After irradiation with ultraviolet light at low temperature KJ crystals doped with SH^? or SeH^? ions show the ESR spectra of interstitial hydrogen atoms (U ₂ centers). The behavior of the spectra is studied at 9 and 35 GHz respectively, and the parameters of the spin Hamiltonian have been determined. Forbidden transitions with changes Δm=±1 of the nuclear quantum number are found to occur with appreciable intensity in KJ. Above 95 K the hydrogen atoms become unstable and react to new paramagnetic hydrogen centers.     

氢离子注入对硅单晶电子辐照缺陷和氢泡形成的影响

以50keV和100keV能量的氢离子注入p型(100)直拉硅单晶薄膜。注入剂量为10¹⁵—2×10¹⁷H⁺/cm²。试样在HU-1300型超高压透射电子显微镜中进行电子辐照和原位加热动态观察。结果表明在20—300℃温度范围内与未注氢硅相比,注氢硅在相同的电子辐照条件下产生的电子辐照缺陷较少,电子辐照缺陷形成所需的潜伏时间较长。在电子显微镜中加热试样时于190℃开始观察到氢泡,190—220℃范围内氢泡逐渐产生并长大 关键词：     

Optical and EPR investigations of a new hydrogen center in potassium chloride

In KCl interstitially diffusing neutral hydrogen atoms (H _i ⁰ ) can be trapped near substitutional Li⁺ ions. The new center possesses a characteristic absorption band at 250nm, at the long wavelength side of the knownH _i ⁰ absorption band (235nm). EPR measurements reveal, that the hydrogen atoms are closely connected to the Li⁺ ions at a cation lattice site forming (LiH)⁺ molecules. Below 70K hydrogen and lithium occupy a fixed relative position to each other in a (111) crystal direction: the hydrogen shows a superhyperfine interaction to three equivalent Cl^– neighboring ions. Above 70K the hydrogen exhibits a superhyperfine interaction to six equivalent chlorine neighbors, interpreted by a rapid reorientational motion of the (LiH)⁺ molecule within the cation vacancy. The high temperature interaction parameters can be explained as the time average of the low temperature values. A qualitative explanation of the optical absorption of the (LiH)⁺ center is given.     

Critical point and mechanism of the fluid–fluid phase transition in warm dense hydrogen

The density functional theory is used to calculate the equation of state and the proton–proton pair correlation functions in the range of hydrogen temperatures and densities where the fluid–fluid phase transition is expected. The metastable states are considered. The critical temperature has been estimated to be ~4000 K. We propose a two-step mechanism: the partial ionization of molecules to produce H ₂ ⁺ ions at the phase transition followed by the formation of H ₃ ⁺ ions.     

Interaction of hydrogen and deuterium with intrinsic atomic defects in high-purity electron-irradiated nickel

Abstract

High-purity nickel was irradiated with 2 MeV electrons at temperatures below 80 K to a dose of 1 × 10²³ e^?/m² in the as-prepared state and after charging with H or D. By means of magnetic after-effect measurements relaxations of anisotropic radiation-induced defects and of defect-hydrogen complexes were investigated in the temperature range between 4.2 and 500 K. The isochronal annealing behaviour of these relaxations and the isochronal recovery of the residual resistivity was measured simultaneously on the same specimens. At temperatures below the hydrogen mobility (< 160 K) in charged irradiated specimens relaxation maxima are observed at 45, 100, 115 and 140 K which show no isotope shift for H and D charging. The maxima below 160 K are explained by defect-hydrogen complexes, where radiation-induced defects reorient around immobile hydrogen atoms. Above 160 K, where hydrogen atoms get mobile, in charged irradiated specimens a broad relaxation maximum appears at 170 K which shows an inverse isotope shift for H and D charging. This 170 K maximum anneals in Stage III. A hydrogen diffusion maximum observed in charged specimens at 215 K prior to irradiation is missing after electron irradiation. The 170 K relaxation is explained by defect-hydrogen complexes, where hydrogen atoms reorient around immobile radiation-induced defects while the long-range hydrogen diffusion is suppressed by these defects. In such relaxation measurements hydrogen and deuterium atoms are used as a “probe” to investigate radiation-induced defects.     

Investigation of structure and magnetic characteristics of Ni-implanted AlGaN films

The structural, valence of elements and magnetic characteristics of Ni-implanted Al_0.5Ga_0.5N films, deposited on Al₂O₃ substrates by metalorganic chemical vapor deposition (MOCVD), were reported. Ni ions were implanted into Al_0.5Ga_0.5N films by Metal Vapor Arc (MEVVA) sources under the energy of 100 keV for 3 h. The films were annealed at 900 K in the furnace for the transference of Ni ions from interstitial sites to substitutional sites in AlGaN and activating the Ni³⁺ ions. Characterizations were carried out in situ using X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS) and Vibrating sample magnetometer (VSM), indicating that the films have wurtzite structure without forming a secondary phase after annealing. Ni ions were successfully implanted into substitutional sites of Al_0.5Ga_0.5N films and the chemical bonding states of Ni³⁺ is Ni–N. The apparent hysteresis loops prove the films exhibited ferromagnetism at 300 K. The room temperature (RT) M_s and H_c obtained were approximately 0.22 emu/g and 32.97 Oe, respectively. From the first-principles calculation, A total magnetic moment of 2.86 μB per supercell is calculated: the local magnetic moment of NiN₄ tetrahedron, 2.38 μB, makes the primary contribution. The doped Ni atom hybridizes with its four nearby N atoms in NiN₄ tetrahedron, then N atoms are spin polarized and couple with Ni atom with strong magnetization, which result in ferromagnetism. Therefore, the p-d exchange mechanism is responsible for ferromagnetism in Ni-doped AlGaN. It is expected that the room temperature ferromagnetic Ni-doped Al_0.5Ga_0.5N films can make it possible to the applications for the spin electric devices.     

Localisation of iron ions in NH4,Na-Y zeolite: A Mössbauer effect study

Localisation of Fe ions in deep-bed treated NH₄,Na-Y zeolite at 830K, 940K, and 1050K, as well as after reduction by hydrogen, and dealumination with subsequent calcination is studied by⁵⁷Fe Mössbauer spectroscopy. Most of the incorporated iron is present in the form of octahedrally coordinated ferric species with two distinct sets of hyperfine parameters assigned to atoms inside the zeolite structure and in extraframework positions. Fe²⁺ ions with high coordination are also detected and their amount increases with the temperature of deep-bed treatment. Low-temperature Mössbauer effect measurements at 77K and 4.2K were employed to facilitate the identification of iron sites.     

Bose–Einstein condensation of atomic hydrogen

The recent creation of a Bose–Einstein condensate of atomic hydrogen has added a new system to this exciting field. The differences between hydrogen and the alkali metal atoms require other techniques for the initial trapping and cooling of the atoms and the subsequent detection of the condensate. The use of a cryogenic loading technique results in a larger number of trapped atoms. Spectroscopic detection is well suited to measuring the temperature and density of the sample in situ. The transition was observed at a temperature of 50 μK and a density of 2×10¹⁴ cm^-3. The number of condensed atoms is about 10⁹ at a condensate fraction of a few percent. A peak condensate density of 4.8×10¹⁵ cm^-3 has been observed. Received: 22 June 1999 / Published online: 3 November 1999     

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter ~ 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid–liquid transition of supercooled confined water) on a “wet” sample with hydration h ~ 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually “dry” sample at h ~ 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid–liquid transition hypothesis.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.     

快重离子辐照引起Ni/SiO2界面原子混合及相变研究

在室温下用308 MeV的Xe离子和853 MeV的Pb离子辐照Ni/SiO2样品, 用卢瑟福背散射和X射线衍射技术对样品进行了分析。 通过分析Ni/SiO2样品中元素成分分布和结构随离子辐照剂量和电子能损的变化, 探索了离子辐照在Ni/SiO2样品中引起的界面原子混合与结构相变现象。 实验结果显示, Xe和Pb离子辐照均能引起明显的Ni原子向SiO2基体的扩散并导致界面附近Ni, Si和O原子的混合。 实验观测到低剂量Xe离子辐照可产生NiSi2相, 而高剂量Xe离子辐照则导致了Ni3Si和NiO相的形成。 根据热峰模型, Ni原子的扩散和新相的形成可能由沿离子入射路径强电子激发引起的瞬间热峰过程驱动。Ni/SiO2 interface were irradiated at room temperature with 308 MeV Xe ions to 1×1012, 5×1012 Xe/cm2 and 853 MeV Pb ions to 5×1011 Pb/cm2, respectively. These samples were analyzed using Rutherford Backscattering Spectrometry (RBS) and X ray diffraction spectroscopy (XRD), from which the intermixing and phase change were investigated. The obtained results show that both Xe and Pb ions could induce diffusion of Ni atoms to SiO2 substrates and result in intermixing of Ni with SiO2. Furthermore, 1.0×1012 Xe/cm2 irradiation induced the formation of NiSi2 and 5.0×1012 Xe/cm2 irradiation created Ni3Si and NiO phases. The diffusion of Ni atoms and the formation of new phase may be driven by a transient thermal spike process induced by the intense electronic energy loss along the incident ion path.     

The topography of nickel crystals during the reaction towards Ni(CO)4; A field ion microscope study

The structural aspect of the formation of Ni(CO)₄ by the reaction of CO with solid nickel has been studied. The nickel initial state was a nearly hemispherical single crystal as prepared by field evaporation of a nickel field emitter tip. Field-free reaction of CO with the clean nickel surface took place at pressures up to 2 mbar, reaction times up to 45 h, and at a temperature of 373 K, which as a result from work by others was found optimum for highest rates of Ni(CO)₄ formation. Neon field ion imaging at 80 K after reaction with CO showed the crystal always in an intermediate state, which had the features: (1) Areas of {;111} were increased; (2) at half angles between a central (111) and peripherical {111} planes there were {110} planes flanked by {210}, and {100} flanked by {511}, respectively; (3) with the exception of the planes mentioned in feature (2), the remaining surface area was more than mono-atomically stepped. From these results and in accordance with the theory of crystal growth (Kossel, Stranski) and the theory of crystal dissolution (Lacmann, Franke, Heimann) a pure octahedron is expected to be the final state of the crystal. This implies that nickel atoms removed by the reaction are most frequently taken from 〈110〉 atom chains of the {111} planes.     

A photoemission study of the interaction of Ni(100), (110) and (111) surfaces with oxygen

Photoelectron spectroscopic studies of the oxidation of Ni(111), Ni(100) and Ni(110) surfaces show that the oxidation process proceeds at 295 and 485 K in two distinct steps: a fast dissociative chemisorption of oxygen followed by oxide nucleation and lateral oxide growth to a limiting coverage of 3 NiO layers. The oxygen concentration in the 295 K saturated oxygen layer on Ni(111) was confirmed by ¹⁶O(d,p) ¹⁷O nuclear microanalysis. At 295 and 485 K the oxide growth rates are in the order Ni(110) > Ni(111) > Ni(100). At 77 K the oxygen uptake proceeds at the same rate on all three surfaces and shows a continually decreasing sticking coefficient to saturation at ~2.1 layers (based upon NiO). An O 1sb.e. = 529.7 eV is associated with NiO, and O ls b.e.'s of ~531.5 and 531.3 eV can be associated, respectively, with defect oxide (Ni₂O₃) or (in the presence of H₂O) with an NiO(H) species. The binding energies (Ni 2p, O 1s) of this NiO(H) species are similar to those for Ni(OH)₂. Defect oxides are produced by oxidation at 485 K, or by oxidation of damaged films (e.g. from Ar⁺ sputtering) and evaporated films. Wet oxidation (or exposure to air) of clean nickel surfaces and oxides, and exposure of thick oxide to hydrogen at high temperature results in an O 1s b.e. ~531.3 eV species. Nuclear microanalysis ²H(³He,p) ⁴He indicates the presence of protonated species in the latter samples. Oxidation at 77 K yields O 1s b.e.'s of 529.7 and ~531 eV; the nature of the high b.e. species is not known. Both clean and oxidised nickel surfaces show a low reactivity towards H₂O; clean nickel surfaces are ~10³ times less reactive to H₂O than to oxygen.     

Lateral interactions in the thermal desorption of H2 from clean Cu/Ni(110) alloy surfaces

The adsorption of hydrogen on a clean Cu10%/Ni90% (110) alloy single crystal was studied using flash desorption spectroscopy (FDS), Auger electron spectroscopy (AES), and work function measurements. Surface compositions were varied from 100% Ni to 35% Ni. The hydrogen chemisorption on a-surface of 100% nickel revealed strong attractive interactions between the hydrogen atoms in accordance with previous work on Ni(100). Three desorption states (β₁, β₂ and α) appeared in the desorption spectra. The highest temperature (α) state was occupied only after the initial population of the β₂-state. As the amount of copper was increased in the nickel substrate, desorption from the higher energy binding α-state was reduced, indicating a decrease in the attractive interactions among hydrogen atoms. The hydrogen coverage at saturation was not affected by the addition of copper to the nickel substrate until the copper concentration was greater than 25% at which a sharp reduction in saturation coverage occurred. This phenomenon was apparently due to the adsorption of hydrogen on Ni atoms followed by occupation of NiNi and CuNi bridged adsorption sites, while occupation of CuCu sites was restricted due to an energy barrier to migration.     

A cems study of119Sn ion-implanted into Ni

Conversion electron Mössbauer spectroscopy (CEMS) was applied to study the behaviour of¹¹⁹Sn atoms implanted into Ni at the accelerating energy of 100–400KeV and doses of 5×10¹⁵–5×10¹⁶ ions/cm² at room temperature. All CEMS spectra were measured at room temperature and successfully analyzed by two components. The energy and dose dependence of CEMS spectra were well explained by the depth distribution of¹¹⁹Sn atoms.     

The theoretical and experimental study of the ionization processes during the low energy ion sputtering

The process by which atoms are ionized as they are sputtered from a metal surface has been analyzed both theoretically and experimentally. In the theoretical part the expressions for ionization coefficient R⁺ of atoms having the ionization energy much larger than the metal work function have been derived using a molecular orbital method. The effect of the level crossing was estimated in an approximate way. In the experimental part the SIMS experiments on clean Ni and Al surfaces and on Ni surface covered with a submonolayer of adsorbed K, Na and Al are reported. It has been found and it is for the first time reported that the energy distribution of ions sputtered from a submonolayer of adatoms is independent of energy (200–2500 eV) and mass (Ar⁺ Xe⁺ of incident ions and depends only upon the adsorption energy of the adatom. The energy distribution of ions sputtered from bulk samples has been found dependent on the primary ion energy. The measurement of the absolute value of R⁺ has shown that there is a strong correlation between the number of the adatom valence d-electrons and the value of R⁺, the value of R⁺ being smaller for atoms with more d-electrons. These experimental data have been compared with the theoretical expressions and the important role of the mechanism which takes into account the bending of the adatom energy level has been assessed.     

Matrix ENDOR of ion-exchange systems

Electron nuclear double resonance (ENDOR) has been investigated in sulfocation exchangers, containing free radicals stabilized in polymeric matrix or Cu²⁺ and (VO)²⁺ as counterions. It was shown that the ENDOR signal is mainly due to electron-nuclear dipole-dipole interactions between the unpaired electron and nuclei of polymeric matrix or hydrogen atoms of water molecules which hydrate the charge groups. In order to quantitatively describe the ENDOR line shape and intensity, the theory of matrix ENDOR is developed. The correctness of this theory was tested by comparing the temperature dependence of spin-lattice relaxation times calculated from ENDOR line intensities with the corresponding dependence obtained from stationary saturation electron spin resonance spectra. A good agreement was observed in the temperature range from 200 to 350 K. The structural parameters of surroundings of paramagnetic ions Cu²⁺ and (VO)²⁺, which include four coordinated spheres on the distance from 0.3 to 1.2 nm, were calculated. The motional parameters, correlation time and activation energy of mobile protons were also determined. It is concluded that the activation processes of water self-diffusion and proton exchange take place at high temperature, whereas the proton tunneling transfer is possible at low temperature.     

Method for measuring chemical diffusion coefficients in solids

Experiments were performed with temperature programmed desorption of hydrogen and deuterium adsorbates on small platinum spheres. Beyond the expected desorption peak of these adsorbates at around 300 K sample temperature an additional desorption peak at higher temperatures was observed. This additional peak is explained by the diffusion of hydrogen or deuterium atoms from the inside of the spheres to their surfaces with final desorption from these surfaces. The visibility of this second high temperature desorption peak is supported by a small diameter of the platinum spheres. Platinum spheres with diameters around 64 μm were used. The sample temperature at which the second peak was observed depends on the parameters: diameter of the platinum spheres, heating rate of the sample and chemical diffusion coefficient of hydrogen or deuterium in platinum. A theory, which assumes that the chemical diffusion coefficient can be described with an Arrhenius ansatz, was developed to simulate the occurrence of the second peak. The combination of these kinds of experiments with the theory gives a method to measure chemical diffusion coefficients. This method can be called temperature programmed diffusion. At 510 K sample temperature the diffusion coefficient 1.61×10⁻¹² m²/s of hydrogen in platinum and the diffusion coefficient 1.40×10⁻¹² m²/s of deuterium in platinum was measured.     

Isotopic ratio of evaporated ions,critical ionization distances,and ionization regions in the process of the field evaporation of molybdenum at high temperatures

A magnetic mass spectrometer with a field ion source has been used to study the steady-state field evaporation of molybdenum at a temperature of 1000–2000 K. Ions of all seven molybdenum isotopes have been observed in the process of evaporation; only low-charge ions Mo⁺² and Mo⁺ have been detected. The critical ionization distances and ionization regions for single- and double-charge Mo ions have been identified based on the measured ion energies and the experimentally determined intensity of the evaporation field. It has been demonstrated that ions are produced in the process of field evaporation of surface atoms at certain distances from the emitter surface in a very narrow spatial region.     

A 1H NMR study of the effects of Ni additions on the behavior of hydrogen in β-vanadium hydride

The behavior of hydrogen in the hydrides of vanadium metal containing small amounts of nickel was studied by ¹H NMR spectroscopy. FT spectra and spin-spin and spin-lattice relaxation times for VH_0.77, V_0.95Ni_0.05H_0.73, and V_0.90Ni_0.10H_0.65 were measured at temperatures between 77 and 400 K. On the addition of nickel the number of hydrogen atoms on O₂₂ sites decreases and the superstructure of hydrogen is altered. Different effects of nickel on hydrogen diffusion are observed above and below about 200 K, and, therefore, the mechanism of hydrogen diffusion is assumed to change at this temperature.