Synthesis of ZnO/Zn2SiO4/SiO2 composite pigments with enhanced reflectance and radiation-stability under low-energy proton irradiation

ZnO/Zn₂SiO₄/SiO₂ composite pigments with nano-sized α-Zn₂SiO₄ interface phase were synthesized by a simple solid-state reaction method. It was found that the composite pigments exhibit significant improvement on the spectral reflectance and the proton radiation-stability compared with the pure ZnO pigment. The investigations have demonstrated that the enhancements on the spectral reflectance and the radiation-stability are attributed to the introduction of willemite Zn₂SiO₄ interface phase on the surface of ZnO matrix particles. In addition, the enhancement mechanisms of radiation-stability for ZnO/Zn₂SiO₄/SiO₂ composite pigments were discussed.     

Preparation and luminescent properties of Rh6G-doped lamellar, hexagonal, and cubic mesostructured SiO2 waveguides

We successfully fabricated laser dye (Rh6G)-doped lamellar, hexagonal, and cubic mesostructured SiO₂ waveguides with a combined method of inorganic/organic co-assembly and soft-lithography. These mesostructured SiO₂ waveguide arrays were made on low-refractive index mesoporous SiO₂ clad films (the upper cladding is air), and waveguiding was confirmed for all samples. When pumping the waveguides with an excitation light at normal incidence, they exhibited a broad emission peak (yellow in color) below certain pumping intensity (pumping threshold), and above the threshold a sharp emission peak (orange in color) was observed from the end of the waveguides. The gain-narrowing is attributed to amplified spontaneous emission that results from the homogenous distribution of highly doped dye molecules (up to 0.8 mol%) within the organized mesochannels of the arrays. The pumping threshold values for the respective mesostructured waveguides are different from each other, increasing in the order of lamellar<hexagonal<cubic mesostructure.     

Effect of the SiO2/TiO2 ratio on the solid acidity of SiO2-TiO2/montmorillonite composites

SiO₂-TiO₂/montmorillonite composites with varying SiO₂/TiO₂ molar ratios were synthesized and the effect of the SiO₂/TiO₂ ratio on the solid acidity of the resulting composites was investigated. Four composites with SiO₂/TiO₂ molar ratios of 0, 0.1, 1 and 10 were synthesized by the reaction of colloidal SiO₂-TiO₂ particles prepared from alkoxides with sodium-montmorillonite at room temperature. The composites showed slight expansion and broadening of the XRD basal reflection, corresponding to the intercalation of fine colloidal SiO₂-TiO₂ particles into the montmorillonite sheets and incomplete intercalation to form disordered stacking of exfoliated montmorillonite and colloidal SiO₂-TiO₂ particles. The colloidal particles crystallized to anatase in the low SiO₂/TiO₂ composites but remained amorphous in the high SiO₂/TiO₂ composites. The specific surface areas (S_BET) of the composites measured by N₂ adsorption ranged from 250 to 370 m²/g, considerably greater than in montmorillonite (6 m²/g). The pore size increased with decreasing SiO₂/TiO₂ molar ratio of the composites. The NH₃-TPD spectra of the composites consisted of overlapping peaks, corresponded to temperatures of about 190 and 290 °C. The amounts of solid acid obtained from NH₃-TPD were 186-338 μmol/g in the composites; these values are higher than in the commercial catalyst K10 (85 μmol/g), which is synthesized by acid-treatment of montmorillonite. The present sample with SiO₂/TiO₂ = 0.1 showed the highest amount of acid, about four times higher than K10.     

Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films

Sol-gel SiO₂/TiO₂ and TiO₂/SiO₂ bi-layer films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO₂/TiO₂ and CS TiO₂/SiO₂ bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO₂/TiO₂ bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO₂ single-layer component and arrangement of the bi-layer structure, i.e. TiO₂ underlayer or overlayer.     

Influence of SiO2 interlayer on the hydrophilicity of TiO2/SiO2/glass produced by RF-magnetron sputtering

The effect of silicon dioxide (SiO₂) on the hydrophilicity of the TiO₂ thin film is investigated. SiO₂ and TiO₂ films were deposited on the glass by RF-magnetron sputtering. Heat-treatment for 15 h at 573 K on TiO₂/glass and TiO₂/SiO₂/glass is carried out to make Na⁺-ion diffused from the glass to the TiO₂ thin film, which results in no band-gap change but instead the enhanced crystallinity of the anatase phase-TiO₂. This in turn leads to the improvement in hydrophilicity. Irrespective of the SiO₂ interlayer, the anatase phase-TiO₂ thin film with enhanced crystallinity shows outstanding super-hydrophilicity. Consequently, under the heat-treatment condition, the SiO₂ interlayer played an important role in improving the crystallinity of the anatase phase-TiO₂ rather than preventing Na⁺-ion diffusion.     

High-performance ZnO thin film transistors with sputtering SiO2/Ta2O5/SiO2 multilayer gate dielectric

A high-performance ZnO thin film transistor （ZnO-TFT） with SiO₂/Ta₂O₅/SiO₂ (STS) multilayer gate insulator is fabricated by sputtering at room temperature. Compared to ZnO-TFTs with sputtering SiO₂ gate insulator, its electrical characteristics are significantly improved, such as the field effect mobility enhanced from 11.2 to 52.4 cm²/V s, threshold voltage decreased from 4.2 to 2 V, and sub-threshold swing improved from 0.61 to 0.28 V/dec. The improvements are attributed to the high gate capacitance (from 50 to 150 nF/cm²) as well as nice surface morphology by using dielectric with high～k Ta₂O₅ sandwiched by SiO₂ layers. The capacitance-voltage characteristic of a metal-insulator-semiconductor capacitor with the structure of Indium Tin Oxide/STS/ZnO/Al was investigated and the trap charges at the interface or bulk is evaluated to be 2.24 × 10¹² cm⁻². From the slope of C⁻² versus gate voltage, the doping density N_D of ZnO is estimated to be 1.49 × 10¹⁶ cm⁻³.     

Temperature-dependent and pump-probe ellipsometric studies of TlInSe2

Temperature-dependent phase-modulated spectroscopic ellipsometry over the photon energies 1.5-5.5 eV and temperatures 300-400 K, as well as pump-probe single wavelength rotating-analyzer laser ellipsometry at photon energy 1.61 eV and pumping power-density up to 160 W/cm² has been carried out on TlInSe₂ that has a quasi one-dimensional crystalline structure and apparently undergoes an incommensurate phase transition with temperature. Refractive indices and extinction coefficients, as well as their variation with temperature and pumping power-density have been determined. The change of the surface profile under pumping has been disclosed. The reversibility of the effect has been confirmed by the dynamic reflectance examination. Obtained results are discussed in terms of thermal effects and incommensurate phase transition in TlInSe₂. It is proposed that a giant thermo-elastic effect and a soliton wave formation are behind the observed reversible change of the surface profile.     

SiO2 layer thickness effects on the (001) texture of FePtCu:SiO2 nanocomposite films

The influence of SiO₂ layer thickness of (Fe₅₂Pt₄₈)₈₈Cu₁₂:SiO₂ multilayer nanocomposite films on their structural and magnetic properties were investigated. The films were deposited on (001) textured FePt films, and then annealed at 873 K. The crystalline texture of (Fe₅₂Pt₄₈)₈₈Cu₁₂:SiO₂ films changes drastically with respect to the thickness of the SiO₂ layers. In the film with 50-Å thick SiO₂ layers, the (111) peak was strong although the (001) orientation is dominant, and self-organized spherical FePtCu particles were formed in the SiO₂ matrix. However, in the film with 19-Å thick SiO₂ layers, flat FePt grains with perfect (001) orientation were obtained. In addition, twins with different crystalline orientations were seen in the above films with different thicknesses of the SiO₂ layers. Accordingly, different perpendicular hysteresis loops were obtained.     

Grazing incidence X-ray study of Ge-nanoparticle formation in (Ge:SiO2)/SiO2 multilayers

We present the study of formation of Ge-nanoparticles (Ge-NP) in germanosilicate (Ge:SiO₂) multilayer (ML) films under thermal treatment. In anticipation of controllable formation of Ge-NP, ML films were prepared by magnetron deposition at room temperature as 20 bi-layer stacks, each bi-layer comprised of a 7 nm thick layer of (Ge + SiO₂) (molar ratio: 60:40) succeeded by a 7 nm thick layer of pure SiO₂, and then annealed for 1 h, up to T_a = 900 °C. Formation and morphology of Ge-NP were analyzed by combining the information obtained from the grazing incidence small angle X-ray scattering and X-ray diffraction. It was found that precipitation of Ge-NP starts at T_a = 600 °C, while high degree of in-plane confinement and lateral ordering of rather uniform precipitated particles is achieved at T_a =  700-800 °C range. At still higher annealing temperature T_a > 800 °C, volume fraction of precipitated Ge-NP in SiO₂ matrix diminishes due to the out-diffusion of Ge atoms from the film, while Ge-NP are no more well confined to (Ge + SiO₂) layers.     

Hierarchical electrospun SiO2 nanofibers containing SiO2 nanoparticles with controllable surface-roughness and/or porosity

Herein we report that hierarchical electrospun SiO₂ nanofibers incorporated with SiO₂ nanoparticles with fiber diameters being ∼ 500 nm and particle sizes being tens of nanometers were developed through the combination of sol-gel process and electrospinning technique followed by high-temperature pyrolysis; and their morphologies and BET surface areas were examined. The study revealed that the pre-gelation of tetraethyl orthosilicate (TEOS) in spin dopes was important to achieve the morphological consistence of the electrospun precursor nanofibers and the resulting final SiO₂ nanofibers; additionally, SiO₂ nanoparticles appeared to be enriched on the fiber surface, while the surface-roughness and/or porosity of the nanofibers could be controlled through adjusting the incorporation amount of SiO₂ nanoparticles. The developed hierarchical electrospun SiO₂ nanofibers are expected to have important applications in composites (particularly dental composites) as well as catalyst support and adsorption.     

Gravitational waves detector mirrors: Spectroscopic ellipsometry study of Ta2O5 films on SiO2 substrates

A stack of Ta₂O₅/SiO₂ layers is presently used as coating layer of mirrors in interferometric detectors for gravitational waves. The sensitivity of these detectors is limited in the 50-300 Hz frequency range by the mirror thermal noise, and it was suggested that mechanical losses in the Ta₂O₅ are the dominant source of noise. We focus here on Spectroscopic Ellipsometry (SE) results (in the 0.75 ÷ 5 eV spectral range) obtained on high quality Ta₂O₅ films deposited on SiO₂ substrates by Double Ion Beam Sputtering at the Laboratoire des Matériaux Avancés (Lyon, France). The films are extremely flat as indicated by the 0.2 nm RMS roughness determined by Atomic Force Microscopy (AFM) on (20 × 20) μm² areas. The comparison of the optical properties determined by SE with literature data, corroborated by X-ray Photoelectron Spectroscopy (XPS) data, suggests that the films present a non-ideal bulk stoichiometry and/or some degree of nanoporosity. The possible influence of an interface layer is also discussed.     

Luminescence response and CL degradation of combustion synthesized spherical SiO2:Ce nanophosphor

This study was aimed to systematically investigate the luminescence response of SiO₂:Ce³⁺ nanophosphors with different excitation sources. The powders were synthesized by using an urea assisted combustion method. SiO₂:Ce_1m% samples were also annealed at 1000 °C for 1 h in a charcoal environment to reduce incidental Ce⁴⁺ to partial Ce³⁺ ions. High resolution transmission electron microscopy (HRTEM) images of the as synthesized and annealed powder samples confirmed that the particles were spherical and in the size range of 3-8 nm in diameter. X-ray diffraction (XRD) and electron dispersion spectroscopy (EDS) results showed that the SiO₂ was crystalline and pure. Diffused reflectance, photoluminescence (PL) and cathodoluminescence (CL) results of the SiO₂:Ce³⁺ samples were obtained and compared with each other. The CL degradation and the surface reactions on the surface of the SiO₂:Ce³⁺ were studied with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). A clear improvement in the chemical stability of the SiO₂:Ce³⁺ annealed at 1000 °C were obtained.     

Improvement in light output intensity of InGaN/GaN multiple-quantum-well blue light-emitting diode by SiO2/Si3N4 distributed Bragg reflectors and silver back mirror

In this article, the light output intensity of InGaN/GaN multiple-quantum-well (MQW) light emitting diodes (LEDs) is improved by using SiO₂/Si₃N₄ distributed Bragg reflectors (DBRs) as window layer and Ag back mirror. The SiO₂/Si₃N₄ DBRs can take several advantages, such as high reflectance with less number of DBR, passive characteristics, and high reliability due to growth in one pump down growth system. The experimental results indicated that InGaN/GaN LEDs with the 3-pair of SiO₂/Si₃N₄ DBRs show a maximum light output intensity of 64 mcd under 20 mA driving current and an improvement of 42% as compared to that of InGaN/GaN LEDs without SiO₂/Si₃N₄ DBRs. In addition, the turn-on voltage, forward resistance, and full width at half maximum (FWHM) of the emission spectra for InGaN/GaN LEDs with the 3-pair of SiO₂/Si₃N₄ DBRs and Ag back mirror are 3.23 V, 16 Ω, and 22.4 nm under 20 mA forward current.     

Fabrication of thermochromic composite using monodispersed VO2 coated SiO2 nanoparticles prepared by modified chemical solution deposition

Monodispersed thermochromic VO₂ particles were fabricated by VO₂ coating onto monodispersed SiO₂ nanoparticles with the modified chemical solution deposition technique using vanadium isopropoxide solution and monodispersed SiO₂ particle suspension solution. The average size of the resultant VO₂–SiO₂ particle was 57 nm and the coating thickness of the VO₂ layer was 6 nm. A thermochromic composite was fabricated using the VO₂–SiO₂ particles and a poly lactose acid polymer as a transparent matrix, and the transmittance of the composite at a high temperature was 10% less than that at a low temperature.     

Synthesis and characterization of ZnO/SiO2 core/shell nanocomposites and hollow SiO2 nanostructures

In this paper, we prepared the ZnO nanoparticles by a simple hydrothermal method and fabricated the ZnO/SiO₂ core/shell nanostructures through a sol-gel chemistry process successfully. The hollow SiO₂ nanostructures were obtained by selective removal of the ZnO cores. The structure, morphology and composition of the products were determined by the techniques of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The results indicated that the ZnO nanoparticles were sphere-like shape with the average size of 60 nm and belonged to hexagonal wurtzite crystal structure. With the coating of SiO₂, the vibration modes of Si-O-Si and Si-OH were found. Furthermore, the measurement results of optical properties showed that spectra of bare ZnO nanoparticles and ZnO/SiO₂ core/shell nanocomposites exhibited similar emission features, including a blue emission peak and an orange emission band.     

YAG laser-induced structural modification in transition metal ion containing 40K2O-40Nb2O5-20SiO2 glasses

Glasses with the compositions of 40K₂O-40Nb₂O₅-20SiO₂ (in mol%) containing different concentrations (0.01, 1 and 2 mol%) of NiO were prepared by a melt quenching technique. The glasses were irradiated with a continuous wave Nd:YAG laser with a wavelength of 1064 nm, and a metastable crystalline phase of KNbO₃ was obtained. In 2 mol% NiO-doped glass, lines with a width of ∼10 μm are successfully patterned by laser irradiations with a power of 0.9 W and a scanning speed of 15 μm/s. It is found from micro-Raman scattering spectra that the lines are composed of the metastable crystalline phase of KNbO₃. The crystallization mechanism in Nd:YAG laser-induced crystallization in the glasses is discussed in comparison with the usual crystallization in an electric furnace.     

Characterization of SiO2 and TiO2 films prepared using rf magnetron sputtering and their application to anti-reflection coating

Preparation of TiO₂ and SiO₂ films for optical applications was attempted using conventional rf magnetron sputtering in the sputtering ambient with various O₂/Ar+O₂ ratios and at substrate temperatures between room temperature and 400 °C. X-ray photoelectron spectroscopy (XPS) and optical spectroscopy investigations indicated that oxygen addition in the sputtering ambient was essential for growing TiO₂ films with stoichiometric compositions and good transmittance, while SiO₂ films had a stoichiometric composition of O/Si ratio=2.1-2.2 and were highly transparent in the visible wavelength region, independent of gas composition in the growing ambient. It was also identified from scanning electron microscope (SEM), atomic force microscope (AFM) and Fourier transform infrared spectroscopy (FTIR) measurements that the structural characteristics of both TiO₂ and SiO₂ films were significantly improved with O₂ addition in the sputtering ambient, showing smoother surface morphologies and higher resistances to water absorption when compared with films grown without O₂ addition. Heating of the substrate between 200 and 400 °C considerably increased the refractive index of TiO₂ layers, resulting in dense structures along with an improvement of crystallinity. For optical applications, AR coatings composed of 2-4 multi-layers on glass were designed and manufactured by stacking in turn the SiO₂ and TiO₂ films at room temperature and O₂/Ar+O₂=10%, and the performance of the produced coatings was compared with simulation results.     

Blue-shifted stimulated emission from ZnO films deposited on SiO2 by atomic layer deposition

ZnO films were prepared by atomic layer deposition upon a SiO₂ layer on a Si substrate and treated by rapid thermal annealing. The optically-pumped random lasing actions with low threshold values were observed in the ZnO films on SiO₂/Si substrates. With the decrease in ZnO film thickness or the increase in post-annealing duration, the stimulated emission shifted toward the shorter wavelength and the lasing threshold increased. The results can be attributed to the inter-diffusion between ZnO and SiO₂, which causes the modification of bandgap renormalization in ZnO.     

N2 adsorption curve of mesoporous SiO2: A neglected characterization technique

Mesoporous SiO₂ sieve and SiO₂ nanoparticles were synthesized by a traditional method in the presence and absence of tri-block copolymer surfactant P123 as structure directed agent respectively. The characterization results show that the mesoporous SiO₂ sieve has larger specific area (789 m²/g) than SiO₂ nanoparticles (373 m²/g), and there exists a substantial difference in the N₂ adsorption curves between the two samples. A speculative scheme shows that the formation of bottleneck during the N₂ adsorption process of mesoporous SiO₂ sieve should be responsible for the phenomenon.     

SiO2 and Al2O3/SiO2 coatings for increasing emissivity of Cu(In, Ga)Se2 thin-film solar cells for space applications

In this study, optical coatings were investigated as substitutes for the coverglass on flexible thin-film space solar cells. The inherent low emissivity of copper-indium-gallium-diselenide (CIGS) thin-film solar cells was increased using optical coatings for thermal balance in space. Evaporated silicon dioxide (SiO₂) and an additional aluminum oxide (Al₂O₃) coating on the CIGS solar cell increased the emissivity from 0.18 to 0.77. Higher emissivity was realized with the Al₂O₃/SiO₂ double-layer coating than with the SiO₂ single-layer coating. The straightforward double-layer coating gives the CIGS solar cells appropriate radiative properties for keeping the cell within a permissible temperature range in space.