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.     

Fabrication of Ceramic Photonic Crystals with Diamond Structure for Microwave Applications

A process for fabricating three-dimensional photonic crystals composed of SiO₂–TiO₂-based ceramics with a diamond structure was investigated. An epoxy structure having an inverse diamond configuration was fabricated by stereolithography, a rapid prototyping method. The epoxy structure was infiltrated with a ceramic slurry and then cold isostatically pressed. After sintering at 670°C for 5 h in air, the epoxy was burned off, leaving behind the desired structure of a ceramic photonic crystal. The calculated band diagram indicated that an absolute photonic band gap for all wave vectors existed. The measurement of transmission in the 〈100〉 direction from 10 to 20 GHz showed that a complete band gap formed at about 14.7–18.5 GHz. The magnitude of the maximum attenuation was as large as 30 dB at 17 GHz, which indicated that the fabricated structure worked well as a photonic crystal.     

Microwave Absorption in Photonic Crystals Composed of SiC/Resin with a Diamond Structure

Three-dimensional photonic crystals were fabricated by infiltrating an epoxy mold with a SiC/polyester mixture. The epoxy molds with normal or inverse diamond structures were formed by stereolithography. The size of the mold was 45 mm × 18 mm × 18mm, and the lattice constant of the photonic crystals was 18 mm. The effects of the epoxy mold type, aspect ratio (the ratio of height and diameter of a diamond lattice rod), and number of sample units on the formation of photonic band gap (PBG) and microwave absorption ability along the 〈100〉 direction were studied. The attenuations of microwave transmission and reflection were measured through the photonic crystal samples at a frequency range of 3–12 GHz with a network analyzer. The results obtained suggest that the combination of the absorbing material SiC and diamond structure has a dual effect to form a PBG with a high absorption ability.     

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.     

Fabrication and Characterization of Three-Dimensional ZrO2-Toughened Al2O3 Ceramic Microdevices

Dense three-dimensional (3D) microdevices of ZrO₂-toughened Al₂O₃ (ZTA) were fabricated using microstereolithography and a subsequent sintering process. Using microstereolithography, 3D green bodies could be formed from a 40 vol% ZTA ceramic–resin paste. After sintering, the fabricated 3D devices are converted into dense ceramic devices without deformation. In this study, a gear (with a tooth edge of 25 μm) and a photonic crystal (with a lattice constant of 500 μm) were designed and fabricated. The dimensional accuracy of the fabrication process is within 20 μm and the sintering shrinkage is around 26% for these microdevices. The relative density of the sintered ZTA ceramics reached 96.5% of theoretical value. The measured hardness and toughness were about 14 GPa and 11 MPa m^1/2, respectively, in both the top and side surfaces. A band gap between 320 and 420 GHz was observed in the ZTA photonic crystal. The microstereolithography process can be easily applied to other ceramic materials and devices.     

Band Gap Modification of Diamond Photonic Crystals by Changing the Volume Fraction of the Dielectric Lattice

Photonic crystals with a diamond structure of epoxy lattices in which TiO₂-based ceramic particles are dispersed were fabricated by stereolithography. The periodicity of the lattice was designed to reflect electromagnetic waves in the gigahertz range. The volume fraction (β) of the dielectric lattice medium was modified from 14% to 33% by changing the rod diameter of the lattice. The photonic band gap was observed along Γ-L 〈111〉, Γ-X 〈100〉, and Γ-K 〈110〉 directions and the complete photonic band gap was formed at over β= 20%. The width of the forbidden gap increased gradually when the β increased over 14%, and reached 2.4 GHz at β= 33%. These results agreed with the band calculation using 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.     

Visible Frequency Thin Film Photonic Crystals from Colloidal Systems of Nanocrystalline Titania and Polystyrene Microspheres

This work describes a simple and novel ceramic processing technique to form periodic ordered structures in ceramic materials with a uniform pore size distribution. This material shows photonic gaps at visible/near-IR wavelengths. Monodisperse colloidal polystyrene microspheres are self-organized into a crystalline structure of close-packed spheres in a suspension of nanocrystalline titania. The nanoparticle titania fills the intersphere region simultaneously during colloidal crystallization. Removal of the polystyrene microspheres by calcination at a temperature of 520°C results in a periodic porous structure with a high refractive index background material. Crystals having ordered regions, a few millimeters across with typical grain sizes of 50–70 μm, are grown as thin films on substrates including glass and silicon. Optical reflectivity measurements indicate peaks at the stop band wavelengths that scale with the pore size. Visual inspection and optical microscopy reveal uniform colored regions for crystals with periodicity comparable to visible wavelengths. Despite the presence of cracks resulting from drying and heat treatment as well as numerous grain boundaries, optical characterization clearly demonstrates a photonic band gap. Reflectance peaks due to a pseudogap can be shifted by application of high pressure. In the following sections we will describe the experimental procedure and discuss optical reflectance and transmission measurements that can reveal information about the crystals, namely, the lattice constant, the refractive index, and the filling fraction of the background material.     

Microwave Dielectric Properties of Hexagonal 12R-Ba3LaNb3O12 Ceramics

The dielectric properties of dense ceramics of the n =0 member of a newly identified homologous series Ba_{3+ n} LaNb₃Ti _n O_{12+3 n} , where n =0, 1, and 2, are reported. Single-phase powders can be obtained from the mixed-oxide route at 1350°C and dense ceramics (>97% of the theoretical X-ray density) with uniform microstructures (3–5 μm) can be obtained by sintering in air at 1500°C. The ceramics are excellent dc insulators with a band gap >2.6 eV that resonate at microwave frequencies with a relative permittivity, ɛ_r∼44, a quality factor, Q × f _r, of ∼9000 at f _r∼5.5 GHz and a temperature coefficient of resonant frequency, TC_f,∼−100 ppm/K.     

Film Synthesis of Y3Al5O12 and Y3Fe5O12 by the Spray–Inductively Coupled Plasma Technique

Thin films of yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) and yttrium iron garnet (YIG, Y₃Fe₅O₁₂) were synthesized on single-crystal Al₂O₃ substrates by a modification of spray pyrolysis using a high-temperature inductively coupled plasma at atmospheric pressure (spray–ICP technique). Using this technique, films could be grown at faster rates (0.12 μm/min for YAG and 0.10 μm/min for YIG) than using chemical vapor deposition (0.005–0.008 μm/min for YAG) or sputtering (0.003–0.005 μm/min for YIG). The films were dense and revealed a preferred orientation of (211). The growth of YIG was accompanied by coprecipitation of α-Fe₂O₃. The coprecipitation, however, could be largely suppressed by preliminary formation of a Y₂O₃ layer on the substrate.     

Spark Plasma Sintering of Nano-Sized TiN Prepared from TiO2 by Controlled Hydrolysis of TiCl4 and Ti(O-i-C3H7)4 Solution

Nano-sized TiO₂ powders were prepared by controlled hydrolysis of TiCl₄ and Ti(O-i-C₃H₇)₄ solutions and nitrided in flowing NH₃ gas at 700°–1000°C to form TiN. Nano-sized TiN was densified by spark plasma sintering at 1300°–1600°C to produce TiN ceramics with a relative density of 98% at 1600°C. The microstructure of the etched ceramic surface was observed by SEM, which revealed the formation of uniformly sized 1–2 μm grains in the TiCl₄-derived product and 10–20 μm in the Ti(O-i-C₃H₇)₄-derived TiN. The electric resisitivity and Vickers micro-hardness of the TiN ceramics was also measured.     

Synthesis of an AlN Polycrystalline Bulk Layer and Nanotubes by Using NH3 and Bi

A bulk layer of aluminum nitride (AlN) polycrystals was synthesized on a boron nitride crucible surface by heating Al chunks with 5 mol% of bismuth at 1273 K for 3 h under NH₃ gas flow. The fragments of the layer were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The platelet grains of AlN with a size of 0.1–1.0 μm and having preferred orientation of the c -axis perpendicular to the layer were formed at the crucible side. Nanotubes 6–15 μm long and about 20–100 nm thick grew on the gas phase side of the layer.     

Synthesis of High Aspect Ratio Platelet SrTiO3

A method for synthesis of high aspect ratio platelet seeds by growth of SrTiO₃ on Sr₃Ti₂O₇ core particles is reported. The aim of this study was to identify and control the morphology and size of SrTiO₃ particles via molten salt synthesis. Platelet and tabular morphologies with rectangular faces were obtained using rutile and anatase, respectively. Platelet SrTiO₃ particles with an edge length of 10–40 μm and a thickness of 1–4 μm were obtained. High aspect ratios (edge length to thickness) of 7–10 were measured for platelet particles as opposed to lower aspect ratios of 2–4 for tabular particles. Highly anisotropic platelets are suitable template candidates to achieve textured ceramics.     

Controlled Crystallization of GeSe2–Ga2Se3–CsI Chalcohalide Glasses During Molding

This is an attempt to produce molded 8–14 μm transmitting glass–ceramics by a one-step molding technique. Controlled crystallization is expected to be carried out during application of an appropriate molding process to pure glasses. GeSe₂–Ga₂Se₃–CsI chalcohalide glass was used for the attempt, and well-designed molding parameters were applied to the glass. The results indicate that large quantities of submicrometer crystalline particles are formed and regularly distributed inside the glass matrix during the molding, leading to improved toughness without influencing the 8–14 μm transmittance. This phenomenon implies that it is possible and convenient to produce molded glass–ceramics by a one-step molding technique.     

Molten-Salt Synthesis of Ba1–xPbxTiO3 in the System BaTiO3–PbCl2

Ba_{1– x} Pb _x TiO₃ powder with a fixed composition was prepared by the reaction of BaTiO₃ powders with molten PbCl₂at various PbCl₂/BaTiO₃ molar ratios at 600° and 800°C in a nitrogen atmosphere. When 0.1 μm powder was used, the reaction was finished when x = 0.9. Two phases of BaTiO₃and a solid solution of Ba_{1– x} Pb _x TiO₃ coexisted, but the final phase gave a solid solution of Ba_{1– x} Pb _x TiO₃ at 800°C. When 0.5 μm powder was used, the two phases coexisted in the products at 600°C at PbCl₂/BaTiO₃= 1.0. A sintered compact of Ba_{1– x} Pb _x TiO₃ powders solid solution was prepared by hot isostatic pressing, and its dielectric constant was measured in the temperature range 20°–550°C.     

Terahertz Wave Control Using Ceramic Photonic Crystals with a Diamond Structure Including Plane Defects Fabricated by Microstereolithography

The fabrication and terahertz wave properties of alumina microphotonic crystals with a diamond structure were investigated. Acrylic diamond structures with alumina particles' dispersion were formed using microstereolithography. Fabricated precursors were dewaxed and sintered in air. The electromagnetic wave properties were measured by terahertz time-domain spectroscopy. A complete photonic band gap was observed from 0.40 to 0.47 THz, and showed good agreement with the simulation of a plane wave expansion method. Moreover, a localized mode was observed by introducing a plane defect between twinned diamond structures. The localized mode was analyzed using transmission line modeling simulation.     

Fabrication of Metallodielectric Photonic Crystals with a Diamond Structure and their Microwave Properties

Three-dimensional (3D) metallodielectric photonic crystals with a diamond structure were fabricated in order to investigate the formation of stop bands and the absorption ability for microwaves with the dielectric absorbing media embedded into the 3D metal lattice. First, the metallic photonic crystals were prepared by filling the epoxy molds formed by stereolithography with a metal alloy having a low melting point of 70°C, followed by removal of the molds. The metallodielectric photonic crystals were then fabricated by infiltrating the porous metal crystal with a SiC/polyester mixture. The lattice constant of photonic crystals was 15 mm. The effects of different aspect ratios of diamond lattice rods, number of metallic lattice units along Γ-L 〈1 1 1〉, Γ-X 〈1 0 0〉, and Γ-K 〈1 1 0〉 directions, and metallodielectric samples along the Γ-X 〈1 0 0〉 direction on the formation of stop band and microwave absorption ability were investigated in the frequency range from 3 to 30 GHz. Metallodielectric photonic crystals formed showed good absorption ability. The measured transmission spectra of the metallic and metallodielectric crystals agreed well with the simulation of the transmission line modeling method.     

Near-Surface Deformation in an Alumina–Silicon Carbide-Whisker Composite due to Surface Machining

Deformation due to two different surface-machining conditions—grinding (126 μm diamond) and polishing (3 μm diamond)—in an uniaxial hot-pressed Al₂O₃–30%-SiC-whisker composite has been investigated. A Warren–Averbach analysis of grazing incidence X-ray diffractometry data shows that the deformation is localized to the very top surface zone. The cell size and the root mean square of the strain show a gradient in the deformed layer. Transmission electron microscopy studies, in cross-sectional view, also show a near-surface deformation zone containing dislocations, twins, and cracks. This is seen for both machining procedures, but the depth of the zone and the degree of deformation, in terms of dislocation density and number of cracks, is much higher in the roughly ground specimen than in the polished one. For comparison, a monolithic Al₂O₃ sample also has been studied after grinding. The deformation zone is very similar to the Al₂O₃–SiC sample with the same grinding condition, but cracks and dislocations are present at a slightly larger depth. The deformation depth for the polished Al₂O₃–SiC sample is ∼50 nm. In the ground Al₂O₃–SiC sample, the deformation depth is 1–1.5 μm and corresponds to the grain size. The deformation zone in the ground monolithic Al₂O₃ sample is 1.5–2 μm deep. The observed grain-boundary cracks are almost parallel to the surface and may originate from nonaccommodated plastic flow between grains.     

Abrasive Wear Behavior of Heat-Treated ABC-Silicon Carbide

Hot-pressed silicon carbide, containing aluminum, boron, and carbon additives (ABC-SiC), was subjected to three-body and two-body wear testing using diamond abrasives over a range of sizes. In general, the wear resistance of ABC-SiC, with suitable heat treatment, was superior to that of commercial SiC. When the fine-scale (3 μm) diamond abrasives were used, it was found that thermal annealing at 1300°C increased the resistance to three-body wear by a factor of almost three, and two-body wear by a factor of almost two, compared with as-hot-pressed samples. Higher annealing temperatures, however, led to a decline in wear resistance from its highest value. Similar behavior was seen for 1300°C-annealed samples subjected to 15 μm diamond abrasive, although higher-temperature annealing at 1500°–1600°C enhanced the wear resistance again. When coarse abrasives (72 μm) were used, the wear resistance progressively increased with increased annealing temperature from ∼1000° to 1600°C. Corresponding transmission and scanning electron microscopy studies indicated that, whereas transgranular, conchoidal cracking was dominant in the mild abrasive wear with fine-scale (3 μm) abrasives, intergranular cracking and subsequent grain pullout was far more predominant in the more severe abrasive wear with coarse abrasives. Because the hardness and indentation toughness were barely altered during thermal treatment, the observed wear behavior was attributed mainly to the thermally induced microstructural changes, including the crystallization of glassy grain-boundary films, the possible strengthening of the boundaries due to the enhancement of the aluminum, and the formation of aluminum-rich, coherent nanoscale precipitates in the matrix grains above 1300°C.     

Extrinsic OH− Absorption in Transparent Polycrystalline Lanthana-Doped Yttria

Transparent lanthana-doped yttria fabricated by transient solid second-phase sintering under wet hydrogen typically has a broad absorption band with a peak at 3.08 μm. The absorption band shift observed in samples treated in wet deuterium indicated that the 3.08-μm absorption was due to OH⁻ ions. The diffusion rates of hydrogen defects in lanthana-doped yttria were determined in the temperature range from 1000° to 1400°C. The changes in the concentrations of OH⁻ ions upon anneals were determined by measuring infrared absorbance at 3.08 μm. The diffusion coefficient is 1.3 × 10⁻⁷, 9.9 × 10⁻⁷, and 4.1 × 10⁻⁶ cm²/s at 1000°, 1200°, and 1400°C, respectively, with an activation energy of 140 kJ/mol. Annealing in a controlled oxygen partial-pressure environment can remove the OH⁻ absorption band and bring the total absorption in the 3- to 5-μm range closer to the intrinsic values.