Sol–Gel Preparation of Thick PZN–PZT Film Using a Diol-Based Solution Containing Polyvinylpyrrolidone for Piezoelectric Applications

Dense and crack-free lead zinc niobate–lead zirconate titanate (PZN–PZT) films were deposited on silicon and glass substrates by spin coating using a sol containing propanediol and polyvinylpyrrolidone. Single-layer PZN–PZT films as thick as 0.80 μm were deposited by a single spin coating with successive heat treatments at 250° and 700°C. After heat treatment, the films were dense, crack free, and optically transparent. In addition, the crystallographic orientation of the thick film was controllable by adjusting the heat-treatment conditions. The ferroelectric properties of the (111)-oriented film were superior to those of the (100)-oriented film. On the other hand, the piezoelectric and dielectric properties of the (100)-oriented film were better than those of the (111)-oriented film. The piezoelectric coefficients ( d ₃₃) of the PZN–PZT films of 4.0-μm-thickness were 192 and 110 pC/N for the (100)-and (111)-oriented films, respectively.     

Preparation of Transparent Thick Films by Electrophoretic Sol-Gel Deposition Using Phenyltriethoxysilane-Derived Particles

Thick films were prepared on glass substrates coated with indium tin oxide (ITO) via electrophoretic deposition using sols that contained phenylsilsesquioxane (PhSiO_3/2) particles derived from phenyltriethoxysilane. The transparency of the thick PhSiO_3/2 films was significantly improved via heat treatment at temperatures >200°C. Scanning electron microscopy observation showed that the thick films changed in morphology, from aggregates of particles with several open spaces among the particles to a monolith with no open spaces after the heat treatment. Transparent films ~3 µm thick were obtained when the films were heat-treated at a temperature of 400°C for 2 h.     

Multilayer Actuator Composed of PZN–PZT and PZN–PZT/Ag Fabricated by Co-Extrusion Process

A multilayer ceramic actuator composed of piezoelectrically active Pb(Zn_1/3Nb_2/3)_0.2–Pb(Zr_0.5Ti_0.5)O_0.8 (PZN–PZT) layers and electrically conducting PZN–PZT/Ag layers was fabricated by the co-extrusion process. For the piezoelectric layers, PZN–PZT, which is sinterable at a low temperature (900°C), was used. For the conducting layers, a PZN–PZT/Ag composite, made by mixing silver particles with the PZN–PZT matrix, was employed. For the co-extrusion process, piezoelectric and conducting feedrods were made by mixing the PZN–PZT and PZN–PZT/Ag, respectively, with a thermoplastic polymer. The initial feedrods, which were composed of five 3 mm-thick PZN–PZT layers, two 1.5 mm-thick PZN–PZT layers, and six 1 mm-thick PZN–PZT/Ag layers, were co-extruded through a 24 mm × 2 mm reduction die at 105°C to produce continuous multilayered green sheets. The sheets were stacked, warm pressed, and sintered at 900°C for 4 h after binder burnout. The sintered multilayer actuator showed distinct layers without any reaction products or cracks at the interface. The thicknesses of the piezoelectric and conducting layers were about 200 and 70 μm, respectively. The displacement of the multilayer actuator, composed of 40 piezoelectric layers (with a total height of 10.8 mm), was about 10 μm at an applied voltage of 500 V.     

New Preparation Method for PZT Films Using Electrochemical Reduction

PZT perovskite films on stainless steel were prepared by electrochemical reduction in solutions containing TiO²⁺, ZrO²⁺, and Pb²⁺ ions. Heat treatment at temperatures higher than about 500°C was necessary for crystallization, because the as-deposited oxide films were amorphous. The deposited oxides consisted of a mixture of hydroxides and oxide produced by an increase of pH due to some electrochemical reduction reactions of NO₃⁻, H⁺, and H₂O on the electrode surface. The composition of the PZT films was easily controlled by the composition in solution during the electrolysis. The mechanism of the PZT precursor deposition is discussed.     

等离子体化学气相沉积法制备致密性超浸润纳米硅氟薄膜

以含氟丙烯酸酯功能单体和硅烷为原料、无水乙醇为溶剂、氩气为工艺气体,经等离子体化学气相沉积在表面绝缘阻抗(SIR)测试板和无尘布上制得硅氟薄膜.探讨了硅烷种类和用量、含氟单体用量对镀硅氟薄膜试件性能的影响.结果表明,采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH 570)、γ-氨丙基三乙氧基硅烷(KH 550)和乙烯基三...     

Oxidation Behavior of Ferritic Steel Alloy Coated with Highly Dense Conducting Ceramics by Aerosol Deposition

Conducting La_0.8Sr_0.2MnO₃ (LSM) ceramic layers with a thickness of ∼10 μm were deposited on ferritic stainless steel (SS) by aerosol deposition for use as an oxidation resistance coating layer in the metallic interconnects of solid oxide fuel cell. The microstructural evolution and electrical properties of the LSM-coated SS were observed. The coated layers were fairly dense without pores or cracks, and maintained good adhesion even after oxidation at 800°C for 1000 h in air atmosphere. The surface of the bare SS after heat treatment at 800°C for 1000 h was covered with Cr-containing oxide scales, and the electrical conductivity was sharply decreased. However, the LSM-coated SS alloy showed a surface microstructure with almost no chromic oxide formation and maintained good electrical conductivity after the heat treatment. Close observation of the interface between LSM and SS indicated the presence of ∼500-nm-thick Cr₂O₃ and MnCr₂O₄ spinel phase, which may have caused the long-time deterioration of the interconnector performance. The area-specific resistance of the LSM-coated alloy after heat treatment at 800°C for 1000 h was 10.4 mΩ·cm².     

Photonic Sintering of Aerosol Jet Printed Lead Zirconate Titanate (PZT) Thick Films

Lead Zirconate Titanate (PZT) is a commonly used piezoelectric material due to its high piezoelectric response. We demonstrate a new method of printing and sintering micro‐scale PZT films with low substrate temperature increase. Self‐prepared PZT ink was Aerosol‐Jet printed on stainless steel substrates. After drying for 2 h in vacuum at 200°C, the printed PZT films were divided into two groups. The first group was traditionally sintered, using a thermal process at 1000°C for 1 h in an Argon environment. The second group was photonically sintered using repetitive sub‐msec pulses of high intensity broad spectrum light in an atmospheric environment. The highest measured substrate temperature during photonic sintering was 170.7°C, enabling processing on low melting point substrates. Ferroelectric measurements were performed with a low‐frequency sinusoidal signal. The remanent polarization (P_r) and coercive field (E_c) for thermally sintered PZT film were 17.1 μC/cm² and 6.3 kV/cm, respectively. The photonically sintered film had 32.4 μC/cm² P_r and 6.7 kV/cm E_c. After poling the samples with 20 kV/cm electric field for 2 h at 150°C, the piezoelectric voltage constant (g₃₃) was measured for the two film groups yielding ?16.9 × 10^?3 (V·m)·N^?1 (thermally sintered) and ?17.9 × 10^?3 (V·m)·N^?1 (photonically sintered). Both factors indicate the PZT films were successfully sintered using both methods, with the photonically sintered material exhibiting superior electrical properties. To further validate photonic sintering of PZT on low melting point substrates, the process and measurements were repeated using a polyethylene terephthalate (PET) substrate. The measured P_r and E_c were 23.1 μC/cm² and 5.1 kV/cm, respectively. The g₃₃ was ?17.3 × 10^?3 (V·m)·N^?1. Photonic sintering of thick film PZT directly on low melting point substrates eliminates the need for complex layer transfer processes often associated with flexible PZT transducers.     

NiZnCu Ferrite Thick Film with Nano Scale Crystallites Formed by the Aerosol Deposition Method

This paper describes the magnetic properties of NiZnCu ferrite film deposited at room temperature by an aerosol deposition method (ADM). The thickness of the film was 6 μm and the deposition rate was estimated as 2 μm/min. The microstructure of as-deposited at room temperature films consists of randomly oriented nanocrystallites with a size of 20 nm. As-deposited and annealed films exhibited the following magnetic properties: intensity of magnetization M _s= 0.147 T (117 emu/cm³), coercivity H _c= 40.58 kA/m (510 Oe); and M _s= 0.3 T (250 emu/cm³), H _c= 14.95 kA/m (188 Oe), respectively.     

Dense Nanostructured Hydroxyapatite Coating on Titanium by Aerosol Deposition

In order to improve biocompatibility of Ti metal substrates, 1-μm-thick nanostructured hydroxyapatite (HAp) coatings were deposited on the substrates through aerosol deposition, which sprays HAp powder with an average particle size of 3.2 μm at room temperature in vacuum. The original HAp particles were fractured into nanoscale fragments to form highly dense coating during the deposition process. Density of the HAp coating was 98.5% theoretical density (TD). Transmission electron microscopy observation revealed that the as-deposited coating consisted of HAp crystallites with average grain size of 16.2 nm and amorphous phase. Tensile adhesion strength between the coating and the substrate was 30.5±1.2 MPa. Annealing up to 500°C in air increased crystallinity and grain size in the coating without any delamination or crack according to X-ray diffraction analysis and electron microscopy. MTS assay and alkaline phosphatase activity measurements with MC3T3-E1 preosteoblast cell revealed that the biocompatibility was greatly improved by postdeposition heat treatment at 400°C in air due to well-crystallized HAp with average grain size of 29.3 nm. However, further heat treatment at 500°C deteriorated biocompatibility due to rapid growth of HAp grains to average size of 99 nm. Cross section of the coating on a commercially available Ti dental implant revealed full coverage of the surface with HAp.     

Superhydrophilic Transparent Titania Films by Supersonic Aerosol Deposition

Photocatalytic and hydrophilic TiO₂ thin‐film applications include water purification, cancer therapy, solar energy conversion, self‐cleaning devices, and antifogging windows. We demonstrate superhydrophilicity of aerosol‐deposition (AD) TiO₂ films on a glass substrate without use of a carrier solvent, thereby removing the possibility of impurity contamination. AD films exhibit high visible light transmittance (greater than 80%) and superhydrophilicity (0° contact angle) with even minimal UV‐light irradiation exposure. This AD method represents a significant step toward the realization of economically viable, functional thin films for the aforementioned applications.     

Dielectric and Piezoelectric Properties of PZT Composite Thick Films with Variable Solution to Powder Ratios

The use of PZT films in sliver-mode high-frequency ultrasonic transducers applications requires thick, dense, and crack-free films with excellent piezoelectric and dielectric properties. In this work, PZT composite solutions were used to deposit PZT films >10 μm in thickness. It was found that the functional properties depend strongly on the mass ratio of PZT sol–gel solution to PZT powder in the composite solution. Both the remanent polarization, P _r, and transverse piezoelectric coefficient, e _{31, f} , increase with increasing proportion of the sol–gel solution in the precursor. Films prepared using a solution-to-powder mass ratio of 0.5 have a remanent polarization of 8 μC/cm², a dielectric constant of 450 (at 1 kHz), and e _{31, f} =−2.8 C/m². Increasing the solution-to-powder mass ratio to 6, the films were found to have remanent polarizations as large as 37 μC/cm², a dielectric constant of 1250 (at 1 kHz) and e _{31, f} =−5.8 C/m².     

Aerosol Deposition of Ceramic Thick Films at Room Temperature: Densification Mechanism of Ceramic Layers

A novel method for depositing ceramic thick films by aerosol deposition (AD) is presented. Submicron ceramics particles are accelerated by gas flow up to 100–500 m/s and then impacted on a substrate, to form a dense, uniform and hard ceramic layer at room temperature. However, actual deposition mechanism has not been clarified yet. To clarify densification mechanism during AD, a mixed aerosol of α-Al₂O₃ and Pb(Zr, Ti)O₃ powder was deposited to form a composite layer in this study. The cross-section of the layer was observed by HR-TEM to investigate the densification and bonding mechanism of ceramic particles. As a result, a plastic deformation of starting ceramic particles at room temperature was observed.     

Stress Modulation and Ferroelectric Properties of Nanograined PbTiO3 Thick Films on the Different Substrates Fabricated by Aerosol Deposition

Nanograined PbTiO₃ (PT) thick films were deposited on Si, yttria‐stabilized zirconia (YSZ), and Ni substrates using an aerosol deposition (AD) method at room temperature. The AD PT thick films on each different substrate were annealed at 500°C and 700°C for 1 h to increase the crystallinity. The stresses in the PT film were modulated by controlling the difference in the coefficient of thermal expansion (CTE) between the films and substrates during the thermal annealing process. The morphology of the AD PT films was examined from the polycrystalline dense structure (thickness ~8 μm), and the changes in the crystallographic phase, in‐plane stresses, and ferroelectric properties in annealed films were investigated. In‐plane stress analysis showed that the PT films annealed at 500°C and 700°C on each substrate exhibited compressive stress. Owing to the effects of compressive stress in the PT film, the film showed less tetragonality (c/a ratio) and enhanced ferroelectric behaviors. The change in the polarization–electric field (P–E) hysteresis loop of the PT films was explained by the stress induced from CTE mismatch between the films and substrates.     

Deposition of Multifunctional Titania Ceramic Films by Aerosol Routes

Aerosol coating processes were developed to deposit titania ceramic films onto steel and silica substrates. In situ light-scattering measurements were used to understand the deposition mechanisms in different system configurations. The conditions that were necessary to obtain uniform, nonporous, and well-adhered titania films on steel substrates were established. The as-coated films had excellent anticorrosion characteristics at room temperature, as established by the standard salt-fog test. Film crystallinity and morphology were examined using X-ray diffractometry and scanning electron microscopy; these analysis methods revealed an oriented, nanocrystalline anatase phase. Film composition was established, as a function of film thickness, using Auger electron spectroscopy and was confirmed to be stoichiometric (Ti:O = 1:2). The optical band gap and optical phonons of the deposited films were probed using spectrophotometry and Raman scattering, respectively; these analysis methods revealed a blue shift of the gap, relative to bulk anatase, and a localization of carriers in the nanometer-sized crystallites.     

应用电泳沉积技术制备钛酸钡铁电陶瓷薄膜

采用电泳沉积技术在Pt电极基片上制备BaTiO3铁电陶瓷薄膜，探讨了电泳沉积过程中的控制因素（悬浮液体系，电场强度，料浆浓度，沉积时间等）对成膜性能的影响，并对薄膜材料的结构，性能进行了表征，实验结果表明；在1050℃（2h)的烧成温度下，经重复沉积一烧结2-3次可得到基本无缺陷的BaTiO3陶瓷薄膜，测量频率在1kHz，测量频率在1kHz时，室温（23℃）下的介电常数ε=2300，介电损耗tanδ=0.2。     

Growth of Highly Conformal TiCx Films Using Atomic Layer Deposition Technique

TiC_x films were deposited by atomic layer deposition using tetrakis–neopentyl–titanium [Ti(CH₂C(CH₃)₃)₄] and H₂ plasma as the precursor and reactant, respectively. The growth of the rock‐salt–structured TiC_x films was confirmed by X‐ray and electron diffraction. The C‐to‐Ti ratio determined by Rutherford backscattering spectrometry was ~0.52 and the film resistivity was as low as ~600 μΩ cm with a high density of 4.41 g/cm³. The step coverage was approximately 90% over the trench structure (top opening diameter of 25 nm) with an aspect ratio of ~4.5.     

Micropatterning on Methylsilsesquioxane– Phenylsilsesquioxane Thick Films by the Sol–Gel Method

Prismatic patterns with a pitch of 30 μm and a slant height of 30 μm were embossed successfully in 70:30 (in mol%) methylsilsesequioxane:phenylsilsesqeioxane (MeSiO_3/2–PhSiO_3/2) thick films on glass substrates by laminating an organic polymer sheet as a stamper with the patterns against the films. The embossed shape of the prismatic patterns precisely agreed with the negative shape of those of the stamper that was used. The resultant MeSiO_3/2–PhSiO_3/2 films were transparent, and the refractive index of the films was adjusted to 1.51, to match that of the glass substrate.     

Preparation of Highly Dispersed Ultrafine Barium Titanate Powder by Using Microbial-Derived Surfactant

To uniformly disperse ultrafine BaTiO₃ particles with a stoichiometric composition and several tens of nanometers in diameter to primary particles during the sol–gel synthesis process, a new aqueous surfactant with a high hydrophilic group density and special cis-structure was prepared from a microbial product and added to solution before the sol–gel synthesis reaction. Because of the rapid formation of large and porous aggregates which were 30–50 μm in diameter in suspension without addition of this unique structural surfactant, the prepared ultrafine BaTiO₃ particles caused rapid sedimentation in suspension. The addition of the surfactant in the range of 7.1 wt% for the synthesized BaTiO₃ particles made it possible to decrease the size of the aggregates in suspension as well as the sedimentation velocity while maintaining the stoichiometric composition. The optimum additive content to obtain the minimum aggregate size of about 100–200 nm in diameter and the highest dispersion stability in suspension while maintaining the stoichiometric composition of prepared ultrafine BaTiO₃ particles without other phases was determined at about 7.1 wt%. Because the excess addition of this surfactant at more than 8.5 wt% inhibited the uniform synthesis of BaTiO₃ particles, an amorphous phase with a highly specific surface area and a BaCO₃ phase formed in the synthesized particles.     

Micropatterning of Transparent Poly(Benzylsilsesquioxane) Thick Films Prepared by the Electrophoretic Sol–Gel Deposition Process Using a Hydrophobic–Hydrophilic-Patterned Surface

Poly(benzylsilsesquioxane) (BnSiO_3/2) particles show glass transition behavior, and the particles become a supercooled liquid when they are heated at temperatures above the glass transition temperature. Contact angles of BnSiO_3/2 molten liquid on the hydrophobic surface with fluoroalkylsilane and hydrophilic surface with silica were found to be around 77° and 12°, respectively. Using the difference in wettability for BnSiO_3/2 molten liquid between the hydrophobic and hydrophilic surfaces, micropatterns of transparent BnSiO_3/2-thick films were formed by the electrophoretic deposition of BnSiO_3/2 particles on indium tin oxide substrates with hydrophobic–hydrophilic patterns and subsequent heating above the glass transition temperature.     

Lead Zirconate Titanate Thin Films by Aerosol Plasma Deposition: Microstructure Analysis

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) thin films were grown on silicon 〈100〉 substrate by aerosol plasma deposition (APD) using solid-state-reacted powder containing donor oxide Nb₂O₅ when keeping the substrate at room temperature and 200°C. Crystalline phases of the deposited films have been analyzed via X-ray diffractometry (XRD), and microstructure via scanning and transmission electron microscopy (SEM and TEM). Cross-sectional TEM revealed that the microstructure comprised several layers including the deposited PZT film and the platinum-electrode-and-titanium-buffered layers on SiO₂–Si substrate. The Pt-electrode layer contained (111)_Pt twinned columnar grains with a slight misorientation and forming low-angle grain boundaries among them. The PZT layer contained randomly oriented grains embedded in an amorphous matrix. Some of the PZT grains, oriented with the zone axis Z = [[Twomacr]11]_PZT parallel to Z = [111]_Pt, were grown epitaxially on the Pt layer by sharing the (111)_PZT plane with the (111)_Pt twinned columnar Pt crystals. However, the existence of such an orientation relationship was confined to several nanosize grains at and near the PZT-Pt interface, and no gross film texture has been developed. An amorphous grain boundary phase, generated by pressure-induced amorphisation (PIA) in the solid state, was identified by high-resolution imaging. Its presence is taken to account for the densification of the PZT thin films via a sintering mechanism involving an amorphous phase on deposition at 25° and 200°C.