The synthesis of polycrystalline H3O+β″βAl2O3 ceramics from conventional precursor NaKβ″/βAl2O3 powders

H₃O⁺β″Al₂O₃, H₃O⁺/βAl₂O₃ and H₃O⁺β″/βAl₂O₃ /ZrO₂ ceramics of equiaxed, fine-grained microstructure were prepared by conventional synthesis techniques, gas-phase and vapour-phase ion exchange to the potassium form and field-assisted ion exchange in dilute HCl vapour to the hydronium form. The bend strength of the polycrystalline H₃O⁺β″Al₂O₃ and H₃O⁺β″/βAl₂O₃ was > 200 MPa. The conductivity of H₃O⁺β″Al₂O₃, H₃O⁺β″/βAl₂O₃ ZrO₂ was 8×10⁻⁶, 2×10⁻⁶ and 9×10⁻⁷ (Ω cm)⁻¹, respectively, at 25°C. The materials were demonstrated to perform in steam electrolysis cells at 100°C.     

Luminescent collisions of He+ and He++ ions with H2 molecules at energies below 2 keV

Spectroscopic studies of collisions between He⁺ and He⁺⁺ ions with H₂ gas target have been performed in the 200–600 nm wavelength range. Atomic lines of hydrogen Balmer series and several helium lines were identified and their excitation functions between 50 eV and 1 keV (2 keV for He⁺⁺) were determined.     

Ionized physical vapor deposited Al2O3 films: Does subplantation favor formation of α‐Al2O3?

The broad energy distributions of the condensing particles typically encountered in ion assisted vapor deposition techniques are often a drawback when attempting to understand the effect of the energetic bombardment on the film properties. In the current study, a monoenergetic Al⁺ beam generated by a filtered cathodic arc discharge is employed for the deposition of alumina (Al₂O₃) films at well defined Al⁺ ion energies between 4 eV and 200 eV at a substrate temperature of 720 °C. Structural analysis shows that Al⁺ energies of 40 eV or larger favor the formation of the thermodynamically stable α‐Al₂O₃ phase at the expense of other metastable Al₂O₃ polymorphs. The well defined ion energies are used as input for Monte‐Carlo based simulations of the ion–surface interactions. The results of these simulations reveal that the increase of the Al⁺ ion energy leads to an increase in the fraction of ions subplanted into the growing film. These findings underline the previously not considered role of subsurface processes on the phase formation of ionized physical vapor deposited Al₂O₃ films. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The structural and electric behavior of SrBi2Ta2O9 ferroelectric thin films with H+ implantation

The structural and electrical characteristics of H⁺-implanted SrBi₂Ta₂O₉ (SBT) ferroelectric thin films were investigated by X-ray diffraction analysis and electrical measurements. 25 keV H⁺ with doses ranging from 1 × 10¹⁴/cm² to 3 × 10¹⁵/cm² were implanted into the Sol-Gel prepared SBT ferroelectric thin films. The X-ray diffraction patterns of SBT films show that no difference appears in the crystalline structure of H⁺-implanted SBT films compared with unimplanted films. Ferroelectric properties measurements indicate that both remnant polarization and the coercive electric field of H⁺-implanted SBT films decrease with increasing the implantation dose. The disappearance of ferroelectricity was found in the H⁺-implanted SBT films up to a dose of 3 × 10¹⁵/cm². The leakage current-voltage (I-V) and capacitance-voltage (C-V) characteristics of the H⁺-implanted SBT films were also discussed before and after a recovery process.     

High-rate reactive magnetron sputtering of zirconia films for laser optics applications

ZrO₂ exhibits low optical absorption in the near-UV range and is one of the highest laser-induced damage threshold (LIDT) materials; it is, therefore, very attractive for laser optics applications. This paper reports explorations of reactive sputtering technology for deposition of ZrO₂ films with low extinction coefficient k values in the UV spectrum region at low substrate temperature. A high deposition rate (64 % of the pure metal rate) process is obtained by employing active feedback reactive gas control which creates a stable and repeatable deposition processes in the transition region. Substrate heating at 200 °C was found to have no significant effect on the optical ZrO₂ film properties. The addition of nitrogen to a closed-loop controlled process was found to have mostly negative effects in terms of deposition rate and optical properties. Open-loop O₂ gas-regulated ZrO₂ film deposition is slow and requires elevated (200 °C) substrate temperature or post-deposition annealing to reduce absorption losses. Refractive indices of the films were distributed in the range n = 2.05–2.20 at 1,000 nm and extinction coefficients were in the range k = 0.6 × 10^?4 and 4.8 × 10^?3 at 350 nm. X-ray diffraction analysis showed crystalline ZrO₂ films consisted of monoclinic + tetragonal phases when produced in Ar/O₂ atmosphere and monoclinic + rhombohedral or a single rhombohedral phase when produced in Ar/O₂ + N₂. Optical and physical properties of the ZrO₂ layers produced in this study are suitable for high-power laser applications in the near-UV range.     

Zirconia‐Alumina Nanoparticles Prepared by Laser Evaporation: Powder Characterisation by TEM and 27Al MAS NMR

Contrary to predictions of the ZrO₂‐Al₂O₃ phase diagram powders of solid solutions of alumina in zirconia with up to 40 mol% Al₂O₃ are described in the recent literature. Up to now the interpretations of the microstructure of these materials are still inconsistent. Therefore we reinvestigated nanopowders prepared by laser evaporation starting from a mixture of 55 mol% ZrO₂ and 45 mol% Al₂O₃ by analytical high resolution transmission electron microscopy (TEM) and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR). The results reveal that in case of this preparation route a heterogeneous powder system is formed consisting dominantly of nanocrystallites of zirconia with an incorporation of, obviously, only a very small amount of alumina, and that the crystallites are surrounded by an amorphous layer of predominantly alumina. No indication was found that Al³⁺ ions occupy seven‐ or eight‐fold co‐ordinated sites of Zr⁴⁺ ions. A simple kinetic model for the formation of the nanoparticles' microstructure is given.     

Enhanced memory performance by tailoring the microstructural evolution of (ZrO2)0.6(SiO2)0.4 charge trapping layer in the nanocrystallites-based charge trap flash memory cells

ZrO₂ nanocrystallites based charge trap memory cells by incorporating a (ZrO₂)_0.6(SiO₂)_0.4 film as a charge trapping layer and amorphous Al₂O₃ as tunneling and blocking layer were prepared and investigated. The precipitation reaction in charge trapping layer forming ZrO₂ nanocrystallites during rapid thermal annealing was investigated by transmission electron microscopy. The density and size of ZrO₂ nanocrystallites are the critical factors for controlling the charge storage characteristics. The ZrO₂ nanocrystallites based memory cells after postannealing at 800 ^°C for 60 s exhibit the best electrical characteristics and a low charge loss ～5 % after 10⁵ write/erase cycles operation.     

Luminescence in collisions of low-energy ions with graphite and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Excitation of H⁺, H₂ ⁺, H₃ ⁺, He⁺, and Ar⁺ ions by impact on graphite and Al₂O₃ was investigated by means of emission spectroscopy in the 50–1000 eV energy range of the projectiles. Emission of Balmer series from excited neutral hydrogen is observed for both targets. In addition, for the Al₂O₃ target a continuum emission is observed. The continuum probably originates from excited M_nO_m molecules produced in the collision cascade, when surface atoms bound by ionic bonds are released after the bond breaking caused by neutralization. The spectra obtained under Ar⁺ -bombardment show Ar II lines emitted by backscattered ions.     

Surface properties of palladium catalysts supported on ternary ZrO2–Al2O3–WOx oxides prepared by the sol–gel method: Study of the chemical state of the support

The surface properties of Pd and Pd–Pt catalysts supported on binary ZrO₂–WOx and ternary ZrO₂–Al₂O₃–WOx oxides prepared by the sol–gel method were studied. Special attention was paid to the study of the texture of the catalysts as well as the chemical state of tungstated zirconia and tungstated zirconia promoted with alumina in the palladium catalysts. The catalysts were tested in the isomerization of n-hexane and were characterized by N₂ physisorption, XRD, TPR, Raman spectroscopy, XPS and FT-IR of adsorbed pyridine. The catalysts had bimodal pore size distributions with mesopores in the range 55–70 Å and macropores of 1000 Å in diameter. The catalysts had a surface WOx coverage (4.4–6.0 W nm^?2) lower than that of the theoretical monolayer (7.0 W nm^?2). A lower acidity of the ternary ZrO₂–Al₂O₃–WOx oxide as compared to the binary ZrO₂–WOx oxide was found. Higher activity in the isomerisation of n-hexane was obtained in the Pd–Pt catalysts supported on ternary ZrAlW oxides prepared by sol–gel that is correlated with the coexistence on the surface of W⁴⁺ (WO₂) or W⁰ and W⁶⁺ (Al₂(WO₄)₃) species, ZrO₂ in the tetragonal phase and a high amount of ZrOx suboxides species in a low oxidation state (Zr³⁺ and Zr²⁺).     

Manipulating Bonding at a Cu/(0001)Al2O3 Interface by Different Substrate Cleaning Processes

Growth of Cu films on (0001)Al₂O₃ substrates can result in metallic Cu—Al or ionic-covalent Cu—O bonds at atomically abrupt interfaces. The type of bonding depends on the substrate cleaning procedure prior to film growth. Cu films deposited on Ar⁺-ion sputter-cleaned substrates exhibit interfacial Cu-L_2,3, Al-L_2,3 and O-K energy-loss near-edge structures that indicate the formation of metallic Cu—Al bonds at the Cu/Al₂O₃ interface. In contrast, growth on chemically cleaned -Al₂O₃ substrates results in interfacial energy-loss near-edge structures that suggest Cu—O bonding at the interface. The experimental electron energy-loss spectroscopic results are compared to calculated spectra, and the mechanisms causing the changes in the atomic and electronic structure are addressed.     

Structure and properties of CaNb2O6:Sm3+ thin films by pulsed laser deposition

CaNb₂O₆:Sm³⁺ films were prepared on quartz glass and α-Al₂O₃(001) substrates by pulsed laser deposition. The structural, morphological, and optical properties of the CaNb₂O₆:Sm³⁺ films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), emission-scan electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL) measurements. The results show that the structure and properties of CaNb₂O₆:Sm³⁺ films were dependent on substrates. The CaNb₂O₆:Sm³⁺ films on Al₂O₃(0001) substrate have better crystallinity. The full-width at half-maximum (FWHM) of (131) peak are 0.45 and 0.32 for the CaNb₂O₆:Sm³⁺ film on glass and Al₂O₃(001), respectively. The crystallite size of CaNb₂O₆:Sm³⁺ films grown on glass and Al₂O₃(001) was about 8.22 and 9.98 nm, respectively. The oxidation state of the Sm element on the films was Sm³⁺ state. The photoluminescence (PL) spectra were measured at room temperature, the CaNb₂O₆:Sm³⁺ films on Al₂O₃(001) substrate have a better PL intensity, the identified emission bands were by the intra 4f transitions of Sm³⁺ from the excited level to the lower levels at 567 nm for ⁴G_5/2→⁶H_5/2 transition, at 609 nm for ⁴G_5/2→⁶H_7/2 transition, and at 657 nm for ⁴G_5/2→⁶H_9/2 transition.     

On the nature of ion bombardment-induced phase transformations in films of transition metals

Abstract

Electron diffraction studies have been made of polycrystalline Ni films irradiated with well separated beams of ions of different nature, namely ions of inert (He⁺, Ne⁺, Ar⁺, Kr⁺, Xe⁺) and reactive (N⁺ and O⁺) gases. The Ni films were prepared under vacuum conditions (P? 3·10^?6Pa during evaporation) preventing an appreciable contamination of the films with impurities. The samples were irradiated at T? 300 K with ion beams of energies from 10 to 100 keV in the dose range between 5·10¹⁶ cm^?2 and the value leading to sample destruction.

Irradiation with noble gas ions revealed no phase transitions in the Ni films. A similar result was obtained in irradiation of Fe and Cr films with He⁺ ions. The bombardment of Ni films with reactive gas ions does cause changes in the lattice structure of the samples under study, depending on the nature of the bombarding ions. The N⁺ ion bombardment gives rise to the hcp phase with the lattice parameters typical of the Ni₃N compound, and the O⁺ ion bombardment results in the fcc phase with the NiO-type parameter.

The conclusion is drawn on the chemical origin of the phase transformations in the Ni films under ion bombardment. The necessity of revising the concept about the polymorphous nature of phase transformations induced in the films of transition metals by ion bombardment is substantiated.     

A Rutherford scattering study of the chemical composition of native oxides on GaP

The chemical compositions of two types of protective oxide films on single crystal GaP have been studied by Rutherford backscattering (2 MeV He⁺) combined with ion channeling. Films of 350–1400 Å thickness were grown by immersing GaP slices in hydrogen peroxide, with or without externally applied anodic bias. Films grown by a galvanic coupling process have compositions of about 1:1·1:4·5 (Ga:P:O) and are believed to be vitreous mixtures of Ga₂O₃+P₂O₅. Films grown with anodic bias exhibited a deficiency of Ga in a ～200 Å region at the GaP-oxide interface.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.     

The transport and thermal properties of glassy LiPO<Subscript>3</Subscript>/crystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript> (ZrO<Subscript>2</Subscript>) composite electrolytes

Glassy LiPO₃/crystalline Al₂O₃ and glassy LiPO₃/crystalline ZrO₂ (0–12.5 vol.% of oxide fillers) composite solid electrolytes have been prepared by glass matrix softening. Their thermal and transport properties have been investigated by differential scanning calorimetry (DSC) and impedance spectroscopy methods. The addition of ZrO₂ leads to a decrease in the crystallization temperature of LiPO₃ glass. It was found that the conductivity behavior depends on the nature of the dispersed addition. In the case of the Al₂O₃ addition, the increase in the electrical conductivity is observed. The ionic conductivity of the LiPO₃/10% Al₂O₃ composite reaches 5.8 × 10^?8 S/cm at room temperature. In contrast, the conductivity in the LiPO₃/ZrO₂ composite system decreases.     

Permeation barrier properties of an Al2O3/ZrO2 multilayer deposited by remote plasma atomic layer deposition

We report the permeation barrier properties of Al₂O₃/ZrO₂ multi-layers deposited by remote plasma atomic layer deposition. Electrical Ca degradation tests were performed to derive the water vapor transmission rate (WVTR) of Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers at 50 °C and 50% relative humidity (RH). Al₂O₃/ZrO₂ multi-layers exhibit better barrier properties than Al₂O₃ and ZrO₂ layers, and when more individual layers were deposited in the same total thickness, the WVTR value was reduced further, indicating a better barrier property. The WVTR of the Al₂O₃ and ZrO₂ layers were 9.5 × 10⁻³ and 1.6 × 10⁻² g/m² day, respectively, but when deposited alternatively with 1 cycle of each layer, the WVTR decreased to 9.9 × 10⁻⁴ g/m² day. X-ray diffraction results indicated that ZrO₂ has a monoclinic structure but Al₂O₃ and Al₂O₃/ZrO₂ multi-layers show an amorphous structure. Cross sectional Al₂O₃/ZrO₂ multi-layer structures and the formation of a ZrAl_xO_y phase are observed by transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) results indicate that Al₂O₃ and ZrO₂ contain 33.7% and 37.8%, respectively, Al–OH and Zr–OH bonding. However, the ZrAl_xO_y phase contained 30.5% Al–OH and Zr–OH bonding. The results of transmittance measurement indicate that overall, Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers show high transmittance greater than 80% in the visible region.     

In situ 1H NMR Study of Nanoreactor Interaction NH3–H2O in Zeolite Nanopores

The interaction between ammonium NH₃ and H₂O molecules in zeolitic nanopores is studied by in situ ¹H nuclear magnetic resonance (NMR) method. The powder and single crystal samples of natural zeolites, heulandites Ca₄[Al₈Si₂₈O₇₂]·24H₂O and clinoptilolite (Na, K,Ca_1/2)₆[Al₆Si₃₀O₇₂], were used as the model system. It is shown that penetration of NH₃ into the zeolitic nanopores is accompanied by disordering of the hydrogen sublattice of zeolitic water and by the fast proton exchange NH₃ + H₂O ? [NH₄]⁺ + [OH]^? characterized by correlation frequency v _c = ~40 kHz. Another nanoreactor interactions are represented by interaction of [NH₄]⁺ ions with exchangeable Na⁺ and Ca²⁺ ions of the zeolitic structure. The slow ionic exchange [NH₄]⁺ → [Na,Ca_1/2]⁺ and binding of [NH₄]⁺ in cationic sites of the framework were visualized by NMR spectroscopy along with stepwise release of (Na,Ca_1/2)OH from zeolitic pores to the external surface of zeolite grains.     

Thermoluminescence (TL) of europium-doped ZrO2 obtained by sol–gel method

This article reports the preparation and characterization of europium-doped zirconium oxide (ZrO₂:Eu³⁺) formed by homogeneous precipitation from propoxyde of zirconium [Zr(OC₃H₇)₄]. The alkoxide sol gel process is an efficient method to prepare the zirconium oxide matrix by the hydrolysis of alkoxide precursors followed by condensation to yield a polymeric oxo-bridged ZrO₂ network. All compounds were characterized by thermal analysis and the X-ray diffractometry method. The thermoluminescence (TL) emission properties of ZrO₂:Eu³⁺ under beta radiation effects are studied. The europium-doped sintered zirconia powder presents a TL glow curve with two peaks (Tmax) centered at around 204 and around 292 ^°C, respectively. TL response of ZrO₂:Eu³⁺ as a function of beta-absorbed dose was linear from 2 Gy up to 90 Gy. The europium ion (Eu³⁺)-doped ZrO₂ was found to be more sensitive to beta radiation than undoped ZrO₂ obtained by the same method and presented a little fading of the TL signal compared with undoped zirconium oxide.     

Surface modification, martensitic transformation, and optical properties of hydrogenated ZrO2 nanocondensates via pulsed laser ablation in water

Pulsed laser ablation on Zr plate in water under Q-switch mode and a fluence of 700 and 800 mJ/pulse for a rather high power density of 1.5 and 1.7 × 10¹¹ W/cm², respectively, was employed to fabricate hydrogenated ZrO₂ nanocondensates. X-ray diffraction and transmission electron microscopic observations indicated such nanocondensates are full of {111} and {100} facets and predominantly in monoclinic (m-) rather than cubic- and/or tetragonal (t-) crystal symmetry in particular when fabricated at 700 mJ/pulse. The hydrogenated ZrO₂ nanocondensates underwent martensitic t ?? m transformation at a rather small critical size (ca. 20 nm) due to H⁺ signature and hence oxygen vacancy deficiency in the lattice. The resultant m-phase was free of twin and fault due to site saturation and rather limited growth of the nanosized particles. Spectroscopic characterizations indicated that the nanocondensates have a significant internal compressive stress, (H⁺, Zr²⁺, Zr³⁺) co-signature and hence a smaller band gap of 5.2?C5.3 eV for potential applications in UV region.     

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.