ZrO2-SiO2 materials prepared by sol-gel

Gels with composition xZrO₂−(100−x)SiO₂, X = 10−55, were prepared in different conditions using zirconium acetylacetonate and TEOS as precursors.

Gels treated at different temperatures up to 1100°C were characterized by X-ray diffraction, IR spectroscopy and TEM. Preparation conditions determined the subsequent development of crystalline phases following thermal treatment.

Monoclinic zirconia segregation dispersed in a silica matrix occurred when the gels were prepared in a strong hydrocloric acid medium. Preparation with a lower acid content favours instead the formation of very small crystals of tetragonal zirconia.     

HREM investigations of intermediate ZnO and ZnO/Y–ZrO2 layers in Y–ZrO2 bicrystals and ZnO films grown on Y–ZrO2 bicrystal substrates

The structure of yttrium-stabilized ZrO₂ (YSZ) bicrystals with ZnO and ZnO/YSZ/ZnO/YSZ/ZnO intermediate layers, as well as ZnO films grown on YSZ bicrystal (1 1 0)/90° substrates, has been investigated by means of high-resolution electron microscopy (HREM) and microanalysis. All bicrystals were produced by the solid-phase intergrowth (SPI) method. The internal ZnO film in the bicrystal formed at the SPI temperature of 1400°C consisted of domains with two symmetrical orientations: , and , . A bicrystal with a ZnO/YSZ/ZnO/YSZ/ZnO internal film was formed at the temperature of 1200°C. There was no mixing of ZnO and YSZ films and no traces of any solid-phase reactions were observed. Grains in all internal ZnO films and ZnO films grown on the bicrystal substrates had numerous stacking faults. It was found that SPI does not influence the density and structure of these defects. Orientational relationships between YSZ and ZnO in all samples were determined. The ZnO films grown on (1 1 0)/90° bicrystal substrates inherited the grain boundary (GB) from the substrate. Its structure and geometry is determined by four variants of ZnO grain growth.     

Characterization of ALCVD-Al2O3 and ZrO2 layer using X-ray photoelectron spectroscopy

The atomic layer chemical vapor deposition (ALCVD) deposited Al₂O₃ and ZrO₂ films were investigated by ex situ X-ray photoelectron spectroscopy. The thickness dependence of band gap and valence band alignment was determined for these two dielectric layers. For layers thicker than 0.9 nm (Al₂O₃) or 0.6 nm (ZrO₂), the band gaps of the Al₂O₃ and ZrO₂ films deposited by ALCVD are 6.7±0.2 and 5.6±0.2 eV, respectively. The valence band offsets at the Al₂O₃/Si and ZrO₂/Si interface are determined to be 2.9±0.2 and 2.5±0.2 eV, respectively. Finally, the escape depths of Al 2p in Al₂O₃ and Zr 3p3 in ZrO₂ are 2.7 and 2.0 nm, respectively.     

Hydrothermal synthesis of MoS2 nanowires

The MoS₂ nanowires with diameters of 4 nm and lengths of 50 nm were synthesized by a hydrothermal method using 0.36 g MoO₃ and 1.8 g Na₂S as precursors in 0.4 mol/l HCl solution at 260°C. The products are characterized by XRD, XPS, TEM, HTEM and BET. Results show that the as-prepared MoS₂ nanowires consist of 1–10 sulfide layers with BET surface areas of 107 m²/g. The possible reaction route and the formation mechanism of the MoS₂ nanowires are discussed. The effects of exterior conditions such as pH value, temperature, concentration of precursors and additives on the particle size and morphology of MoS₂ crystallites were investigated.     

Atomic layer deposition of Al2O3, ZrO2, Ta2O5, and Nb2O5 based nanolayered dielectrics

Ta₂O₅, Ta-Nb-O, Zr-Al-Nb-O, and Zr-Al-O mixture films or solid solutions were grown on Si(1 0 0) substrates at 300 °C by atomic layer deposition. The equivalent oxide thickness of Ta₂O₅ based capacitors was between 1 and 3 nm. In Zr-Al-O films, the high permittivity of ZrO₂ was combined with high resistivity of Al₂O₃ layers. The permittivity, surface roughness and interface charge density increased with the Zr content and the equivalent oxide thickness was between 2.0 and 2.5 nm. In the Zr-Al-Nb-O films the equivalent oxide thickness remained at 1.8-2.0 nm.     

SAXS investigations of structure of formation in alcoholic ZrO2---SiO2 solutions

Small-angle X-ray scattering was used to examine in situ formation of ZrO₂---SiO₂ structures in alcoholic solution of tetraethoxysilan (TEOS) as a function of the ratio of ZrO₂ to SiO₂. For the moment of the first measurement (15 min after the preparation) primary particles with R_g ≈ 1.5 nm exist in all investigated mixed gels. These particles aggregated to secondary clusters. The resulting clusters can be described by means of fractal theory, where the determining mechanism of formation is cluster-cluster aggregation (diffusion or chemical limited). The time of gelation is a function of the ZrO₂ concentration. The higher the ZrO₂ concentration in the solution, the faster is the aggregation to secondary clusters. Gelation times were between 170 and 970 h.     

烧结工艺对原位合成ZrO2/TiB2复合陶瓷材料的力学性能影响

以TiC和B4C为原料反应生成TiB2,原位合成了TiB2含量为20％的ZrO2/TiB2复合陶瓷材料.分析了烧结工艺中烧结温度、保温时间和烧结压力对力学性能的影响.结果表明:当烧结温度由1650℃提高到1750℃时,复合陶瓷材料的抗弯强度由820 MPa增加到980 MPa,断裂韧性从7.2 MPa·m1/2提高到9.4 MPa·m12;当烧结温度升至1850℃时,抗弯强度和断裂韧性下降;显微硬度随烧结温度的升高而提高.在烧结温度1750℃压力为30MPa保温时间由30 min提高到45 min时,断裂韧性从8.6 MPa·m1/2提高到9.4 MPa·m1/2;保温时间增加至60 min时,断裂韧性下降;保温时间的变化对材料的抗弯强度、硬度影响不大.烧结压力对复合陶瓷材料的力学性能的影响较小.当烧结参数为1750℃、45 min、30MPa,ZrO2/TiB2复合陶瓷材料的抗弯强度、显微硬度、断裂韧性分别达到980 MPa、13.6 GPa、9.4 MPa·m1/2.     

Properties of ZrO2---Al2O3 composite powders prepared from Zr---Al metallo-organic compounds

Zr---Al metallo-organic compounds (zircoaluminates), having (CH₂)₄COOH, (CH₂)₁₂CH₃ and (CH₂)₂NH₂ as the organofunctional groups, were treated preliminary by (1) spray-drying, (2) gelation of addition of 10% NH₄OH aqueous solution followed by spray-drying and (3) rotary evaporation under a reduced pressure. After the treatment they were heated in air to prepare ZrO₂---Al₂O₃ composite powders. The IR and DTA profiles for the treated compounds indicated that the procedures modified the structures for the zircoaluminates. The stability of tetragonal ZrO₂ for the ZrO₂---Al₂O₃ composite powder were dependent on the modification in the structure for the zircoaluminates. Balloon shaped particles, 0.5–2 μm in diameter, were obtained through procedure (1) and spherical particles, 1–4 μm in diameter, through (2). Tetragonal ZrO₂ grains, 0.1–0.2 μm in diameter, were dispersed in the particles when heated at 1400°C.     

Preparation and characterization of ZrO2-SiO2 binary films for planar optical waveguides

ZrO₂-SiO₂ binary films for active optical waveguides were prepared by the sol-gel method with zirconium oxychloride and tetraethoxysilane as precursors. The main factors that influence the film thickness and refractive index have been found. The relationship between the film refractive index composition and heat treatment temperature has been determined. The continuous tuning of the thickness and refractive index of the thin films has also been achieved, which will open up new possibilities in the development of active optical waveguides.     

Glass formation and crystallization in the ZrO2---Al2O3---P2O5 system

The glass formation of the ZrO₂---Al₂O₃---P₂O₅ system in the high phosphate region is determined. The crystallization process and the crystal types formed during heat treatment have been studied. The structure of these glasses is discussed.     

Toughened glass-ceramics containing ZrO2 and Al2O3 prepared by the sol-gel process from metal alkoxides

Glasses of compositions 5ZrO₂·5SiO₂(ZS), 5ZrO₂·Al₂O₃·4SiO₂(ZAS) and 5 5ZrO₂·0.5Al₂O₃·0.5Na₂O·4SiO₂(ZANS) were prepared by the sol-gel process from metal alkoxides and sintered to make glass-ceramics. Tetragonal ZrO₂ was precipitated by heat treatment at 900 to 1300°C. The activation energy for tetragonal ZrO₂ crystal growth was extremely high in Al₂O₃ containing glasses. ZAS and ZS were sintered to the near theoretical densities above 1200°C, at which the predominant phase was tetragonal ZrO₂. On the other hand, for ZANS, high densification was not attained owing to the large pores enclosed by the glass phase. Strength and fracture toughness increased with the densification and the crystal growth of tetragonal ZrO₂, reaching 450 MPa and 9 MN/m^1.5, respectively.     

Growth and characterization of nanostructured Al2O3/YAG/ZrO2 hypereutectics with large surfaces under laser rapid solidification

The preparation of large bulk oxide eutectics with homogeneous and dense structure in nano-scale by melt growth method is a difficult challenge. Fully dense, homogeneous and crack-free ternary nanostructured Al₂O₃/YAG/ZrO₂ hypereutectic plate with large surface is successfully obtained by laser remelting. The hypereutectic in selected composition presents an ultra-fine eutectic-like microstructure consisting of alternating interpenetrating Al₂O₃, YAG and ZrO₂ lamellae with mean interphase spacing of about 150 nm, which is much smaller than the ternary eutectic composition grown at the same growth conditions. With the increase of laser scanning rate, the lamellar spacing is rapidly decreased. The minimum value obtained is 50 nm. The analysis indicates that the strong faceted growth behavior and cooperative branching of the component phases related with high entropies of fusion and large kinetic undercooling during laser rapid solidification are the primary formation reasons for the irregular eutectic growth morphology. Furthermore, the unique cellular microstructure with complex structure is also observed at high growth rate, and their formation mechanism and effect of the composition on the microstructure are discussed.     

Ag precipitation and optical behavior in Na2O---B2O3 glasses

Ag particles of different sizes in the nanometer range were produced in Na₂O---B₂O₃ glasses containing Ag₂O by the melt-quenching and heat-treatment method. The quenching rate was 10³ K s⁻¹ and the heat treatment was at 738 K for 2–300 h. The precipitation was dependent on diffusion limited growth. The optical absorption of Ag particles in the glasses was measured and correlated to the distribution of particle radii. The peak energy of the surface plasmon resonance was blue shifted and the width decreased with increasing average particle radius. These results are compared with previous data on similar systems.     

Solidification of superalloy in a SiO2–ZrO2–B2O3 coating mould

The preparation of glass-lined coating mould from gels in the ternary system of SiO₂–ZrO₂–B₂O₃ has been investigated. The crystallization characterization and high temperature structure stability of this coating mould are demonstrated. We can find that the crystallization of t-ZrO₂ as well as the tetragonal to monoclinic phase transformation are, respectively, retarded and impeded owing to the encasement of SiO₂ matrix. While the inhibitive effect of B₂O₃ on crystallization of the SiO₂–ZrO₂–B₂O₃ coating mould is explained. Finally, DD3 single crystal superalloy melt can realize highly undercooled rapid solidification by adopting this coating mould, which further evinces that SiO₂–ZrO₂–B₂O₃ coating mould has an ideal nucleation inhibition for superalloy.     

Structural and electrical characterization of ALCVD ZrO2 thin films on silicon

We report on the structural and electrical properties of ZrO₂ thin layers grown on Si by atomic layer chemical vapour deposition. Atomic force microscopy, X-ray diffraction, X-ray reflectivity and time-of-flight secondary ion mass spectrometry have been used to characterize as-grown and annealed samples. High frequency capacitance-voltage measurements have been performed to determine the capacitance of the gate dielectric stack. The ZrO₂ film is found to be polycrystalline. Electrical and structural data suggest a coherent picture of film modification upon annealing.     

Band alignment at the interfaces of Al2O3 and ZrO2-based insulators with metals and Si

Internal photoemission of electrons was used to determine the band alignment in metal (Mg, Al, Ni, Cu, Au)-oxide-silicon structures with Al₂O₃- and ZrO₂-based insulators. For Al₂O₃- and ZrO₂ layers grown on Si by atomic layer deposition the barrier height between the Si valence band and the oxide conduction band was found to be 3.25 and 3.1 eV, respectively. Thermal oxidation of the Si/oxide stacks results in a barrier height increase to ≈4 eV for both cases due to formation of a silicate interlayer. However, there is a significant sub-threshold electron emission both from silicon and metals, indicating a high density of states in the band gap of the insulators. These states largely determine the electron transport across metal oxides and may also account for a significant dipole component of the potential barrier at the metal/ZrO₂ and metal/Al₂O₃ interfaces.     

Hydrothermal growth of NiSe2 tubular microcrystals assisted by PVA

NiSe₂ tubular microcrystals assembled of nanoparticles have been prepared via a hydrothermal method in an ethanolamine and water mixed solution assisted by polyvinyl alcohol (PVA). The prepared tubular crystals with hexagonal structure are composed of nanoparticles with average diameter of 30 nm. It was found that the phase of the products could be adjusted by the molar ratio of the reactants (Ni/Se), and the morphology of the products could be greatly influenced by the quantity of surfactant PVA. Based on the experimental results, the possible formation mechanism of NiSe₂ tubular microcrystals is also discussed.     

Structural and optical properties of thin films prepared from surface modified ZrO2

This paper describes the preparation and characterization of ZrO₂ thin films deposited on silicon wafer by spin coating method. Nanocrystalline ZrO₂ was synthesized by hydrothermal method using zirconium (IV)-n-propoxide as a precursor material. Surface of the ZrO₂ particles was then modified with 2-acetoacetoxyethyl methacrylate used as a copolymer for coatings. The optical properties, nanostructure and surface morphology of the thin films prepared from surface modified ZrO₂ nanoparticles were examined by optical spectroscopy, X-ray diffraction and scanning electron microscopy, respectively. It was found that the films deposited on silicon wafer have crystalline structure of monoclinic (111) at temperature of 150 °C. It was observed that films depict very dense material that does not present any granular or columnar structure. It was found that optical transparency of thin ZrO₂ films distributed in the range of 30-40 percent in the spectral range 400-800 nm. Refractive index of ZrO₂ films were determined as functions of ZrO₂ content and it was found that the refractive index increases from 1.547 to 1.643 with increased ZrO₂ content.     

Atomic layer deposition of ZrO2 thin films using a new alkoxide precursor

Zirconium oxide thin films were grown by atomic layer deposition using a new type of Zr alkoxide: [Zr(O^tBu)₂(dmae)₂]₂ (dmae is dimethylaminoethoxide). Water was used as the oxygen source. The films grown at 190-240 °C were amorphous, and the films grown at 290-340 °C were nanocrystalline. The highest refractive index of the films was 2.08 at a wavelength of 580 nm. The permittivity of a film grown at 240 °C was 25.     

Hydrothermal Synthesis, Structural Characterization and Luminescent Property of a New 1-D Chain-like [Er(NC6H4O2)3(H2O)2]n

Abstract  

Erbium (III) coordination compound with the formula [Er(IN)₃(H₂O)₂]_n 1 (HIN = isonicotinic acid) was synthesized by mixing Er₂O₃ with isonicotinic acid under hydrothermal condition. The structure of the title compound was determined by single crystal X-ray diffraction analysis, which reveals that the 1-D chain-like structure is formed by the erbium polyhedra through the carboxyl groups of IN. It crystallizes in the monoclinic system, possesses space group C2/c, with lattice parameters: a = 20.229(10) ?, b = 11.594(6) ?, c = 9.871(5) ?, α = γ=90°, β = 115.509(6)°, V = 2089.3(18) ?³, and D _calc = 1.811 mg/cm³ for Z = 4, F(000) = 1108, GOF = 1.109, R1 = 0.0675. Compound 1 has been characterized by IR absorption spectroscopy, ultraviolet excitation and emission spectrum.