Fabrication and Measurement of Micro Three-Dimensional Photonic Crystals of SiO2 Ceramic for Terahertz Wave Applications

Three-dimensional (3D) photonic crystals with a diamond structure made of a dense SiO₂ ceramic were successfully fabricated using a CAD/CAM micro-stereolithography and sintering process. The designed lattice constant of the diamond unit cell was 500 μm and the forming tolerance from 50 vol% SiO₂ paste (before sintering) was around 15 μm. After the SiO₂-resin photonic crystals were formed via micro-stereolithography, they were converted to pure SiO₂ ceramic photonic crystals of 99% theoretical density by sintering at 1400°C. The electromagnetic wave propagation in these dense SiO₂ photonic crystals was measured by terahertz-time-domain spectroscopy. The results showed that the band gap appeared between 470 and 580 GHz in the Γ– X 〈100〉 direction, between 490 and 630 GHz in the Γ– K 〈110〉 direction, and between 400 and 510 GHz in the Γ– L 〈111〉 direction, resulting in the formation of a common band gap in all directions between 490 and 510 GHz. These results agreed well with the band gaps calculated by the plane wave expansion method.     

Microfabrication of Three-Dimensional Photonic Crystals of SiO2–Al2O3 Ceramics and Their Terahertz Wave Properties

Dense three-dimensional microphotonic crystals of SiO₂–Al₂O₃ ceramics were fabricated using microstereolithography and successive sintering process. The forming dimensional tolerance for a 50 vol% ceramic paste is 10 μm and sintering shrinkage is around 12%. Diamond-type photonic crystals with lattice constants of 500 and 125 μm were formed and sintered successfully. The band gaps of the samples were measured and compared with the theoretically calculated band diagram.     

Fabrication of TiO2–SiO2 Photonic Crystals with Diamond Structure

Ceramic photonic crystals with diamond structure were fabricated using stereolithography and successive sintering. The green body of an epoxy resin incorporating 10 vol% TiO₂–SiO₂ was formed by stereolithography and then heated in air at 1100°–1400°C for 2 h. The sintered products maintained the diamond structure with a linear shrinkage ratio of about 57% and a porosity of 38%. The ceramic photonic crystal with eight unit cells showed a photonic band gap at the center frequency of 23.5 GHz. This fabrication method of three-dimensional (3D) ceramic photonic crystals is applicable to other 3D structural ceramics and does not require any molding techniques.     

Nanostructure of TiO2 Nano-Coated SiO2 Particles

We characterized SiO₂–TiO₂ nano-hybrid particles, prepared using the sol–gel method, using high-resolution transmission microscopy. A few nanometer-ordered TiO₂ anatase crystallites could be observed on the monodispersed SiO₂ nanoparticle surface. The quantum size effect of the TiO₂ anatase crystallites is attributed to the blue shift of the absorption band. The rough surface of the SiO₂–TiO₂ nano-hybrid particles was derived from the developed growth planes of the TiO₂ anatase crystallites, grown from fully hydrolyzed Ti alkoxide that did not react with acetic acid during the crystallization process at 600°C thermal annealing.     

Fabrication and Properties of an Anisotropic TiO2 Dielectric Composite

Thermoplastic co-extrusion was employed to fabricate an anisotropic dielectric composite based on titanium dioxide with a microcellular architecture with 50 μm macropore channels aligned to create unidirectional porosity. The resulting channeled structure exhibits artificial anisotropic dielectric properties, with the dielectric relative permittivity being 9.6 transverse to the channels and 90 in the longitudinal direction.     

PAA/TiO2一维光子晶体的制备

以聚丙烯酸(PAA)和TiO2纳米粒子为电介质材质,采用旋涂技术制备了PAA/TiO2一维光子晶体。用扫描电子显微镜对其层层沉积的结构进行了表征,用紫外可见反射光谱对光子禁带进行了研究,考察了光子禁带与成膜参数的关系。结果表明,通过调控旋涂速度或者PAA溶液质量分数,可以制备出具有不同光子禁带的PAA/TiO2一维光子晶体,且光子禁带随旋涂速度的加快线性蓝移、随PAA溶液质量分数的增大线性红移。     

Solubility of TiO2 in ZrO2

The solubility of TiO₂ in tetragonal ZrO₂ is 13.8±0.3 mol% ui 1300°C, 14.9±0.2 mol% at 1400°C, and 16.1±0.2 mol% at 1500°C. These solid solutions transform to metastable monoclinic solid solutions without compositional change on cooling to room temperature.     

Fabrication and Microstructure Characterization of Continuous Porous TiO2/Al2O3 Composite Membrane

Using a multipass extrusion process, continuous porous Al₂O₃ body (∼41% porosity) was produced and used as a substrate to fabricate continuous porous TiO₂/Al₂O₃ composite membrane. The diameter of the continuous pores of the porous Al₂O₃ body was about 150 μm. The TiO₂ nanopowders dip coated on the continuous pore-surface Al₂O₃ body existed as rutile and anatase phases after calcination at 520°C in air. However, after aging of the fabricated continuous porous TiO₂/Al₂O₃ composite membrane in 20% NaOH at 60°C for 24 h, a large number of TiO₂ fibers frequently observed on the pore surface. The diameter of the TiO₂ fibers was about 150 nm having a high specific surface area. However, after 48-h aging period, the diameter of the TiO₂ fibers increased, which was about 3 μm. Most of the TiO₂ fibers had polycrystalline structure having nanosized rutile and anatase crystals of about 20 nm.     

Formation of Nanometric TiB2 from TiO2

Titanium diboride can be produced by ball-milling a mixture of TiO₂, B₂O₃, and Mg metal for between 10 and 15 h. The reaction was found to be completed during the milling with no evidence of residual Mg. The unwanted phase, MgO, was readily removed by leaching in acid. The leached powder obtained after 15 h milling had a particle size of <200 nm and was highly faceted. The particle size decreased to ∼50 nm after 100 h milling and seemed to be relatively monodisperse. Scherrer calculation of the crystallite size showed that the product particles were probably single crystal.     

Ferroic Phase Transitions in (Na1/2Bi1/2)TiO3 Crystals

The ferroic phase-transition behavior of two (Na_1/2Bi_1/2)TiO₃(NBT) crystals grown by flux and by the Czochralski method has been investigated in the present study. Although both the tetragonal and the rhombohedral phases of NBT are expected to be ferroelastic, these crystals exhibit different ferroelastic behavior. The two NBT crystals also show differences in the amount of temperature hysteresis and the thermal expansion coefficients. These differences can be attributed to nonstoichiometry and structural variations dependent on the growing method. The present investigation has revealed a second maximum at −450°C in dielectric constant (( T )) curves, which could indicate that the intermediate tetragonal phase is either polar or antipolar. This maximum, however, originates from space-charge polarization and interaction between the charge carrier and the electrode, such that the tetragonal phase, in fact, is para-electric. The diffuse phase transition (DPT) of the NBT crystal, therefore, is from a paraelectric and ferroelastic tetragonal phase to a ferroelectric and ferroelastic rhombohedral phase. The crystallographic supergroup-subgroup relationships in the ferroic phase transitions of NBT crystals are discussed.     

Solubility of TiO2 in BaTiO3

Scanning electron microscopy and electron probe micro-analysis were used to investigate the microstructure of both slow-cooled and quenched polycrystalline BaTiO₃ specimens with a small excess of TiO₂ (Ba/Ti=0.995 to 0.999) or of BaO (Ba/Ti=1.002 and 1.005). The electron micrographs of polished and etched TiO₂-excess BaTiOs samples, and of fracture surfaces of quenched samples, showed a second phase in the grain boundaries and triple-point regions, whereas no second phase was observed in samples having Ba/Ti=1.000. Microprobe analysis of the second phase gave compositions near that of the reported adjacent phase of higher TiO₂ content, Ba₆Ti₁₇O₄₀. The results indicate that the solubility of TiO₂ in BaTiO₃ is <0.1 mol%.     

Formation and Sintering of TiO2 (Anatase) Solid Solution in the System TiO2-SiO2

In the TiO₂-SiO₂ system, anatase solid solutions (ss) containing up to similar/congruent ∼15 mol% SiO₂ are formed in the as-prepared state by the hydrazine method. The lattice parameters a and c decrease linearly from 0.3785 to 0.3776 nm and from 0.9514 to 0.9494 nm, respectively, with increased SiO₂ content. At high temperatures, the solid solutions by transformation decompose into rutile and amorphous SiO₂. The anatase(ss) powders have been characterized for particle size and surface area. They consist of very fine particles (7-25 nm). Surface areas at low temperatures are very high and do not drop below 60 m²/g at 1000°C. Nanostructured anatase(ss) ceramics, with greaterthan/equal to 99.5% of theoretical density and an average grain size of 72 nm, have been fabricated by hot isostatic pressing for 1 h at 850°C and 196 MPa. Their mechanical and electrical properties have been examined.     

Fabrication of Micrometer-Scale Anatase-Phase TiO2 Congeries Assembled with Hollow Spheres

Micrometer-scale anatase-phase TiO₂ congeries assembled with hollow spheres have been synthesized by a bubble-template method combined with a facile chemical process. The as-prepared products were characterized by means of X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Some of the congeries exhibited unique three-dimensional hierarchical architectures. The bubble-template strategy used in the synthetic process may represent a general approach to fabricate hollow micro- and nanostructures and therefore contribute to the formation mechanisms of hollow micro- and nanostructures.     

Sol–Gel Fabrication of Epitaxial and Oriented TiO2 Thin Films

Thin films of titania have been prepared by spin coating on fused silica, Si(100), and rutile(110), starting with a sol–gel process. The alkoxide solution was chelated with diisopropanolamine, and the resulting precursor solution was hydrolyzed prior to coating. Oriented rutile films were obtained on fused silica and Si(100), while epitaxially oriented film was formed on rutile (110). X-ray diffraction results indicated that the as-deposited films transformed to rutile via anatase with increasing temperature. The phase transformation temperature was found to be dependent on the substrate, and it was in general higher on the substrates than that observed for the gel powder. Microstructural studies revealed that these films consisted of finely dispersed grains of 0.05 to 0.15 μm in size.     

Growth of TiO2 Single Crystals and Bicrystals by the Laser-Heated Floating-Zone Method

TiO₂ bicrystals with controlled misorientation have been grown by a laser-heated floating-zone method using a [001] oriented bicrystal seed designed for producing a (210)[001] tilt boundary. The grain boundary and crystal morphology are sensitive to the growth atmosphere, as confirmed by optical and transmission electron microscopies and by the Laue X-ray back-reflection method. These observations are discussed with respect to the nonstoichiometry of TiO₂.     

Influence of TiO2 on Properties of Glasses in the System K2O–PbO–SiO2–TiO2 and Its Relation to Structure

By a progressive weight percent substitution of TiO₂ for SiO₂ at various rations of concentration of K₂O and PbO, the entire region of glass formation in the quaternary system K₂O–PbO–SiO₂–TiO₂ was covered with 51 glass compositions. The properties of these glasses were determined and studied with respect to the role of TiO₂ in the system. The results indicated that the dielectric constant increased progressively with increasing TiO₂ concentration whereas the dissipation factor showed an overall decrease, when measured at 1 Mc and 25°C. Density and the refractive index increased progressively with increasing TiO₂ concentration but deviated from the additive relation. Chemical durability, expansivity, and softening temperature vs. composition curves showed definite inflections. The effect of TiO₂ on oxygen packing indicated that Ti⁴⁺ strengthens the network in lower concentrations and weakens the network in higher concentrations in this system. It appears to be likely that Ti⁴⁺ changes its coordination number form 4 to 6.