Influence of PbO content on the dielectric failure of Nb-doped {100}-oriented lead zirconate titanate films

A series of niobium-doped, {100} textured, “gradient free,” lead zirconate titanate (PNZT) films with different PbO contents were fabricated by the chemical solution deposition method. The films’ PbO content was controlled by changing the average PbO content in the solution from 114.7 to 117 at.%. During the dielectric breakdown process of 1.5 μm thick PNZT films with Pt top and bottom electrodes, two phenomena were observed: cracking and thermal breakdown of the piezoelectric film. At 150°C, with an applied 400 kV/cm electric field, the crack density of PNZT films induced by electromechanical failure increased from 0.060/μm to 0.090/μm as the solution's PbO content increased from 114.7% to 117%. In addition, the films showed higher crack densities and more frequent thermal breakdown events when the electric field was oriented downward (from top to bottom electrode) compared with an upward oriented electric field (from bottom to top electrode). The films with higher PbO content had a lower breakdown strength. Also, all films showed lower breakdown strength when measured in the field down direction. The Schottky barrier height (SBH) decreased from 0.82 ± 0.06 to 0.68 ± 0.04 eV in the field up direction measurement as the PbO content increased. The SBH value did not show significant change in the field down direction measurement. This suggests that the asymmetry in the film/electrode interfaces is a function of the PbO content in the original solution.     

Effect of the synthesis conditions on the properties of polycrystalline films of lead zirconate titanate of nonstoichiometric composition

The model representations of the formation of the internal fields at the grain boundaries in polycrystalline lead zirconate titanate (PZT) films are discussed. According to the model proposed, the local distortion of the stoichiometric composition of the PZT films caused by the segregation of the oxygen and lead ions from the bulk PZT grains towards their boundaries during high-temperature annealing gives rise to electrical double layers near the grain boundaries and fixes the polarization in these areas. As a result, the ferroelectric polarization that can be switched by the electric field in polycrystalline PZT films decreases.     

Thickness‐dependent domain wall reorientation in 70/30 lead magnesium niobate‐ lead titanate thin films

Continued reduction in length scales associated with many ferroelectric film‐based technologies is contingent on retaining the functional properties as the film thickness is reduced. Epitaxial and polycrystalline lead magnesium niobate‐lead titanate (70PMN‐30PT) thin films were studied over the thickness range of 100‐350 nm for the relative contributions to property thickness dependence from interfacial and grain‐boundary low permittivity layers. Epitaxial PMN‐PT films were grown on SrRuO₃/(001)SrTiO₃, while polycrystalline films with {001}‐Lotgering factors >0.96 were grown on Pt/TiO₂/SiO₂/Si substrates via chemical solution deposition. Both film types exhibited similar relative permittivities of ~300 at high fields at all measured thicknesses with highly crystalline electrode/dielectric interfaces. These results, with the DC‐biased and temperature‐dependent dielectric characterization, suggest irreversible domain wall mobility is the major contributor to the overall dielectric response and its thickness dependence. In epitaxial films, the irreversible Rayleigh coefficients reduced 85% upon decreasing thickness from 350 to 100 nm. The temperature at which a peak in the relative permittivity is observed was the only measured small signal quantity which was more thickness‐dependent in polycrystalline than epitaxial films. This is attributed to the relaxor nature present in the films, potentially stabilized by defect concentrations, and/or chemical inhomogeneity. Finally, the effective interfacial layers are found to contribute to the measured thickness dependence in the longitudinal piezoelectric coefficient.     

DC Electric Field‐Enhanced Grain‐Boundary Mobility in Magnesium Aluminate During Annealing

Magnesium aluminate spinel was sintered and annealed at 1300°C under an applied 1000 V/cm DC electric field. The experiment was designed such that current could be removed as a variable and just the effect of a noncontact electric field was studied. Enhanced grain growth was observed for both samples that were sintered or annealed after densification in the presence of an electric field. Grain‐boundary character distributions revealed that no microstructural changes were induced due to the field. However, the electric field was found to enhance the kinetic movement of cations within the lattice. Energy‐loss spectroscopy experiments revealed cation segregation resulting in regions of Mg‐rich and Al‐rich layers adjacent the grain‐boundary cores. The defects generated during segregation supported the generation of a space charge gradient radiating from the grain‐boundary core out into the bulk, which was significantly affected by the applied field. The interaction between the field and space charges effectively reduced the activation energy for cation movement across boundaries thereby enhanced grain‐boundary mobility and resultant grain growth.     

Anodization of Al–Nd alloy films in nonaqueous electrolyte solutions for TFT-LCD application

The anodization behavior of Al–Nd alloys in nonaqueous electrolyte solutions and the electronic properties of the resultant anodic oxide films were studied for TFT-LCD application. Sputtered Al–Nd alloy films on glass substrates were anodized at 25 °C and 1 mA cm⁻² up to 100 V in ethylene glycol–water solutions containing 10 wt.% ammonium tartrate or salicylate to give uniform and flat oxide films. The incorporation of organic components into the anodic oxide films from the electrolyte solutions has lowered the relative permittivity and increased the breakdown electric field of the oxide films. This was performed by decreasing the water content in the electrolyte solutions. The tartrate solution caused higher carbon incorporation than the salicylate counterpart at the same water concentrations, giving lower relative permittivity, and higher forward breakdown electric field. The AlO stretching frequency of the oxide films decreased slightly as the amount of incorporated organic moieties increased. Nd was uniformly distributed in the oxide films and an increase in the Nd content was likely to increase both the relative permittivity and the forward breakdown electric field without any apparent change in the anodization behavior.     

Flash sintering of lead zirconate titanate (PZT) ceramics: Influence of electrical field and current limit on densification and grain growth

Flash sintering of lead zirconate titanate ceramics were investigated under DC electric fields ranging from 300 to 600?V/cm. The onset temperature for flash sintering significantly decreased with the electrical field to a lower limit of furnace temperature of 538?°C at 600?V/cm. The retardation of grain growth was observed, and the grain size decreased with increasing the electrical field. The current limit had a great influence on the density and grain size of specimen. During the flash sintering process, power dissipation first rose abruptly to a maximum value, then declined sharply to a steady state. Meanwhile, optical glow of specimen was observed. Using black body radiation model, the actual specimen temperature was estimated, which was too low to obtain the full dense ceramics in 30?s. It was suggested that Joule heating, ultra-high heating rate and high concentrations of defects were responsible for flash sintering of PZT ceramics.     

Phase transitions of antiferroelectric lead zirconate thin films in high electric field

Phase transitions in antiferroelectric lead zirconate thin films were studied at room temperature and at 77 K. The lead zirconate films were prepared on Pt coated Si substrates by a reactive magnetron co-sputtering mthod followed by a rapid thermal annealing process at 700 °C. An electric field induced antiferroelectric — ferroelectric phase transition was observed at room temperature with a maximum polarization value of 70 μC/cm². The average field required to induce the ferroelectric state and that for the reversion to the antiferroelectric state were 294 kV/cm and 179 kV/cm respectively. At 77 K a metastable ferroelectric — ferroelectric transition was observed with a maximum polarization of 58 μC/cm². These transitions were found to be coincident with those of lead zirconate single crystals.     

Effects of Excess Bismuth Content in Precursor Solutions on Ferroelectric Properties of BiFeO3 Thin Films Prepared by a Chemical Solution Deposition

Cr-substituted BiFeO₃ (BFCr) thin films prepared from precursor solutions with stoichiometric composition and various excess Bi contents ranged from 5 to 20 mol% were fabricated on Pt/TiO₂/SiO₂/Si(100) substrates by a chemical solution deposition method, and the effects of excess Bi content in precursor solutions on the ferroelectric properties of the as-deposited BFCr thin films were studied. It was found that the BFCr thin film prepared from precursor solution with excess Bi content of 5 mol% exhibited the best dielectric constant-frequency and polarization-electric field characteristics. In detail, its dielectric constant is 158 at frequency of 100 kHz and remnant polarization (P_r) value is 49 μ C/cm² at electric field of 600 kV/cm.     

Effect of casting solvent on characteristics of hexanoyl chitosan/polylactide blend films

Blend films of hexanoyl chitosan (H‐chitosan) and polylactide (PLA) were cast from corresponding blend solutions in chloroform, dichloromethane, or tetrahydrofuran. Thermal degradation behavior of the as‐prepared blend films was intermediate to those of the pure components and no significant effect from the type of the casting solvent was observed. All of the blend films exhibited one composition‐dependent glass transition temperature, but the results only suggested partial miscibility of the components in the amorphous phase at “low” contents of H‐chitosan. As revealed by solvent etching technique, the as‐prepared blend films prepared from the blend solutions in chloroform and dichloromethane showed extensive phase separation of the two components, with the minor phase forming into discrete domains throughout the matrix. Both thermal and X‐ray analyses showed that the apparent degree of crystallinity of the PLA component in the blends decreased monotonically with increasing H‐chitosan content and the choice of the casting solvent did not have an effect on the structure of PLA crystals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

电刷镀纳米晶镍镀层

采用电刷镀的方法,通过在刷镀溶液中加入不同类型及含量的表面活性剂,在铁基体上制备出了纳米晶镍镀层。通过原子力显微镜、扫描电子显微镜观察,分析纳米晶镍镀层的二维和三维表面形貌。利用X-射线衍射仪,估算纳米晶镍镀层的晶粒平均尺寸。     

Antimicrobial Activity of Pd‐Doped ZnO Sol‐Gel‐Derived Films

Palladium doped ZnO was prepared by the sol‐gel and dip‐coating techniques, starting with zinc acetate and palladium chloride as precursors, followed by its hydrolysis in methanol. Acetic acid was incorporated to adjust pH, as well as acetylacetonate and monoehtylamine as stabilizers. The sol was later dipped 3 times in silica substrates. Structural, morphological, and antimicrobial properties of the films were investigated for three palladium contents (1.0, 2.5, and 5 mol %). X‐ray diffraction (XRD) showed that the films have a hexagonal structure after been annealed at 500°C. X‐ray photoelectron Spectroscope (XPS) showed that Pd is present in its oxidized form. Atomic force microscopy (AFM) from films showed a crack free and smooth surface (Ra= 18 nm), composed of cross‐linked particles. The synthesized films presented antibacterial activity against Escherichia coli and Pseudomona aeruginosa. It was observed that the higher Pd content (5 mol %) presents the higher antimicrobial ratio, 64.07%, for the E. coli, whereas for the P. aeruginosa, the lower Pd content (1 mol %), shows the higher antimicrobial ratio, 76.43%.     

Effect of thermal insulation on microstructural homogeneity and onset temperature of flash sintered materials

The present work aimed to reduce the microstructure heterogeneity inherent to flash sintering by using alumina blankets as a thermal insulator around ZnO cylindrical samples during the sintering process, under different electric field conditions. Thermal insulation significantly reduced the flash onset temperature and the grain size heterogeneity. For higher electric fields, a temperature reduction as high as 480 °C was observed, which also led to lower densification. These findings were discussed in terms of changes in the heat loss dynamics coupled with the adsorbed water retention, both promoted by the applied thermal insulation. A model to estimate the temperature at stage III of flash sintering was proposed. The final temperature reached with thermal insulation did not differ significantly from the ones without it. Thus, thermal insulation could represent an alternative route to flash sinter materials with lower furnace temperatures with energy savings up to 78 % and a more homogeneous microstructure.     

Impedance Spectroscopy and Dielectric Properties of Flash Versus Conventionally Sintered Yttria‐Doped Zirconia Electroceramics Viewed at the Microstructural Level

The defect chemistry‐modulated dielectric properties of dense yttria‐doped zirconia ceramics prepared by conventional sintering (at 1350°C–1500°C) and electric field‐assisted flash sintering (55 V/cm at 900°C) were studied by impedance spectroscopy. While the bulk dielectric properties from both sets of samples showed only small and insignificant changes in conductivity and permittivity, respectively, a huge increase of these properties was measured for the grain boundaries in the flash sintered specimens. A close analysis of these results suggests that flash sintering reduced grain‐boundary thickness (by about 30%), while increasing the concentration of oxygen vacancies near these interfaces (by about 49%). The underlying mechanism proposed is electric field‐assisted generation and accommodation of defects in the space‐charge layers adjacent to the grain surface. The changes in measured permittivity are attributed to the boundary thickness effect on capacitance, while conductivity involved variations in its defect density‐dependent intrinsic value, accounting for changes also observed in grain‐boundary relaxation frequencies. Therefore, in terms of modifications to the specific dielectric properties of these materials, the overall consequence of flash sintering was to considerably lower the semi‐blocking character of the grain boundaries.     

Development of crystallographic texture in chemical solution deposited lead zirconate titanate seed layers

Direct seeding of {001} textured lead zirconate titanate (PZT) on platinized silicon substrates was achieved by chemical solution deposition. The processing space for {001} PZT texturing was explored, under fixed PZT pyrolysis and crystallization conditions, by varying the lead content in solution, dopant species, and PZT layer thicknesses for deposition on platinized Si substrates with different platinum grain sizes. Strong {001} texture was achieved on fine‐grained (25 nm) platinum deposited at room temperature and dense, large‐grained platinum (80 nm) deposited at elevated temperature. Increases in lead content of solutions (from lead excesses of 10 at.% to 16 at.%) reduced surface pyrochlore coverage, with no substantial influence on orientation or grain size. Seed layer texturing was found to be insensitive to doping (Mn and Nb) on room temperature platinum, although niobium doping increased pyrochlore coverage. Conversely, on platinum deposited at high temperature, manganese doping reduced the perovskite nucleation, producing a rosette microstructure. Undoped seed layers from 30 to 70 nm thick were found to be strongly {001} textured while thicker layers were {111} textured and thinner layers were poorly crystallized.     

Corrosion resistance of ternary NiP based alloys in sulfuric acid solutions

NiP based alloy films were prepared by autocatalytic deposition and their structure, chemistry and corrosion behaviors in sulfuric acid solutions were studied as a function of their composition. The as-prepared Ni-based alloys are nanocrystalline, and their grain size decreases with increasing P content. Addition of a third element (W or Mo) influences the observed grain size. At low anodic overpotential NiP based alloys present a lower exchange current and lower reactivity than Ni, both improving with increasing P content. Contrary to Ni however, the NiP based alloys do not passivate at higher anodic overpotentials. Addition of W to NiP alloys can improve their corrosion resistance, while addition of Mo has little or no beneficial effects on corrosion properties.     

碳化钛/聚酰亚胺高介电复合薄膜的制备及性能研究

采用机械共混法将经硅烷偶联剂改性的碳化钛粉体掺杂入聚酰亚胺中,制备了碳化钛/聚酰亚胺复合薄膜。分析了不同碳化钛粒子含量对复合薄膜的显微结构、力学性能及介电性能的影响。实验结果表明,随着纳米TiC含量的不断升高,复合薄膜的拉伸强度呈现先上升后下降的趋势,复合薄膜的耐电击穿场强迅速下降。与此同时,复合材料的介电常数则显著提高。     

Flash Sintering of Nanocrystalline Zinc Oxide and its Influence on Microstructure and Defect Formation

We report the sintering behavior of nanocrystalline zinc oxide under external AC electric field between 0 and 160 V/cm. In situ acquisition of density by means of laser dilatometry, evaluation of specimen temperature, real‐time measurement of electric field and current help analyze this peculiar behavior. Field strength and blocking electrodes significantly affect densification and microstructure, which was evaluated in the vicinity of the flash event and for the fully sintered material. High current densities flow through the sample at high electric fields, entailing a sudden increment of the temperature estimated to several hundreds of K and an exaggerated grain growth. In contrast, low current density flows through the sample at lower electric fields, which guarantees normal grain growth and highest final density. Macroscopic photoluminescence measurements give insights into the development of the defect structure. Electric fields are expected to enhance defect mobility, explaining the high densification rates observed during the sintering process.     

A comparison between chemical and sputtering methods for preparing thin-film silver electrodes for in situ ATR-SEIRAS studies

Stable silver thin films were prepared either by chemical deposition or by argon sputtering on germanium and silicon substrates, respectively, and used as electrodes for in situ infrared spectroscopy experiments with a Kretschmann internal reflection configuration. The spectra obtained for acetate anions adsorbed from neutral solutions showed a noticeable intensity enhancement (SEIRA effect). This enhanced absorption has been related to the surface structure of the films that have been characterized by ex situ STM and in situ electrochemical measurements (lead underpotential deposition, UPD). STM images of the chemically deposited silver films show mean grain sizes ranging from ca. 20 to 90 nm for deposition times between 2 and 20 min, and the absence of flat domains. On the other hand, STM images of the films deposited by argon sputtering show mean grain sizes around 30 nm for a film growth rate of 0.05 nm s⁻¹ and 70 nm for a film growth rate of 0.005 nm s⁻¹. In this latter case, atomically flat domains up to 50 nm wide have been observed. This observation is consistent with a more defined voltammetric profile for lead UPD, that indicates a higher degree of surface order. Moreover, the roughness factor obtained from the charge density involved in lead UPD in the case of the sputtered silver film is lower than that measured for the chemically deposited silver film. All these structural data can be connected with the observations on the effect of deposition conditions of the silver film on the SEIRA effect for adsorbed acetate. Maximum enhancement is observed for chemically deposited films and sputtered films at high deposition rate for which the grain size is around 40-60 nm. The increase of the grain size for the sputtered silver films deposited at decreasing deposition rates can be related to the observed decrease in the SEIRA effect.     

Strengthening of electromechanical properties for poly(vinylidene fluoride‐trifluoroethylene) films under tailored electric cycling

Copolymers of polyvinylidene fluoride and trifluorethylene [P(VDF‐TrFE)] have potential applications in wearable and implantable electromechanical devices since they are mechanically flexible, and biocompatible. A tailored electric cyclic process is employed to enhance both electrical and mechanical properties in P(VDF‐TrFE) 65/35 mol % copolymer films. The films are subjected to lower and higher field magnitude electric cycling successively. For electrical properties, enhancement in remnant polarization, dielectric and piezoelectric constants occurs. From mechanical point of view, strengthening in the fracture strength happens. Wide‐angle X‐ray diffraction techniques examine changes of the orientation of the molecular chains, grain size, and crystallinity after electric cycling for the copolymer films. Scanning electron microscopy reveals evolutions of the microstructure, including rod‐like textures and fractography of the films. The results indicate that electric cycling causes the molecular chains to orient gradually along the direction perpendicular to the applied electric field. Consequently, an enhancement of 12.2% and 45% is realized for the remnant polarization and fracture strength, respectively for P(VDF‐TrFE) 65/35 copolymer film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45926.     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.