Liquid phase low temperature sintering of niobate and cerate fine powders

The efficiency of simultaneous application of chemically-derived starting powders and melt-forming sintering aids in low temperature sintering has been demonstrated. Doping of cryochemically processed BiNbO₄ powders with CuO/V₂O₅ causes reducing sintering temperatures from 850–900^∘C to 700–720^∘C. Similar doping of Zn₃Nb₂O₈ fine powders allows to obtain ceramics with density 97–98% and Q × F values up to 40 000 GHz at T > 720^∘C. The sintering of solution-derived BaCeO₃ powders doped with CuO results in dense ceramics at T = 1000^∘C. Morphological evolution during sintering was observed using hot stage SEM. Low temperature liquid phase sintering of fine powders is rather sensitive to the traces of secondary phases and to the micromorphology of starting powders though observed reduction of sintering temperatures is substantially larger than for traditional liquid phase sintering of coarse-grained oxide powders.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Hydrothermal growth of BaTiO3 thin films on printed circuit boards for integral capacitor applications

Polycrystalline BaTiO₃ films were hydrothermally grown on Ti-coated substrates from 80^∘C to 200^∘C. Films grown at 200^∘C exhibited the lowest dielectric loss of around 0.1. Proton incorporation was more severe for the 80^∘C film resulting in higher dielectric losses and leakage currents about two orders of magnitude higher. Post deposition oxygen plasma treatment removed incorporated protons and reduced the loss tangent but did not reduce defect density. As such, the leakage current of the 80^∘C film remained high. The films had dielectric constants of 275 to 675 from 100 Hz to 100 kHz and a value of 67 from 100 MHz to 3 GHz.     

Synthesis of nanocomposites of PMN-PT-BT with metal oxides via surface modification

Low-temperature-sinterable PMN-PT-BT [0.96 (0.91Pb(Mg_1/3Nb_2/3)O₃-0.09PbTiO₃)-0.04BaTiO₃] powder was first prepared by the modified mixed oxide method and then metal (M = Cu, Mg, Ag) oxides were introduced as their nitrate salts. Precalcined PMN-PT-BT/MO composite powders were surface modified with the magnesia sol to suppress diffusion of Ag or metal oxides. Such prepared composite powders were sintered > 98% T.D. at 850–900^∘C and showed homogeneous microstructures with <100 nm Ag or metal oxide particles. Nanoparticles were located mostly in grains and some on grain boundaries. Grain growth was substantially inhibited and resulted in grain size of ∼2 μm. The nanocomposites of PBT/Ag and PBT/MgO showed substantially improved sintered densities and dielectric properties at sintering temperature below 1000^∘C, but the PBT/CuO composite was hardly affected. The PBT/Ag composites treated with the MgO sol showed good handling strength of MOR > 120 MPa. The proper amount of the magnesia sol for surface modification seemed to be 0.5–1.0 wt.     

Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C     

Structure and dielectric properties of BaTi4O9 thin films for RF-MIM capacitor applications

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using RF magnetron sputtering. A homogeneous BaTi₄O₉ crystalline phase developed in the films deposited at 550^∘C and annealed above 850^∘C. When the thickness of the film was reduced, the capacitance density and leakage current density increased. Furthermore, the dielectric constant was observed to decrease with decreasing film thickness. The BaTi₄O₉ film with a thickness of 62 nm exhibited excellent dielectric and electrical properties, with a capacitance density of 4.612 fF/μm² and a dissipation factor of 0.26% at 100 kHz. Similar results were also obtained in the RF frequency range (1–6 GHz). A low leakage current density of 1.0 × 10⁻⁹ A/cm² was achieved at ± 2 V, as well as small voltage and temperature coefficients of capacitance of 40.05 ppm/V² and –92.157 ppm/^∘C, respectively, at 100 kHz.     

Crystallinity and photocatalytic activity of liquid phase deposited TiO2 films

Anatase TiO₂ films were deposited on glass substrates at 50 and 200^∘C to investigate the effect of growth temperature on the photocatalytic acitivity of the films. It was observed that the films grown at 200^∘C were composed of columnar crystallites and were more porous than the films grown at 50^∘C which had more compact structures. Also, the film crystallinity increased from 75 to 90% if the higher growth temperature was used. Despite the higher crystallinity, it was observed that for crystallinities between 60 and 90%, the photocatalytic behavior of the films was more significantly affected by changes in the surface area.     

Preparation of Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films by MOCVD using ultrasonic nebulization

Thin films of Pb(Mg_1/3,Nb_2/3)O₃ (PMN) and Pb(Mg_1/3,Nb_2/3)O₃-PbTiO₃ (PMN-PT) were fabricated on Si and Pt/Ti/SiO₂/Si substrates by MOCVD using ultrasonic nebulization and their characteristics were investigated. PMN-PT films deposited at 350^∘C were annealed in a RTA (Rapid Thermal Annealing) system at 650^∘C for 30 sec to improve the micostructural properties. The crystallographic properties of PMN-PT films strongly depend on the content ratio of PbTiO₃. The content of pyrochlore phase in PMN-PT films decreased with the increase of Ti content and nearly single phase perovskite films were obtained at the composition of 80PMN-20PT. The PMN-PT films with perovskite phase showed a typical butterfly type C-V curve which verifies the ferroelectricity and had the relative dielectric constant of about 60.     

Study of nanocrystal TiO2 thin films by thermal annealing

The amorphous films were annealed in a wide temperature range (250–1000^∘C) and film properties of TiO₂ thin films were studied. Nano-sized anatase polycrystallites had been induced by thermal annealing for the films annealed at and above 300^∘C as confirmed by X-ray diffraction. Strong LO-phonon Raman modes, especially B_1g (395 cm⁻¹) and E _g (636 cm⁻¹) in Raman spectra and the absorption peak at 436 cm⁻¹ in absorbance spectra by Fourier transform infrared spectroscopy also indicated the existence of anatase phase in crystalline thin films. In addition, with the increase of the annealing temperature, the wettability of the film surface was enhanced as shown by the decrease of water contact angle from over 90^∘ to less than 40^∘. Moreover, upon UV laser irradiation on film surface, the water contact angle saturated at 10^∘ indicative of a highly hydrophilic surface for all the films, which arose from the dissociative adsorption of water molecules on the defect sits of the surface generated by the photocatalysis reactions of TiO₂. This behavior makes the film a good potential candidate for self-clean coatings.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Growth and characterization of device quality ZnO on Si(111) and c-sapphire using a conventional rf magnetron sputtering

In this article, it is shown that high quality ZnO films were grown on Si(111) and Al₂O₃(0001) substrates using a conventional rf magnetron sputtering. High-resolution X-ray diffractometry (HR-XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and photoluminescence (PL) investigations clearly confirmed that the ZnO films grown on Al₂O₃ (0001) at substrate temperatures above 650^∘C are single crystal as well as high optical quality. It is also estimated in both cases grown on Si and Al₂O₃ that an introduction of template pre-grown at 500^∘C can induce a homogeneous interface and improvement of emission characteristic by relaxing the strain caused by large lattice and thermal mismatch between the film and substrate and by reducing defect density in interface region.     

Spray pyrolysis of La0.6Sr0.4Co0.2Fe0.8O3-δ thin film cathodes

Spray pyrolysis has been used to prepare La_0.6 Sr_0.4Co_0.2Fe_0.8O_3-δ thin film cathodes for solid oxide fuel cell (SOFC) applications. The films are polycrystalline with nano-meter sized grains and less than 1 μm in thickness. Deposition parameters for film deposition have been established. The ratio of deposition temperature to solvent boiling point is found to be the most important processing parameter that determines whether a crack free homogeneous and coherent film is obtained. The morphology can be tailored by the deposition parameters. Annealing at 650^∘C for four hours in air results in coherent films of the desired perovskite phase. The films are potential cathodes for thin film micro-solid oxide fuel cells.     

Synthesis and properties of ferroelectric Si-doped (Bi, Nd)4Ti3O12 thin films by chemical solution deposition

Ferroelectric Si-doped (Bi,Nd)₄Ti₃O₁₂ thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates through metal-organic compounds by the chemical solution deposition. The Bi_3.25Nd_0.75Ti_2.9Si_0.1O₁₂ (BNTS) precursor films were found to crystallize into the Bi-layered perovskite Bi₄Ti₃O₁₂ single-phase above 600^∘C. The synthesized BNTS films revealed a random orientation having a strong 117 reflection. The BNTS thin films prepared between 600^∘C and 700^∘C showed well-saturated P-E hysteresis loops with P _r of 13–14 μ C/cm² and E _c of 100–110 kV/cm at an applied voltage of 5 V. The surface roughness of the BNTS thin films was improved by Si doping compared with that of undoped Bi_3.35Nd_0.75Ti₃O₁₂ films.     

ZnGa2O4 thin films fabricated by Sol-gel spinning coating process

ZnGa₂O₄ thin film phosphors have been synthesized on ITO coated glass and soda-lime glass at a firing temperature of 500^∘C and an annealing temperature of 500^∘C and 600^∘C via a chemical solution method using Zinc acetate dihydrate, Gallium nitrate hydrate and 2-methoxiethanol as a solution. XRD patterns of the film phosphors synthesized showed the peaks of ZnGa₂O₄ crystalline phases. AFM surface morphologies of the ZnGa₂O₄ thin film phosphors revealed marked differences according to an annealing temperature of 500^∘C and 600^∘C under an annealing atmosphere (3% H₂/Ar). On the other hand, the sheet resistance of ZnGa₂O₄ thin film phosphors, which were measured by four-point probe instrument, was approximately 5.76 Ω /square and 7.86 Ω /square with annealing temperature, respectively. The ZnGa₂O₄ thin film phosphors exhibited blue emission spectra with peak wavelength of 434 nm and 436 nm by ultra-violet excitation around 230 nm.     

Ferroelectric properties of heterolayered lead zirconate titanate thin films

Heterolayered Pb(Zr_{1 − x} Ti _x )O₃ thin films consisting of alternating PbZr_0.7Ti_0.3O₃ and PbZr_0.3Ti_0.7O₃ layers were successfully deposited via a multistep sol-gel route assisted by spin-coating. These heterolayered PZT films, when annealed at a temperature in the range of 600–700^∘C show (001)/(100) preferred orientation, demonstrate desired ferroelectric and dielectric properties. The most interesting ferroelectric and dielectric properties were obtained from the six-layered PZT thin film annealed at 650^∘C, which exhibits a remanent polarization of 47.7 μC/cm² and a dielectric permittivity of 1002 at 100 Hz. Reversible polarization constituents a considerably high contribution towards the ferroelectric hysteresis of the heterolayered PZT films, as shown by studies obtained from C-V and AC measurement.     

Improvement of the thermal and chemical stability of Al doped ZnO films

To improve the stability of sputter-deposited ZnO:Al (AZO) films at high temperature above 300^∘C, an amorphous Zn-Sn-O (ZTO) film was deposited on the top of AZO films as an protective layer by co-sputtering of pure ZnO and SnO₂ targets. Amorphous ZTO films had resistivity in the range from 10⁻² to 10⁻³ Ωcm and were stable up to temperature of 400^∘C. Heat treatments of bare AZO films in the atmosphere at 400^∘C resulted in a dramatic increase in the resistivity accompanied by substantial decrease in carrier concentration and Hall mobility. The AZO films covered with the ZTO film showed remarkable improvement in thermal stability for subsequent heat treatments in the temperature range from 200 to 400^∘C in the atmosphere as well as chemical stability in weak acidic solution. X-ray photoelectron spectroscopy analysis showed that the improvement was attained by ZTO layer acting as diffusion barrier of oxygens and/or water vapors.     

Optical Properties of LiTaO3 Thin films crystallized by RTA processes

High-performance pyroelectric infrared detectors have been fabricated using Lithium tantalite (LiTaO₃) thin films deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by diol-based sol-gel method and rapid thermal annealing (RTA) technique. The dielectric and pyroelectric properties of IR detectors of LiTaO₃ thin films crystallized by conventional and RTA processes are investigated. Experimental results reveal that the heating rate will influence strongly on dielectricity and pyroelectricity of LiTaO₃ thin films. The voltage responsivities (Rv) measured at 80 Hz increase from 5496 to 8455 V/W and the specific detecivities (D^∗) measured at 300 Hz increase from 1.94 × 10⁸ to 2.38 × 10⁸ cmHz^1/2/W with an increase of heating rate from 600 to 1800^∘C/min. However, the voltage responsivity and the specific detecivity decrease with heating rate in excess of 1800^∘C/min. The results show that the LiTaO₃ thin film detector with a heating rate of 1800^∘C/min exists both the maximums of voltage responsivity and specific detecivity.     

Effects of Mn-doping on TSDC and degradation of BaTiO3

The effects of Mn-doping on TSDC (Thermally Stimulated Depolarization Current) and electrical degradation of BaTiO₃ have been investigated. TSDCs of un-doped BaTiO₃ and Ba(Ti_1−x Mn_x)O_3−δ exhibited the three sharp TSDC peaks around phase transition temperatures. TSDC of Ba(Ti_0.995Mg_0.005)O_2.995 increased gradually from 50^∘C and this anomalous depolarization current kept going up well above the Curie temperature (∼130^∘C). TSDCs of un-doped BaTiO₃ and Ba(Ti_0.995Mn_0.005)O_3−δ decreased in the temperature range above the Curie point, whereas a slight increase in TSDC was confirmed at the specimen of Ba(Ti_0.99Mn_0.01)O_3−δ. TSDCs of Ba(Ti_0.995−y Mg_0.005Mn_y)O_3−δ (y = 0.005, 0.01) were lower than that of Ba(Ti_0.995Mg_0.005)O_2.995.     

Zeolite coating on foamed stainless steel by in-situ crystallization method

Faujasite-type zeolite films were prepared on foamed stainless steel by the in-situ crystallization method. Precursor solutions were prepared by dissolving water glass and NaAlO₂in a NaOH solution and aged at room temperature for two days. The concentrations of the starting materials were varied from 0.29 to 2.3 M (in SiO₂concentration) keeping the molar ratios of Na₂O:SiO₂:Al₂O₃fixed at 3.6:3.0:1.0. The foamed stainless steel substrate had about 90% of porosity and an average pore size of 600 μ m. It was dip-coated in the precursor solution four times, then hydrothermally treated at 80^∘, 110^∘ and 150^∘C for 6–48 h. The XRD patterns and SEM photographs revealed that faujasite-type zeolite was formed predominantly at a SiO₂concentration of 1.1 M, temperature of 110^∘C and duration of 24 h, with a product particle size of 2–5 μ m. At higher concentrations of the precursor solution, hydroxylsodalite becomes the major product rather than faujasite-type zeolite. The adherence strength of the zeolite grains deposited on the foamed stainless steel is higher in the in-situ crystallization method than when a conventional solution method is used. Thus, the in-situ crystallization method is concluded to be effective for preparing zeolite films even on metal substrates.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.