Depth profiles of Ta2O5/SiO2/Si structures: a combined X-ray photoemission, Auger electron, and secondary ion mass spectroscopic study

Summary We prepared thin films of tantalum oxide on SiO₂/Si substrates by thermal oxidation of tantalum. The different oxide layers and their interfaces were characterized by SIMS, AES, and XPS. Characteristic structures were obtained after different oxidation procedures. The comparative discussion of AES and SIMS depth profiles makes possible an unequivocal characterization of the reactive interfaces between the oxides of Ta and Si. The Ta₂O₅/SiO₂ interface in particular shows non-stoichiometries which depend on the oxidation procedures and which determine the performance characteristics of pH-sensitive Ta₂O₅ field-effect transistors.

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Tiefenprofile von Ta₂O₃/SiO₂/Si-Strukturen: Eine kombinierte Untersuchung mit Röntgen-Photoemissions-, Auger-Elektronen- und Sekundär-Ionen-Massen-Spektrometrie

     

Ta2O5 Nanocrystals Strengthened Mechanical,Magnetic, and Radiation Shielding Properties of Heavy Metal Oxide Glass

In this study, for the first time, diamagnetic 5d⁰ Ta⁵⁺ ions and Ta₂O₅ nanocrystals were utilized to enhance the structural, mechanical, magnetic, and radiation shielding of heavy metal oxide glasses. Transparent Ta₂O₅ nanocrystal-doped heavy metal oxide glasses were obtained, and the embedded Ta₂O₅ nanocrystals had sizes ranging from 20 to 30 nm. The structural analysis of the Ta₂O₅ nanocrystal displays the transformation from hexagonal to orthorhombic Ta₂O₅. Structures of doped glasses were studied through X-ray diffraction and infrared and Raman spectra, which reveal that Ta₂O₅ exists in highly doped glass as TaO₆ octahedral units, acting as a network modifier. Ta⁵⁺ ions strengthened the network connectivity of 1–5% Ta₂O₅-doped glasses, but Ta⁵⁺ acted as a network modifier in a 10% doped sample and changed the frame coordination units of the glass. All Ta₂O₅-doped glasses exhibited improved Vicker’s hardness, magnetization (9.53 × 10⁻⁶ emu/mol), and radiation shielding behaviors (RPE% = 96–98.8%, MAC = 32.012 cm²/g, MFP = 5.02 cm, HVL = 0.0035–3.322 cm, and Z_eff = 30.5) due to the increase in density and polarizability of the Ta₂O₅ nanocrystals.     

MAl2Ta35O70 (M = Na,K, Rb), niedervalente Oxotantalate mit isolierten kuboktaedrischen Ta6O12-Clustern

MAl₂Ta₃₅O₇₀ (M = Na, K, Rb), Low-Valent Oxotantalates with Discrete Cuboctahedral Ta₆O₁₂ Clusters The title compounds were prepared by reducing Ta₂O₅ with tantalum and aluminium in the presence of alkali metal carbonates at 1650 K. NaAl₂Ta₃₅O₇₀ was characterized by means of a single crystal X-ray structure determination: space group P 3, lattice parameters a = 780.15(7) pm, c = 2621.7(8) pm, Z = 1, 167 variables, R_F = 0.048. The structure can be described in terms of a close packing of oxide ions with specific defects. The sequence of the layers is hhcchchcchh. The characteristic structural units are Ta₆O₁₂ clusters being substantially stabilized by Ta–Ta bonding (d_Ta–Ta = 279.3–283.3 pm, 14 electrons per cluster). The sodium cations occupy acentrically and statistically half of the anti-cuboctahedral sites. The compounds are semiconductors with band gaps E_a of 0.2 to 0.3 eV.     

Interfacial properties of thermally oxidized Ta2Si on Si

Many refractory metal silicides have received great attention due to their potential for innovative developments in the silicon‐based microelectronic industry. However, tantalum silicide, Ta₂Si, has remained practically unnoticed since its successful application in silicon carbide technology as a simple route for a high‐k dielectric formation. The thermal oxidation of Ta₂Si produces high‐k dielectric layers, (O? Ta₂Si)‐based on a combination of Ta₂O₅ and SiO₂. In this work, we investigate the interfacial properties of thermally oxidized (850–1050 °C) Ta₂Si on commercial silicon substrates. The implications of diffusion processes in the dielectric properties of an oxidized layer are analyzed. In particular, we observe migration of tantalum pentoxide nanocrystals into the substrate with increasing oxidation temperature. An estimation of the insulator charge and interfacial O? Ta₂Si/Si trap density is also presented. Copyright © 2008 John Wiley & Sons, Ltd.     

Syntheses and characterizations of complex perovskite oxynitrides LaMg1/3Ta2/3O2N, LaMg1/2Ta1/2O5/2N1/2, and BaSc0.05Ta0.95O2.1N0.9

The following complex oxynitride perovskites have been prepared: LaMg_1/3Ta_2/3O₂N, LaMg_1/2Ta_1/2O_5/2N_1/2, and BaSc_0.05Ta_0.95O_2.1N_0.9. Synchrotron X-ray powder diffraction analyses show that LaMg_1/3Ta_2/3O₂N and LaMg_1/2Ta_1/2O_5/2N_1/2 are isostructural to the oxide La₂Mg(Mg_1/3Ta_2/3)O₆ (space group P2₁/n), whereas BaSc_0.05Ta_0.95O_2.1N_0.9 has a simple cubic symmetry similarly to BaTaO₂N. The orderings of octahedral cations are markedly diminished in the above oxynitrides, as compared with the related oxides such as La₂Mg(Mg_1/3Ta_2/3)O₆ and Ba₂ScTaO₆. The optical band gaps are similar for the homologous compositions, LaMg_1/3Ta_2/3O₂N, LaMg_1/2Ta_1/2O_5/2N_1/2 and LaTaON₂ (1.9 eV), and BaSc_0.05Ta_0.95O_2.1N_0.9 and BaTaO₂N (1.8 eV), while the absorption edges become broader for the complex derivatives. As revealed from the impedance spectroscopic analysis, the oxynitrides have clearly different dielectric components from those of comparable oxides containing Ta⁵⁺. Impedance spectroscopy reveals interesting capacitor geometry in BaSc_0.05Ta_0.95O_2.1N_0.9 in which the semiconducting oxynitride grains are separated by insulating secondary phases. Most notably BaSc_0.05Ta_0.95O_2.1N_0.9 has a bulk component with a high relative permittivity (κ=7300) and the grain boundary component with an even higher κ.     

The chemistry and thermal stability of HfTaO/Si interface by x‐ray photoelectron spectroscopy

The chemistry and thermal stability of HfTaO/Si interface as a function of annealing temperature have been investigated by x‐ray photoelectron spectroscopy. For the as‐deposited sample, the formation of Hf‐silicate bond is observed on Hf 4f core‐level spectra, which contributes to bulk HfO₂ and SiO₂. Besides, the suboxide of tantalum (Ta⁺¹) is formed at the interface at room temperature because of oxygen‐deficient conditions. HfSi₂, Hf_xSi_yO_4, and HfO₂ coexists in interfacial region at 850 °C, meanwhile, an evidence for transforming from the Ta¹⁺ to tantalum oxide (Ta⁵⁺) is verified. The peaks of Hf–O–Si and Hf–O have disappeared, only one peak of Hf silicide remained after the annealing at 950 °C. A stable SiO₂ phase in HfTaO/Si is formed under different annealing conditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and Approximated Crystal and Electronic Structure of a Proposed New Tantalum Oxide Nitride Ta3O6N

In the quasibinary system Ta₂O₅/Ta₃N₅ we prepared a new oxide nitride phase, Ta₃O₆N, by the reaction of 1T–TaS₂ with water‐saturated ammonia gas. The determination of the unit cell metric and the crystal structure indicated that Ta₃O₆N is structurally related to the TiNb₂O₇‐type. Quantum‐chemical calculations on DFT level were used to rank the relative stabilities of possible N/O distributions and to provide a plausible structural model of the ground state with a minimum in the total energy. In agreement with Paulings 2nd rule, nitrogen ions prefer sites with high coordination numbers.     

Theoretical investigation on the IR spectra of four‐membered silicon oxide ring

To test the mass effect on the ring vibrational frequencies (SiO₂) shift of the four‐membered silicon oxide ring, the deuterium and the tritium substituted cyclodisiloxanes on the hydrogen positions are examined at the CCSD(T)/cc‐pVTZ level of theory. The SiO₂ ring vibrations for a silicon oxide surface model compound, substituted cyclodisiloxane (Si₃O₅? O₂? Si₃O₅) with two six‐membered ring, are also calculated at the B3LYP/cc‐pVTZ level of theory. Our results of 909 and 920 cm^?1 are in good agreement with the experimental result. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Helical Mesoporous Tantalum Oxide Nanotubes: Formation,Optical Activity,and Applications

Nanomaterials with helical morphologies have attracted much attention owing to their potential applications as nanosprings, chirality sensors and in chiral optics. Single‐handed helical Ta₂O₅ nanotubes prepared through a supramolecular templating approach are described. The handedness is controlled by that of the organic self‐assemblies of chiral low‐molecular‐weight gelators (LMWGs). The chiral LMWGs self‐assemble into single‐handed twisted nanoribbons through H‐bonding, hydrophobic association, and π‐π stacking. The Ta₂O₅ nanotubes are formed by the adsorption and polycondensation of Ta₂O₅ oligomers on the surfaces and edges of the twisted organic nanoribbons followed by removal of the template. The optical activity of the nanotubes is proposed to originate from the chiral defects on the inner surfaces of the tubular structures. Single‐handed twisted LiTaO₃ nanotubes can also be prepared using Ta₂O₅ nanotubes.     

Physicochemical Study of Ta2O5 and SiO2-Ta2O5 Film Formation from Film-Forming Solutions

In order to study physicochemical processes of formation of Ta₂O₅ and SiO₂-Ta₂O₅ films from film-forming solutions, the properties of these solutions, and also the thermal-oxidative breakdown and the properties of the obtained films, were studied.     

Changes in the surface structure of Pd/Ta2O5 by oxygen and CO studied using X‐ray Photoelectron Spectroscopy (XPS)

Behaviors of Pd structures with different thicknesses supported by Ta₂O₅/Ta in the reaction with oxygen and CO were studied by XPS and SEM. For the samples with a Pd thickness of 3 nm, a new low‐binding‐energy component appeared in the Pd 3d level upon O₂ exposure at ～200 °C and was reduced in intensity after a subsequent CO exposure at 150 and 200 °C. The change in the Ta 4f state could also be found upon oxygen and CO exposure, indicating that both Pd and the Ta‐oxide substrate participate in the chemical reactions. For the sample with a higher Pd thickness, a positive shift in the Pd 3d level due to the oxidation of Pd was observed after exposure to O₂ at a higher temperature (280 °C). A subsequent CO exposure at ～150 °C could not reduce Pd‐oxide layers, as confirmed by the unchanged Pd 3d spectra after CO treatment, i.e. Pd‐oxide was not reactive for CO oxidation. Copyright © 2010 John Wiley & Sons, Ltd.     

Ordered Mesoporous Thin Films of Rutile TiO2 Nanocrystals Mixed with Amorphous Ta2O5

Ordered mesoporous thin films of composites of rutile TiO₂ nanocrystals with amorphous Ta₂O₅ are fabricated by evaporation‐induced self‐assembly followed by subsequent heat treatment beyond 780 °C. Incorporation of selected amounts of Ta₂O₅ (20 mol %) in the mesoporous TiO₂ film, together with the unique mesoporous structure itself, increased the onset of crystallization temperature which is high enough to ensure the crystallization of amorphous titania to rutile. The ordered mesoporous structure benefits from a block‐copolymer template, which stabilizes the mesostructure of the amorphous mixed oxides before crystallization. The surface and in‐depth composition analysis by X‐ray photoelectron spectroscopy suggests a homogeneous intermixing of the two oxides in the thin film. A detailed X‐ray absorption fine structure measurement on the composite film containing 20 mol % Ta₂O₅ and heated to 800 °C confirms the amorphous nature of the Ta₂O₅ phase. Photocatalytic activity evaluation suggests that the rutile nanocrystals in the synthesized ordered mesoporous thin film possess good ability to assist the photodegradation of rhodamine B in water under illumination by UV light.     

Na0.74Ta3O6, ein niedervalentes Oxotantalat mit einer Ta–Ta‐Mehrfachbindung

Na_0.74Ta₃O₆, a Low‐Valent Oxotantalate with Multiple Ta–Ta Bonds The title compound was prepared in a sealed tantalum tube through the reaction of Ta₂O₅, tantalum and Na₂CO₃ in a NaCl flux at 1570 K within 5 d. The crystal structure of Na_0.74Ta₃O₆ (a = 713.5(1), b = 1027.4(2), c = 639.9(1) pm, Immm, Z = 4) was determined by single crystal X‐ray means. The structure is isomorphous with NaNb₃O₅F [1]. The characteristic structural units are triply bonded Ta1₂ dumb‐bells with eight square‐prismatically co‐ordinated O ligands. Four Ta2, each octahedrally surrounded by O atoms, are side‐on bonded weakly to the binuclear Ta₂O₈ complex, thus forming a Ta₆ propellane‐like cluster. The lattice parameters of three additional M_xTa₃O₆ phases, M = Li, Mn, and Yb, are reported.     

A Redox‐Mediator‐Free Solar‐Driven Z‐Scheme Water‐Splitting System Consisting of Modified Ta3N5 as an Oxygen‐Evolution Photocatalyst

Tantalum nitride (Ta₃N₅) modified with various O₂‐evolution cocatalysts was employed as a photocatalyst for water oxidation under visible light (λ>420 nm) in an attempt to construct a redox‐mediator‐free Z‐scheme water‐splitting system. Ta₃N₅ was prepared by nitriding Ta₂O₅ powder under a flow of NH₃ at 1023–1223 K. The activity of Ta₃N₅ for water oxidation from an aqueous AgNO₃ solution as an electron acceptor without cocatalyst was dependent on the generation of a well‐crystallized Ta₃N₅ phase with a low density of anionic defects. Modification of Ta₃N₅ with nanoparticulate metal oxides as cocatalysts for O₂ evolution improved water‐oxidation activity. Of the cocatalysts examined, cobalt oxide (CoO_x) was found to be the most effective, improving the water‐oxidation efficiency of Ta₃N₅ by six to seven times. Further modification of CoO_x/Ta₃N₅ with metallic Ir as an electron sink allowed one to achieve Z‐scheme water splitting under simulated sunlight through interparticle electron transfer without the need for a shuttle redox mediator in combination with Ru‐loaded SrTiO₃ doped with Rh as a H₂‐evolution photocatalyst.     

A Newly Competitive Electrochemical Sensor for Sensitive Determination of Chrysin Based on Electrochemically Activated Ta2O5 Particles Modified Carbon Paste Electrode

A novel electrochemically activated doped Ta₂O₅ particles modified carbon paste electrode (EA‐Ta₂O₅‐CPE) was prepared and applied for selective and sensitive determination of chrysin. X‐ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) techniques and cyclic voltammetry (CV) were used to characterize the Ta₂O₅ particles and investigate the electrochemical response of the sensor. Compared with bare CPE, the doped Ta₂O₅ modified electrode got much more porous by electrochemical treatment and exhibited larger effective surface area, more reactive site and excellent electrochemical catalytic activity toward the oxidation of chrysin. Under optimum conditions by LSV, the oxidation peak currents responded to chrysin linearly over a concentration range from 5.0×10⁻⁸ to 7.0×10⁻⁶ mol L⁻¹ with a detection limit of 2.0×10⁻⁸ mol L⁻¹ (5.08 ng mL⁻¹). The fabricated sensor showed anti‐interference ability against the biological common interferents (i.e. baicalein, baicalin) and provided to be reliable for the determination of chrysin in Chinese medicinal herb Oroxylum indicum and chrysin capsules samples with satisfactory results.     

Pyrochlore and Perovskite Potassium Tantalate: Enthalpies of Formation and Phase Transformation

Alkali niobates and tantalates are currently important lead‐free functional oxides. The formation and decomposition energetics of potassium tantalum oxide compounds (K₂O?Ta₂O₅) were measured by high‐temperature oxide melt solution calorimetry. The enthalpies of formation from oxides of KTaO₃ perovskite and defect pyrochlores with K/Ta ratio of less than 1 stoichiometry—K_0.873Ta_2.226O₆, K_1.128Ta_2.175O₆, and K_1.291Ta_2.142O₆—were experimentally determined, and the values are (?203.63±2.92) kJ mol^?1 for KTaO₃ perovskite, and (?339.54±5.03) kJ mol^?1, (?369.71±4.84) kJ mol^?1, and (?364.78±4.24) kJ mol^?1, respectively, for non‐stoichiometric pyrochlores. That of stoichiometric defect K₂Ta₂O₆ pyrochlore, by extrapolation, is (?409.87±6.89) kJ mol^?1. Thus, the enthalpy of the stoichiometric pyrochlore and perovskite at K/Ta=1 stoichiometry are equal in energy within experimental error. By providing data on the thermodynamic stability of each phase, this work supplies knowledge on the phase‐formation process and phase stability within the K₂O?Ta₂O₅ system, thus assisting in the synthesis of materials with reproducible properties based on controlled processing. Additionally, the relation of stoichiometric and non‐stoichiometric pyrochlore with perovskite structure in potassium tantalum oxide system is discussed.     

Novel Flower‐Like Ag‐SiO2‐MgO‐Al2O3 Material: Preparation,Characterization and Catalytic Application in Methanol Dehydrogenation

Catalytic direct dehydrogenation of methanol to formaldehyde was carried out over Ag‐SiO₂‐MgO‐Al₂O₃ catalysts prepared by sol‐gel method. The optimal preparation mass fractions were determined as 8.3% MgO, 16.5% Al₂O₃ and 20% silver loading. Using this optimum catalyst, excellent activity and selectivity were obtained. The conversion of methanol and the selectivity to formaldehyde both reached 100%, which were much higher than other previously reported silver supported catalysts. Based on combined characterizations, such as X‐ray diffraction (XRD), scanning electronic microscopy (SEM), diffuse reflectance ultraviolet‐visible spectroscopy (UV‐Vis, DRS), nitrogen adsorption at low temperature, temperature programmed desorption of ammonia (NH₃‐TPD), desorption of CO₂ (CO₂‐TPD), etc., the correlation of the catalytic performance to the structural properties of the Ag‐SiO₂‐ MgO‐Al₂O₃ catalyst was discussed in detail. This perfect catalytic performance in the direct dehydrogenation of methanol to formaldehyde without any side‐products is attributed to its unique flower‐like structure with a surface area less than 1 m²/g, and the strong interactions between neutralized support and the nano‐sized Ag particles as active centers.     

Natural rubber–based composites filled with bioglasses from a CaO‐SiO2‐P2O5‐Ag2O system. Effect of Ag2O concentration in the filler on composite properties

Bioactive glass was first synthesized by L. Hench in 1971. There are many studies on the properties of several metals and metal ions dopants used in the SiO₂‐CaO‐P₂O₅ system of bioglasses, such as Ag, Cu, Zn, and Fe. A number of authors have carried out research related to the influence of silver oxide on the properties of bioglasses . However, publications on the properties of elastomer‐based composites containing bioactive glasses are relatively scarce. We have not found in the literature studies discussing how silver oxide concentration in bioglasses of the CaO‐SiO₂‐P₂O₅‐Ag₂O system affects the significant properties of a natural rubber biocomposite. In this regard, the purpose of the present work is to investigate the aforementioned influence on the properties of this type of composites, namely, vulcanization, physicomechanical, thermal, dynamic, dielectric, electric, and thermoconductive characteristics. We have established those parameters of the composites to be impacted considerably by both degree of filling with bioglass and the silver oxide content in the latter. The improvement in the composites thermostability and some of their physicomechanical performance is the most significant. The volume resistance decreases, and the thermal conductivity coefficients increase. Results from scanning electron microscopy and energy‐dispersive X‐ray (EDX) analyses have confirmed the influence of silver oxide initially on the phase composition of the bioglass, hence on the properties of the biocomposites through changes in the bioglass used as filler. The dielectric characteristics of some of the biocomposites suggest that they can be used as substrates and insulating layers in flexible antennas for short‐range wireless communications.     

Electronic structure and photocatalytic properties of ABi2Ta2O9 (A=Ca, Sr, Ba)

A new series of layered perovskite photocatalysts, ABi₂Ta₂O₉ (A=Ca, Sr, Ba), were synthesized by the conventional solid-state reaction method and the crystal structures were characterized by powder X-ray diffraction. The results showed that the structure of ABi₂Ta₂O₉ (A=Ca, Sr) is orthorhombic, while that of BaBi₂Ta₂O₉ is tetragonal. First-principles calculations of the electronic band structures and density of states (DOS) revealed that the conduction bands of these photocatalysts are mainly attributable to the Ta 5d+Bi 6p+O 2p orbitals, while their valence bands are composed of hybridization with O 2p+Ta 5d+Bi 6s orbitals. Photocatalytic activities for water splitting were investigated under UV light irradiation and indicated that these photocatalysts are highly active even without co-catalysts. The formation rate of H₂ evolution from an aqueous methanol solution is about 2.26 mmol h^-1 for the photocatalyst SrBi₂Ta₂O₉, which is much higher than that of CaBi₂Ta₂O₉ and BaBi₂Ta₂O₉. The photocatalytic properties are discussed in close connection with the crystal structure and the electronic structure in details.     

Phase distribution in the HfO2Er2O3Ta2O5 system

Phase relationships obtained by heating coprecipitated oxide powders in the HfO₂Er₂O₃Ta₂O₅ system were investigated by X-ray diffractometry. Partial isothermal sections at 1100 and 1500°C are presented.