Effect of Mechanical Constraint on Domain Reorientation in Predominantly {111}‐Textured Lead Zirconate Titanate Films

Ferroelectric/ferroelastic domain reorientation was measured in 2.0 μm thick tetragonal {111}‐textured PbZr_0.30Ti_0.70O₃ thin films using synchrotron X‐ray diffraction (XRD). Lattice strain from the peak shift in the 111 Bragg reflection and domain reorientation were quantified as a function of applied electric field amplitude. Domain reorientation was quantified through the intensity exchange between the 112 and 211 Bragg reflections. Results from three different film types are reported: dense films that are clamped to the substrate (as‐processed), dense films that are partially released from the substrate, and films with 3% volume porosity. The highest amount of domain reorientation is observed in grains that are misoriented with respect to the {111} preferred (domain engineered) orientation. Relative to the clamped films, films that were released from the substrate or had porosity exhibited neither significant enhancement in domain reorientation nor in 111 lattice strain. In contrast, similar experiments on {100}‐textured and randomly oriented films showed significant enhancement in domain reorientation in released and porous films. Therefore, {111}‐textured films are less susceptible to changes in properties due to mechanical constraints because there is overall less domain reorientation in {111} films than in {100} films.     

Synthesis and Microstructure of Highly Oriented Lead Titanate Thin Films Prepared by a Sol-Gel Method

Thin films of PbTiO₃ were deposited on fused silica, resistor-grade alumina, and single-crystal (100) MgO by a sol–gel processing method. Whereas the films deposited on silica and alumina substrates were randomly oriented and polycrystalline, highly {100} oriented PbTiO₃ films were grown on the MgO single crystals. The perovskite-type structure was observed with films deposited on the single-crystal MgO and annealed at temperatures as low as 470°C, whereas a pyrochlore-type strcuture was observed with films on fused silica and alumina processed in a similar manner. All films heat-treated at temperatures in excess of 570°C showed significant formation of a second PbTi₃O₇ phase. The films were characterized by electron microscopy and glancing-incidence-angle X-ray diffraction.     

钽镁酸钡缓冲层对锆钛酸铅铁电薄膜性能的影响

采用溶胶–凝胶工艺在Pt/Ti/Si O2/Si基片上,通过引入钽镁酸钡[Ba(Mg1/3Ta2/3)O3,BMT]缓冲层,制备了锆钛酸铅[Pb(Zr0.52Ti0.48)O3,PZT]铁电薄膜。研究了BMT缓冲层对PZT铁电薄膜结晶和性能的影响。结果表明:引入BMT缓冲层利于PZT薄膜的生长;PZT薄膜具有钙钛矿结构,且没有裂纹、结晶良好、致密性好;缓冲层的厚度对PZT铁电薄膜的微观结构和铁电性能有重要影响。随BMT缓冲层厚度增加,PZT晶粒增大,介电损耗tanδ逐渐减少,介电常数εr和剩余极化强度Pr先增大后减少,矫顽场Ec先减少后增大。当BMT缓冲层厚约为10 nm时,PZT薄膜具有最优的铁电性能:εr=1 850,Pr=20.2μC/cm2,Ec=43.9 k V/mm。这与BMT与PZT具有相似的晶格常数、较小的晶格失配度和相近的禁带宽度有关。     

Carbon Monoxide Oxidation on Copper Oxide Thin Films Supported on Corrugated Cerium Dioxide {111} and {001} Surfaces

Thin films of CeO₂with and without a thin layer of copper oxide were prepared by rf magnetron sputtering on surfaces of α-Al₂O₃(sapphire) substrates. Careful characterisation of the surfaces was performed down to the atomic level using high-resolution electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Surprisingly, the as-deposited, corrugated ceria surfaces, nominally (001), consist exclusively of {111}-type lattice planes, but, upon annealing at 800°C, a well-defined portion of (001) surfaces are formed. Oxidation of carbon monoxide to carbon dioxide was studied, having the prepared films in a stirred batch reactor. A batch reactor was chosen so that the conversion over the small sample surface area (ca 10⁻⁴m²) could be monitored as a function of the reaction time. The activity of copper oxide on annealed ceria surfaces is markedly higher than on nonannealed surfaces, indicating a favourable synergetic effect between the ceria (001) surface and the copper oxide phase.     

Hydrothermal Synthesis of Ferroelectric Mixed Potassium Niobate–Lead Titanate Nanoparticles

Potassium niobate–lead titanate solid‐solution nanoparticles have been synthesized using a new hydrothermal method. The key step is an in situ acid–base exothermic reaction with a large excess of KOH, generating an amorphous precipitated gel. This gel, when crystallized in an autoclave for 2 h at 190°C, produces a mixed perovskite solid solution with [KNbO₃]_0.8–[PbTiO₃]_0.2 (KNPT) composition, and parallelepiped particles rang in size from a few tens to a few hundreds of nanometer in length. This study proves that the pure perovskite phase can be obtained in spite of the different solubilities of the reactive cations in an ethanol–water solution. Dielectric measurements show that KNPT ceramic with a grain size of 50 nm is ferroelectric at room temperature. In addition, ceramics sintered at 950°C have an average grain size of 500 nm, and exhibit a maximum permittivity of 2100 at 1 kHz near T_C = 510 K and a remanent polarization P_r = 12 μC/cm²     

Preparation and Characterization of Sol—Gel-Derived Lead Magnesium Niobium Titanate Thin Films with Pure Perovskite Phase and Lead Oxide Cover Coat

A sol–gel-derived Pb(Mg_1/3Nb_2/3)_0.7Ti_0.3O₃ (PMNT) thin film was prepared using spin coating and a PbO cover coat technique. The amount of lead excess in the precursor solution had significant effects on the phase development and microstructure of the PMNT film. The PbO cover coat proved to be effective on suppressing the formation of pyrochlore phases. PMNT thin films with a pure perovskite structure were obtained by adding 30 mol% excess lead in the precursor solution and coating the PbO layer on the top of the film. The remnant polarization ( P _r), the dielectric constant (ɛ_r), and the dissipation factor (tan δ) of these thin films, which had a thickness of 150 nm, were determined to be 9 μC/cm², 1370, and 0.031, respectively.     

铌镁酸钡缓冲层对锆钛酸铅薄膜漏电流的抑制

将铌镁酸钡(Ba(Mg1/3Nb2/3)O3,BMN)作为缓冲层,通过溶胶-凝胶法制备了锆钛酸铅(Pb(Zr0.52Ti0.48)O3,PZT)铁电薄膜.探究BMN缓冲层对PZT铁电薄膜介电、铁电性能影响.研究发现:BMN缓冲层不仅可以改善PZT薄膜晶化生长,同时阻碍了PZT与Pt的互扩散而降低了漏电流.由于对漏电流的抑制作用,适当厚度BMN缓冲层的引入可改善PZT的铁电性能,但随着缓冲层厚度的增加,由于其分压作用,复合膜铁电性减弱.当厚度为10 nm时,薄膜的综合性能最好:介电常数εr=1612.03,介电损耗tanδ=0.024,剩余极化值Pr=31.65 μC/cm2,矫顽场Ec=71.5 kV/cm,漏电流密度J=4.4×10-6 A/cm2.     

Growth of c‐Axis‐Oriented BiCuSeO Thin Films Directly on Si Wafers

Single‐phase, c‐axis‐oriented BiCuSeO thin films have been directly grown on the commercial silicon (001) wafers without any surface pretreatment by using pulsed laser deposition. X‐ray diffraction pole figure confirms that the film does not have any ab‐plane texture, whereas cross‐sectional transmission electron microscopy shows good crystallinity of the film even if there exists an amorphous native oxide layer on the wafers surface. At room temperature, the resistivity of the film is about 14 mΩ cm, which is much lower than that reported for corresponding single crystals as well as polycrystalline bulks. This work demonstrates the possibility of using the available state‐of‐the‐art silicon processing techniques to create BiCuSeO‐based thin‐film thermoelectric devices.     

Characterization of Chemical Solution Deposition-Derived Lead Hafnate Titanate Thin Films

In this paper, lead hafnate titanate (PHT) was derived by chemical solution deposition (CSD) and characterized as a thin film material. The thin films were tested for the usage as a ferroelectric thin film in view of Ferroelectric Random Access Memory (FRAM) devices and compared with an equivalent lead zirconate titanate (PZT) thin film, which was prepared under the same conditions. After determining the thickness and the morphology of the PHT films, electronic measurements were performed to investigate this material as a promising candidate in view of FRAM applications due to failure mechanisms like fatigue and imprint.     

Longitudinal Electrooptic Effects and Photosensitivities of Lead Zirconate Titanate Thin Films

The feasibility of storing and reading high-density optical information in lead zirconate titanate (PZT) and in lead lanthanum zirconate titanate (PLZT) thin films depends on both the longitudinal electrooptic coefficients and the photosensitivities of the films. This paper describes the methods used to measure the longitudinal electrooptic effects and the photosensitivities of the films. The results of these measurements were used to evaluate a longitudinal quadratic electrooptic R coefficient, a longitudinal linear electrooptic r_c coefficient, and the wavelength dependence of the photosensitivity of a composition of PZT polycrystalline thin film. The longitudinal electrooptic R and r_c coefficients are about an order of magnitude less than the transverse R and r_c coefficients of bulk ceramics of similar compositions. This is attributed to clamping of the film by the rigid substrate. The large birefringence of the films after poling (>10⁻²) suggests that the optic axes of the films are preferentially oriented normal to the film surface. The techniques used in this paper for evaluating the photosensitivities of thin films are based on measuring the photocurrent generated rather than the reduction in coercive voltage (as in bulk ceramics) when the film is exposed to light. The thin film photosensitivities appear to be significantly higher than those of bulk ceramics of similar compositions. The high photosensitivities coupled with the substantial longitudinal electrooptic coefficients combine to establish the feasibility of using PZT or PLZT thin films for optical information storage applications.     

Microstructure of Solution-Processed Lead Zirconate Titanate (PZT) Thin Films

Lead zirconate titanate (PZT) thin films with a composition near the morphotropic phase boundary (Zr/Ti = 53/47) were fabricated by spin deposition of an alkoxide-derived solution and annealed at 650°C for 30 min. A complex microstructure is observed in which micrometer-scale rosettes of the desired perovskite phase are surrounded by nanocrystalline (10 to 15 nm) grains of pyrochlore structure. Transmission electron microscopy (TEM) demonstrates that the perovskite rosettes—features of approximately circular cross section which grow rapidly within the confined conditions of the thin film—are single crystals despite being highly porous. Pockets of lead-deficient pyrochlore extend throughout the thickness of the film. The only effects of Nb (2%) doping on the microstructure are to increase the fraction of the perovskite phase and the perovskite grain size. Despite the highly irregular shape of the perovskite particles and the presence of some pyrochlore, reasonable ferroelectric properties are measured (spontaneous polarization P _s∼ 0.2 C/m²).     

Properties of Lead Zirconate Titanate Thin Films Prepared Using a Triol Sol–Gel Route

Microstructure and phase development during the thermal decomposition of sol–gel precursor coatings of PbZr_0.53Ti_0.47O₃ on platinized silicon substrates have been investigated for a triol sol–gel route. The single-layer, 0.4 μm PZT films were heated from below the substrate, over the temperature range 350–600°C, using a calibrated hot plate. The first crystalline phase to appear was a PbPt₃ intermetallic phase at the Pt/PZT interface. Although perovskite PZT formed at ca. 500°C, heating at higher temperatures, for example 550°C for 30 min, was required to develop ferroelectric hysteresis loops. However, the rather low value of remanent polarization, P _r= 11 μC·cm⁻², was consistent with incomplete crystallization at 550°C. The values of remanent polarization increased with increasing processing temperatures, reaching 21 μC·cm⁻² for samples heated at 600°C, with a corresponding E _c value of 57 kV·cm⁻¹. Distinctive spherical precipitates up to ca. 50 nm in size have been identified by TEM in the lower portions of otherwise amorphous coatings, after heating at around 350–400°C. Although their precise composition could not be identified, they were mostly Pb-rich, and it is speculated that they form due to reduction of some of the lead(II) acetate starting reagent, to atomic Pb during the early stages of thermal decomposition of the organic components of the gel; it is possible that subsequent reactions occur to form lead oxides or carbonates. High levels of porosity were present in many of the fully crystallized films. The possible reasons for this are discussed.     

Preparation and Electrical Properties of Lanthanum-Doped Lead Titanate Thin Films by Sol–Gel Processing

Lanthanum-doped lead titanate thin films have been prepared by sol–gel processing. These studies reveal the structural and electrical properties of 18 mol% La-doped PbTiO₃ thin films to be dependent on the annealing conditions. With appropriate annealing conditions, a relative dielectric constant of about 900 was obtained, comparable to the bulk composition.     

Effects of Thickness on Piezoelectric Properties of Highly Oriented Lead Zirconate Titanate Films

Lead zirconate titanate (PZT) films were deposited on platinized silicon substrates by spin coating using PZT sols containing polyvinylpyrrolidone (PVP) as an additive. PZT films with a 60/40 composition and a thickness of up to 8 μm were fabricated by repeating the deposition process 15 times on highly oriented (100) and (111) seed layers with the same composition. The films grew well in the direction of the seed layers and had a uniform and smooth surface without any cracks. As the thickness of the films increased, the grain size remained almost the same, but the effective d ₃₃ value increased steadily. The thickness dependence of the piezoelectric properties was attributed to the residual stress of the films.     

Low‐Cost,Damage‐Free Patterning of Lead Zirconate Titanate Films

The ability to pattern piezoelectric thin films without damage is crucial for the development of microelectromechanical systems. Direct patterning of complex oxides through microcontact printing was explored as an alternative to subtractive patterning. This process utilized an elastomeric stamp to transfer a chemical solution precursor of a piezoelectric material onto a substrate in a desired pattern. Polyurethane‐based stamps improved wetting of polar solutions on the stamp. This allowed for high‐fidelity patterning over multiple stamping cycles. Microcontact printing deposited patterned PbZr_0.52Ti_0.48O₃ layers from 0.1 to 1 μm in thickness. The lateral feature sizes attained varied from 5 to 500 μm. Upon crystallization at 700°C, the features formed phase‐pure perovskite PZT. The printed features had comparable electrical and electromechanical properties to those of continuous PZT films of similar thicknesses. For example, 1 μm thick PZT features had a permittivity of 1050 and a loss tangent of 0.02 at 10 kHz. The remanent polarization was 30 μC/cm², and the coercive field was 45 kV/cm. The piezoelectric coefficient e_31,f was ?7 C/m². These values indicated that the microcontact printing process did not adversely affect the PZT crystallization or properties for the thicknesses explored in this work.     

Synthesis of Highly Oriented Lead Zirconate–Lead Titanate Film Using Metallo-organics

Crack-free Pb(Zr,Ti)O₃ (PZT) thin films with preferred orientation were prepared successfully on MgO (100), SrTiO₃ (100), and Pt/Ti/SiO₂/Si substrates from metal alkoxide solutions. Calcination of precursor films in a H₂O─-O₂ gas mixture was found to be effective not only for low-temperature crystallization of perovskite PZT, but also for obtaining the preferred orientation of PZT films. Single-phase PZT films with high preferred orientation were synthesized on MgO (100) and Pt/Ti/SiO₂/Si substrates at 550° and 600°C for 2 h, respectively. The PZT film on the Pt/Ti/SiO₂/Si substrate showed a permittivity of 520, tan δ of 0.03, a remanent polarization of 24 μC/cm², and a coercive field of 54 kV/cm.     

Strong Near‐Infrared Photoluminescence Emission of (003)‐Oriented MgTiO3 Thin Films

In this study, ilmenite‐MgTiO₃ films were sputtered on p‐type Si(111) substrates and the extrinsic effects, such as grain size, crystallinity, and orientation of photoluminescence (PL) properties of the films are discussed. To reduce the effect of oxygen vacancies (act as shallow defects) on PL emissions in the films, oxygen (O₂) was introduced as the sputtering gas and the excitation light source (λ = 532 nm) which has a corresponding energy (hν = 2.33 eV) below the shallow defect states was used. In this study, intense near‐infrared (NIR) PL emission centered at 810.1 nm at room temperature can be observed when the MgTiO₃ thin films exhibit the preferred (003)‐orientation and accompanied by the presence of hexagon‐shaped grains. In this study, the experiment results reveal that the NIR emission intensity of MgTiO₃ films highly depend on crystal orientation and/or grain morphology.     

Processing and Sol Chemistry of a Triol-Based Sol–Gel Route for Preparing Lead Zirconate Titanate Thin Films

A triol-based sol–gel system has been developed for the fabrication of thin films of lead zirconate titanate (PZT). Starting reagents were lead acetate, zirconium and titanium isopropoxides, acetylacetone, and 1,1,1-tris(hydroxymethyl)ethane (THOME), with 2-methoxyethanol (MOE) being used to dilute the sols for spin coating purposes. Preliminary characterization by NMR spectroscopy suggested that the gels consisted of the metal ions and bound THOME, acetylacetonate, and acetate residues, with some possible M–O–M bridges. Uncracked 0.4 μm single-layer PZT films of nominal composition PbZr_0.53Ti_0.47O₃ were prepared on platinized substrates. Dielectric and ferroelectric properties were determined for samples made from sols containing 10 and 15 mol% excess lead acetate. Improved values were obtained for samples made from sols containing the higher excess; these exhibited a remanent polarization of 34 μC·cm⁻¹, a coercive field of 54 kV·cm⁻¹, and a relative permittivity of 1000.     

Effect of Switching Atmospheric Conditions during Crystallization on the Phase Evolution of Solution‐Derived Lead Zirconate Titanate Thin Films

The crystallization behavior of solution‐derived lead zirconate titanate (PZT) thin films in different atmospheric environments was studied using in situ X‐ray diffraction. The stability of the transient intermetallic Pt₃Pb phase and perovskite PZT is dependent on oxygen partial pressure during crystallization. Based on the relationship between oxygen partial pressure and the resultant phase stability of intermediate phases, a new route to produce PZT thin films was developed. The new route involves switching atmospheres during crystallization and is shown to mitigate the formation of the transient intermetallic Pt₃Pb phase and to promote the perovskite PZT phase. The route evidences a new and significant variable controlling film synthesis and film microstructure.     

Effect of Lead Zirconate Titanate Seeds on PtxPb Formation during the Pyrolysis of Lead Zirconate Titanate Thin Films

Lead zirconate titanate (PZT) thin films were prepared on platinized silicon substrates by dip-coating using a modified diol-based sol–gel route without and with up to 5 mol% PZT nanometric seeds dispersed in the precursor sol. A metastable intermetallic Pt _x Pb phase formed at the early stages of heat treatment. XRD, TEM, and RBS revealed that the thickness and stoichiometry of the Pt _x Pb layer varied with the concentration of seeds and heat treatment of the films. The relation of the Pt _x Pb layer to the final crystalline texture of the PZT thin films is reported and discussed.