Diffusion of nitrogen in ion-implanted chromium and tungsten

The diffusion of N in the group VI B metals Cr and W has been studied in the previously uninvestigated temperature ranges 300°–550 °C (Cr) and 600°–800 °C (W) using ion-beam techniques. Diffusion couples were created by ion-implantation. The timedependent diffusion profiles were monitored by the use of the Nuclear Resonance Broadening (NRB) technique. The linear Arrhenius plots extracted from the measured diffusivities indicate that the diffusivity of implanted N in Cr and W can be described by the activation energyQ=1.39±0.06 eV and 2.32±0.16 eV and the pre-exponential factorD ₀=(7.0±7.2)×10^–4cm^2/s and 4.3±8.3cm^2/s, respectively. The solubilities of N in Cr and W from the implanted distributions were found to deviate from those obtained using conventional metallographical methods.     

Diffusion behaviour of Nb in yttria-stabilized zirconia single crystals: A SIMS, AFM and X-ray reflectometry investigations

Using secondary ion mass spectrometry (SIMS) we have investigated the concentration vs. depth profile of Nb, thermally diffused into (1 0 0)-oriented yttria-stabilized zirconia (YSZ) single crystal substrates. The surface morphology of Nb films and YSZ substrates was analyzed using atomic force microscopy (AFM). The structural disorder and the interface configuration of the samples were investigated by X-ray reflectometry (XRR). Two kinds of substrates were used: as-received (AR) and reduced (R) ones. The R-substrates were obtained by thermal annealing of AR-substrates in air for 2 h at 1250 °C. The bulk diffusion coefficients D_T in the temperature range of 780-1000 °C, activation energy Q, and the pre-exponential factor, D₀, have been obtained for Nb in YSZ. For the AR single crystals, the results can be well represented by the expression:

     

The changes of capacitance-loss and current-voltage characteristics of LaMnO3 + δ/SrTiO3:Nb heterojunctions exposed to ambient air

Effects of moisture absorption on capacitance-loss and current-voltage characteristics of LaMnO_3 + δ/SrTiO₃:Nb heterojunction had been investigated after the heterojunctions were exposed to ambient air. The moisture-absorption-induced increases in loss tangent and breakdown voltage were observed, whereas no changes were found on capacitance and diffusion voltage. These results were discussed by the decrease of oxygen ions in LaMnO_3 + δ and the generation of hydroxide ions at grain boundaries. This work will favor both electronic transport analysis and future device applications.     

Diffusion of Al in ion-implanted α-Zr and α-Hf

The diffusion of Al in the group IVa metals Zr and Hf has been studied for the first time in the temperature ranges 600°–800°C (Zr) and 750°–900°C (Hf) using ion-beam techniques. Diffusion couples were created by ion-implantation. The time-dependent diffusion profiles were monitored by the use of the Nuclear Resonance Broadening (NRB) technique. The linear Arrhenius plots extracted from the measured diffusivities indicate that the diffusivity of implanted Al in Zr and Hf can be described by the activation energyQ=2.9±0.2eV and 3.7±0.3eV and the pre-exponential factorD ₀=17±42cm²/s and 170±600cm²/s, respectively.     

XPS and ToF-SIMS analysis of natural rubies and sapphires heated in an inert (N2) atmosphere

Advanced surface analysis techniques: X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, have been employed in the study of heat treatment of natural corundum as ruby and sapphire. The stones were heat treated in an inert (N₂) atmosphere. The setting temperatures were: 1000, 1100, 1200, 1300, 1400, 1500 and 1600 °C. The XPS studies and the parallel ToF-SIMS experiments revealed diffusion behavior of Fe and Ti in the as-mined stones as evidenced by surface observations. Both metals exhibited broad maxima in surface concentration near 1300 °C. Owing to its superlative detection limit, ToF-SIMS spectra are able to provide the temperature-dependent concentration profiles of trace transition metals such as Cr, Cu and V at a level not detectable by XPS. Visible appearance of the stones is clearly affected by heat treatment. Interestingly, the ruby stones did not exhibit cloudy inclusion (“silk”) on heating, contrary to previous experiments under atmospheric conditions.     

Effects of niobium on thermal stability and corrosion behavior of glassy Cu-Zr-Al-Nb alloys

The corrosion behavior of Cu_95−xZr_xAl₅ (x=40, 42.5 and 45 at.%) in 1 N HCl, 3 mass% NaCl and 1 N H₂SO₄ solutions was studied. As Zr content increases, the corrosion resistance is slightly enhanced. In order to improve the corrosion resistance of the Cu-Zr-Al glassy alloy, Nb was selected to substitute Cu. Although the supercooled liquid region ΔT_x of the Cu-Zr-Al glassy alloys decreases with increasing Nb content, the alloys still retain high glass-forming ability and bulk glassy samples with 1.5 mm diameter can be obtained when up to 5 at.% Nb was added. It is found that the addition of Nb results in improvement of the corrosion resistance of the glassy Cu-Zr-Al alloys.     

Photoluminescence of gold, copper and niobium as a function of temperature

A specially constructed instrument for measuring the low intensity photoluminescence emission spectra of metals is described. It uses low luminescence optical components and dedicated sample mounting techniques. Room temperature measurements agree closely with literature spectra for high-purity gold and are found to be sensitive to 100 ppm impurities. Detailed spectra are presented, which are weakly temperature dependent, for gold, copper and unpolished niobium between room temperature and 100 K. We conclude that this work provides accurate luminescence data for Au from 300 K down to 100 K. Although the (variable temperature) luminescence data for Cu are consistent both with the room temperature experimental data in the literature and theory, we conclude the role of surface adsorbates and/or oxides cannot be ruled out. Theory suggests that Nb has a factor ∼50 lower luminescence intensity than Au and Cu because the real part of the refractive index is a factor ∼5 higher and the density of states ∼2 eV below the Fermi energy is a factor of ∼4 lower than Au and Cu. Measurements are presented for unpolished Nb, but given the lack of signal detection for polished Nb and that theory predicts very weak signals, we conclude that the luminescence signals from pure Nb still remain below the sensitivity of our instrument.     

Properties of reactively sputtered W–B–N thin film as a diffusion barrier for Cu metallization on Si

Thin films of W–B–N (10 nm) have been evaluated as diffusion barriers for Cu interconnects. The amorphous W–B–N thin films were prepared at room temperature via reactive magnetron sputtering using a W₂B target at various N₂/(Ar + N₂) flow ratios. Cu diffusion tests were performed after in-situ deposition of 200 nm Cu. Thermal annealing of the barrier stacks was carried out in vacuum at elevated temperatures for one hour. X-ray diffraction patterns, sheet resistance measurement, cross-section transmission electron microscopy images, and energy-dispersive spectrometer scans on the samples annealed at 500°C revealed no Cu diffusion through the barrier. The results indicate that amorphous W–B–N is a promising low resistivity diffusion barrier material for copper interconnects.     

Subsurface miscibility of metal overlayers with V, Nb and Ta substrates

The high solubility and diffusivity of oxygen in Nb, Ta and V are responsible for the difficulty in the preparation of a clean, well-ordered (1 0 0) surfaces of these early transition metals. The deposition and subsequent annealing of a metal overlayer on Nb(1 0 0) are a convenient route for the preparation of flat surfaces with the Nb lattice constant and a metallic character. Such well-ordered, stable, inert and easily reproducible Nb(1 0 0)-like surfaces can be produced due to the suppression of oxygen surface segregation by a suitable layer blocking sub-surface oxygen diffusion. For example, a Nb(1 0 0)-like surface can be obtained by annealing thin Au or Pd films deposited on Nb(1 0 0), since this results in a Au–Nb or Pd–Nb alloy situated just below the surface which preserves the structure of the Nb-lattice and effectively suppresses the oxygen segregation toward the surface. In contrast, Ag and Cu layers do not show this property as these metals do not form a bulk alloy with Nb. The presence or absence of bulk alloying and its relation to surface oxygen contamination is a general phenomena observed for many metallic layers deposited on V, Nb and Ta substrates. A discussion of results reported in the literature is given for these adsorbate systems.     

Theoretical study of hydrogen dissociation and diffusion on Nb and Ni co-doped Mg(0001): A synergistic effect

The interaction of H₂ with clean, Ni and Nb doped Mg(0001) surface are investigated by first-principles calculations. Individual Ni and Nb atoms within the outermost surface can reduce the dissociation barrier of the hydrogen molecule. They, however, prefers to substitute for the Mg atoms within the second layer, leading to a weaker catalytic effect for the dissociation of H₂, a bottleneck for the hydriding of MgH₂. Interestingly, co-doping of Ni and Nb stabilizes Ni at the first layer, and results in a significant reduction of the dissociation barrier of H₂ on the Mg surface, coupled with an increase of the diffusion barrier of H. Although codoped Ni and Nb shows no remarkable advantage over single Nb here, it implies that the catalytic effect could be optimized by co-doping of “modest” transition metals with balanced barriers for dissociation of H₂ and diffusion of H on Mg surfaces.     

Compositional characterisation of Zn-diffused lithium niobate waveguides

Rutherford backscattering (RBS) and secondary-ion mass spectrometry techniques have been used to investigate the two-step process involved during waveguide fabrication in LiNbO₃ using Zn-vapour diffusion. Compositional analysis (O, Nb, Li and Zn) in the two steps has been characterised. RBS analysis reveals that the first step, involving a heating of the substrate under a metallic Zn atmosphere, gives rise to a partial exchange between the Nb and Li ions from the crystals and the Zn from the vapour source. The second treatment at higher temperature in an open atmosphere diffuses the Zn deeper into the substrate, thus forming an optical waveguide, while the Nb and Li ions recover their bulk values. Received: 16 May 2001 / Revised version: 7 September 2001 / Published online: 30 October 2001     

体心立方金属中间隙杂质原子组态的弹性研究——Ⅰ.间隙杂质原子的位置及扩散激活能

将金属视为一各向同性的、无限大的、均匀的连续弹性介质,利用弹性偶极子的概念,计算了在体心立方金属Fe,W,Mo,Ta,Nb中,间隙杂质原子C,N,O,H在四面体及八面体位置上的位置能。计算结果表明,除了H在W,Mo,Ta,Nb中是占据四面体位置外,其余的情况都是占据八面体位置,并求得了判定间隙原子是处在四面体抑八面体位置的临界半径。后一部分计算了间隙原子在八面体位置间扩散的激活能。所得的结论都与前人的实验结果较好地接近。     

Experimental investigations and DICTRA simulations on formation of diffusion-controlled fcc-rich surface layers on cemented carbides

Wear resistant fcc-rich surface layers were produced on cemented carbides by nitridation of W-Ti-Ta-Nb-Co-C compositions at 1400 °C in nitrogen atmosphere. A 15 ± 3 μm thick (Ti,Ta,Nb,W)(C,N) top-layer formed on the surface of the cemented carbides. The driving force for formation of the fcc-rich layers was the difference in nitrogen activity between the sintering atmosphere and the cemented carbide bulk, which promoted in-diffusion of nitrogen and out-diffusion of Ti, Ta and Nb. The diffusion-controlled process was modeled by DICTRA considering that all diffusion occurred in the liquid binder phase of a dispersed system model with a labyrinth factor of λ(f) = f. Good agreement between experimental and simulations regarding layer thickness, phase fraction distribution and element profiles was obtained for the presented model.     

Advanced design of periodical architectures in bulk metals by means of Laser Interference Metallurgy

Patterning of high-resolution features on large-area metallic substrates has been performed by means of the Laser Interference Metallurgy method. Due to the intensity distribution of the interference pattern, this technique allows to locally and periodically heat the material surface to temperatures higher than the melting point with a long-range order. In this study, commercial stainless steel, copper and aluminum substrates were irradiated using single pulses of a nanosecond Nd:YAG laser with two and three laser-beam configurations operating at 355 nm of wavelength. Thermal simulations have been performed by finite element method and compared to the experiments. The results indicate that the structuring is produced by a surface tension driven mechanism induced by the thermal gradient. Moreover, metals with short thermal diffusion lengths present very homogeneous structures and the structure depth that can be achieved at relatively high laser fluences during single-pulse experiments is on the order of the diffusion length.     

Grain Boundary Diffusion and Segregation in Interstitial Solid Solutions Based on BCC Transition Metals: Carbon in Niobium

Bulk and grain boundary (GB) diffusion of ¹⁴C in Nb has been studied by the radiotracer serial sectioning technique. B and C kinetic regimes were realized for GB diffusion in the temperature range from 800 to 1173 K. The values of P = sD _gb, D _gb and s follow the Arrhenius dependencies: P = 5.15 × 10^–15 exp[–(83.1 kJ/mol)/RT] m³/s (973–1173 K), D _gb = 2.3 × 10^–6 exp[–(133.0 kJ/mol)/RT] m²/s (800–950 K), and s = 4.7 exp[(49.9 kJ/mol)/RT].The increase in the GB diffusion compared with self-diffusion is very large despite the probable retardation effect due to the strong segregation.The results for GB diffusion of C in Nb as well as for other interstitial solutes (P, S) in bcc transition metals (- Fe, Mo) are discussed in the framework of the transition state theory. It is assumed that GB segregation decreases the energy of the ground state whereas the change in the diffusion mechanism (e.g. from vacancy to interstitial) leads to a strong decrease of the transition state energy. This change in the diffusion mechanism results in a fast GB diffusion of interstitial solutes in spite of their large tendency to segregate to GBs.     

Void ordering in hexagonal close-packed metals

Voids occur in solids exposed to high-temperature particle irradiation. In hexagonal metals with lattice-parameter ratiosc/a which are smaller than for ideal close-packing, voids arranged in layers parallel to the basal plane have been observed after high-dose irradiation, whereas more perfect void ordering, e.g. the formation of void lattices like in cubic metals, has not been found. In this paper it is shown that it is the two-dimensional diffusion of self-interstitial atoms in the basal plane which gives rise to the layer-type arrangement of voids. The possibility of other void-ordering phenomena in hexagonal metals is investigated. It is demonstrated that, under certain circumstances, one-dimensional diffusion of a metastable self-interstitial configuration may lead to the arrangement of voids in columns perpendicular to the basal plane.     

Quantum diffusion of light interstitials in metals

A quantum theory of diffusion of self-trapped light interstitials in metals is presented. The theory encompasses both coherent and incoherent tunneling, but the approximation used neglects the dependence of the interstitial transfer matrix element on the vibrational state of the crystal. The coherent tunneling contribution is estimated by fitting the incoherent diffusion rate to experimental data for hydrogen and muon diffusion. It is predicted that coherent diffusion should be dominant below ～ 80 K for H in Nb and below ～ 190 K for μ⁺ in Cu. Experimental verifications of these predictions would require high purity strain free samples and low concentrations of the diffusing species.     

Calculation of the surface energy of bcc transition metals by using the second nearest-neighbor modified embedded atom method

The surface energies for 24 surfaces of all bcc transition metals Fe, Cr, Mo, W, V, Nb and Ta have been calculated by using the second nearest-neighbor modified embedded atom method. The results show that, for all bcc transition metals, the order among three low-index surface energies E_(1 1 0) < E_(1 0 0) < E_(1 1 1) is in agreement with experimental results and E_(1 1 0) is also the lowest surface energy for various surfaces. So that from surface energy minimization, the (1 1 0) texture should be favorable in the bcc films. This is also consistent with experimental results. The surface energy for the other surfaces increases linearly with increasing angle between the surfaces (h k l) and (1 1 0). Therefore, a deviation of a surface orientation from (1 1 0) can be used to estimate the relative values of the surface energy.     

High refractive index and transparent heavy metal oxide glassy thin films

Heavy metal oxide thin films of the ternary system Nb₂O₅–GeO₂–PbO have been prepared by pulsed laser deposition in an O₂ environment from either glassy or crystalline bulk samples. The range of ([Pb]+[Nb]) content in which the films are optically homogeneous and transparent is much broader (0.5–1.0) than that of the bulk samples considered in the present work (0.55–0.62). The imaginary part of the refractive index is very low in all cases (k<10^-3), whereas the real part increases linearly with the ([Pb]+[Nb]) content up to values as high as 2.35. The optical energy gap has been found to be strongly dependent on [Pb], whereas it is almost independent of [Nb]. This dependence is discussed in terms of the role of Pb and Nb as network modifiers or formers. Received: 5 August 2002 / Accepted: 8 August 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. Fax: +34-91/564-5557, E-mail: j.gonzalo@io.cfmac.csic.es     

Temperature dependent preferential sputtering in CoSi2 and NbSi2

Sputtering of CoSi₂ and NbSi₂ has been carried out by Xe ion bombardment at room temperature, as well as at elevated temperatures putting these systems in their radiation-enhanced diffusion regimes. The range of the Xe ions (at 200–260 keV) was appreciably less than the thickness of the silicides. The samples were analyzed by 2 MeV He⁺ backscattering spectrometry, x-ray diffraction and optical microscopy. The ratio of the sputtering yield of Si to that of the metal (i.e., Co or Nb) always exceeds the stoichiometric ratio 21, leading to Si depleted surface layers. The amount of the sputtered species increases almost linearly with dose until intermixing of the silicide with the underlying Si becomes appreciable. This happens at lower doses in the radiation-enhanced diffusion regime than at room temperature. Irradiation of CoSi₂ samples at high temperature leads to a broadening of the implanted Xe profile compared to the room temperature profile. No such phenomenon has been found in NbSi₂. The effect of Xe broadening on the sputtering yields is discussed.