Nanocrystalline buildup,relaxor behavior,and polarization characteristic in PZT–PNZN quaternary ferroelectrics

The Pb(Zr_0.47Ti_0.53)O₃–Pb[(Ni_0.6Zn_0.4)_1/3Nb_2/3]O₃ (PZT–PNZN) quaternary ferroelectrics presenting the high piezoelectric coefficients are the active element in a range of piezoelectric devices. However, the buildup of nanoceramics with stable perovskite structure is still a big challenge, which prohibits the miniaturization of piezoelectric devices. In this work, the high dense PZT–PNZN nanoceramics with average grain size of 130 nm were prepared by a combination of high‐energy ball milling (HEBM) and spark plasma sintering (SPS). The domain configuration and relaxor behavior in this nanoceramic are reported for the first time. Although the noncubic crystal structure and dielectric anomaly suggest a ferroelectric behavior, only very slim polarization–electric (P–E) hysteresis loops are observed. The suppression of macroscopic ferroelectric polarization mainly originates from the decrease in crystal tetragonality and the enhanced clamping effect on domain wall motion. The piezoelectric properties, d₃₃=65 pC/N and k_p=17%, raise the possibility of PZT–PNZN nanoceramics for application in multilayer piezoelectric devices.     

Control of ferroelectric and linear piezoelectric response of PZT films through texture

The high and low field ferroelectric response of freestanding PbZr_0.52Ti_0.48O₃ (PZT) films, with texture varying from 100% (001) to 100% (111) was investigated via 500 nm thick PZT unimorphs deposited on the same substrate. It is shown that the ferroelectric and piezoelectric properties depend strongly on texture, and the effective transverse strain and stress coefficients vary linearly with %(001) and %(111) texture factors. PZT films with 100% (001) orientation displayed 150%, 140%, and 80% larger linear piezoelectric strain coefficient, saturated strain coefficient, and saturated stress coefficient, respectively, compared to films with 100% (111) orientation. As a result, pure (001) textured PZT films with 20% higher dielectric constant have 50% higher figure of merit in sensing than films with pure (111) texture. The piezoelectric and ferroelectric properties of all but one combinations of (001) and (111) texture were shown for the first time to be bounded by the values for 100% (001) and 100% (111) texture. A notable exception was PZT films comprised of 73% (001) and 27% (111) texture which showed stable piezoelectric coefficients at all electric fields, with major technological implication to low power microdevices. Finally, the coercive field was shown to decrease with (001) texture factor and excess‐Pb in the PZT and the PbTiO₃ seed layer.     

Synthesis of spherical lead zirconate titanate (PZT) nanoparticles by electrohydrodynamic atomisation

Abstract

This paper describes the production of spherical-shaped lead zirconate titanate (PZT) nanoparticles by the electrohydrodynamic atomisation (EHDA) process in order to make inks suitable for ink jet printing applications. PZT sols with different concentrations (0·1–0·6 M) were used as starting materials. Two different heating systems, gas heating and direct heating, were used in order to remove the solvent, reduce the particle size and stabilise the PZT particles. Several aspects have been considered, such as liquid flow rate, sol concentration and heat system temperature, and their influence on the particle dimension is determined. Using optimised processing parameters of direct heating at 520°C, 0·2 M precursor sol, flow rate of 0·2 mL h^?1 and field of 3 kV cm^?1, particles of 100–300 nm in diameter were synthesised. Following stabilisation at 300°C, the particles were suspended in a PZT sol to produce an ink suitable for ink jet printing.     

锆钛酸铅（PZT）粉体合成的研究进展

锆钛酸铅（PbZrxTi1-xO3,PZT）陶瓷是一类重要的铁电、压电、介电材料,其粉体的相组成、化学组成、热稳定性和烧结活性影响着陶瓷制品的铁电、压电和介电性能。本文详细综述了合成PZT粉体的固相反应法和湿化学方法的发展现状,并对几种合成方法的特点进行了评介,为低温合成纯相PZT粉体和PZT一维纳米结构指出了可能的方法。     

Control of Crystal Orientation and Piezoelectric Response of Lead Zirconate Titanate Thin Films Near the Morphotropic Phase Boundary

PbZr_0.53Ti_0.47O₃ (PZT) thin films with various preferred crystallographic orientations were synthesized on various substrates using pulsed laser deposition techniques. Larger piezoelectric displacement, which involved the bending vibration of the PZT film/substrate, was observed in randomly oriented PZT thin film than that in (100)- and (111)-preferred texture films. This result was discussed by correlation with the number of effective spontaneous polarization axes in the morphotropic phase boundary of the PZT system. Moreover, polarization fatigue was found to lower the electric-field-induced displacement significantly, indicating a large contribution of ferroelectric domain motion to the piezoelectric response of PZT thin films under bipolar drive.     

Laser-transfer processing of functional ceramic films

Pulsed excimer laser irradiation through a UV-transparent fabrication substrate has been successfully employed to separate PZT thick films from their sapphire host substrates. Films of 20 μm in thickness were prepared by a hybrid particle sol–gel synthesis route. The microstructure, morphology and ferroelectric properties of the thick films after laser-transfer have been examined. Films were irradiated with a 248 nm, 15 ns pulse, and transferred to a platinised silicon substrate (Pt/Ti/SiO₂/Si). A laser fluence of 250 mJ/cm² was sufficient to delaminate the original PZT/sapphire interface. The pulsed energy density used here is lower than reported by other groups utilising a laser-transfer process for PZT. This is believed to be due to higher levels of porosity at the film/substrate interface in this study.     

Low-Temperature Sintering of Lead Zinc Niobate–Lead Zirconate Titanate Ceramics Using Nano-Sized Powder Prepared by the Stirred Media Milling Process

Lead zinc niobate–lead zirconate titanate (PZN–PZT) nano-sized powders with a diameter of ∼35 nm were fabricated by a high-energy stirred media mill using 50 μm diameter zirconia beads as the milling media at a rotation speed of 4000 rpm for 1 h. The sintering temperature of PZN–PZT was greatly reduced, and a fully densified bulk body was obtained at only 750°C when stirred media milled nanopowder was used. The control of evaporation of lead oxide was very important to obtain high electrical properties due to the increased surface area of nano-sized powders. The ferroelectric hysteresis, piezoelectric d ₃₃ coefficient, and dielectric properties of sintered ceramics using nanopowder were measured and compared with the values obtained from a sintered specimen using conventional milled powders. Remanent polarization, d ₃₃ coefficient, and relative dielectric constant of 750°C sintered stirred media milled powders containing 2% of excess PbO and 1% of 4PbO–B₂O₃ liquid phase were 10.3 μC/cm², 277 pC/N, and 1310, respectively.     

Li2CO3掺杂对0.2PMN-0.8PZT陶瓷的影响

利用铌铁矿预产物合成法,研究不同温度烧结下Li2CO3掺杂对0.2 PMN-0.8PZT压电陶瓷(简称PLC)的相结构和电性能的影响。X射线衍射(XRD)和扫描电镜(SEM)的分析结果表明,掺杂LiCO3的0.2PMN-0.8PZT压电陶瓷经不同温度煅烧后,所有陶瓷样品的相组成均为纯钙钛矿相,并随着烧结温度的升高,PLC的相结构有由四方相向菱方相转变的趋势。通过0.2PMN-0.8PZT压电陶瓷掺杂LiCO3煅烧后的微观形貌、介电常数、压电性能、铁电性能的分析,发现经1200℃烧结的样品的介电和压电性能最佳:介电常数(εr)为38512,室温压电常数(d33)为300 pC/N,剩余极化强度(Pr)为31.3 C/cm2,矫顽电场(Ec)为7.5 kV/cm。     

多孔PZT压电陶瓷膜的制备及其抗污染性能

以 PbZr_xTi_1-xO₃（PZT）压电陶瓷粉体为原料,通过干压成型的方法制备多孔PZT陶瓷膜,考察了煅烧温度对多孔PZT陶瓷膜的机械强度、孔隙率以及纯水渗透性能的影响。当煅烧温度为950℃时,可制备出纯水渗透率为850 L·m^-2·h^-1·MPa^-1,孔径为300 nm,机械强度为47.8 MPa,孔隙率为34%的多孔PZT陶瓷膜。在此基础上,考察了极化温度与极化电压对多孔PZT陶瓷膜压电性能的影响,并对极化后的PZT压电陶瓷膜进行萃取和表面等离子刻蚀处理。结果表明：极化温度为120℃、极化电压强度为4 kV·mm^-1,极化后经热乙醇萃取及表面等离子刻蚀4 min后,多孔PZT压电陶瓷膜在外加交流电为20 V时,产生的共振振幅信号值达34.8 mV。将制备的多孔PZT压电陶瓷膜在粒径为600 nm的含油乳化液中进行过滤实验,发现陶瓷膜两端未加交流电时,其通量在2 h内衰减至4%。而加交流电后,其稳定通量可维持在20%左右,表明制备的多孔PZT压电陶瓷膜具有良好的抗污染效果。     

Effect of Zn, Sr, and Y Addition on Electrical Properties of PZT Thin Films

We have investigated methods to increase the efficiency of piezoelectric micromachined ultrasonic transducers (pMUTs). pMUTs are driven by a thin piezoelectric layer on a Si membrane. The efficiency of pMUTs can be increased using a film with better ferroelectric properties. We have used Zn, Sr, and Y doping on PZT-based thin films along the morphotropic phase boundary (MPB) composition to increase their piezoelectric properties. The results obtained were then extended to compositions on both sides of the MPB. The sol–gel method was used to prepare precursor solutions, which were then spin coated on a Pt(100)/Ti/SiO₂/Si substrate to prepare the PZT thin films. It was found that Zn and Sr together had the most significant effect on the ferroelectric properties in which a saturation polarization of 108 μC/cm² and remanent polarization of 54 μC/cm² were achieved.     

Ferroelectric and piezoelectric properties of Ba0.85Ca0.15Ti0.90Zr0.10O3 films in 200 nm thickness range

Lead-free piezoelectric Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ (BCZT) thin films were fabricated on Si/SiO₂/TiO₂/Pt (100) substrates following chemical solution deposition technique. Microstructure of the nano-sized BCZT particles crystallized in the thin film was thoroughly characterized. Ferroelectric, dielectric and piezoelectric properties of the films were investigated in detail. The BCZT films annealed at 800°C temperature exhibited high remanent polarization of 25 ± 1 μC/cm², energy density of 17 J/cm³, dielectric constant of 1550 ± 50 and dielectric tunability of 50%. Converse piezoelectric coefficients (d₃₃) obtained from piezo-response force microscopy (PFM) measurements on BCZT grains of different grain size (20-100 nm) distributed on the BCZT 700 film varied widely from 90 to 230 pm/V. The same for BCZT 800 measured on different grain size (30-130 nm) varied from 120 to 295 pm/V. These BCZT thin films with high dielectric, ferroelectric, and piezoelectric properties might be good alternative to the PZT films for thin film piezoelectric device applications.     

Enhanced dielectric properties and discharged energy density of composite films using submicron PZT particles

Flexible dielectric composite films are highly desirable materials with potential application in capacitors due to their high energy density and discharged efficiency. However, agglomeration induced by the large surface energy of nanoparticles and their large dielectric losses are unfavorable to the improvement of energy density. Submicron lead zirconate titanate (PZT) particles have shown great potential as filler in achieving a high energy storage capacity because of their excellent dielectric properties and good dispersion. In this work, calcined PZT particles were used to prepare PZT/polyvinylidene fluoride (PVDF) composite films. The results showed that composite films of high quality could be obtained even with high contents of submicron PZT particles. The introduction of PZT particles significantly improved the dielectric performance of composite films compared with that of the pristine PVDF film. The discharged energy density of composite films with 10?vol% PZT particles achieved 6.41?J/cm³ at 250?kV/mm. A high efficiency of 87.25% was obtained at 50?kV/mm. These findings confirm the feasibility of PZT particles as inorganic filler in composite films for energy storage applications.     

Synthesis of Porous Submicron Gd0.1Ce0.9O1.95 Particles by Carbon Nanoparticle-Addition Ultrasonic Spray Pyrolysis (CNA-USP) and Nanoparticle Preparation by Ball Milling

A new ultrasonic spray pyrolysis method, called carbon nanoparticle-addition ultrasonic spray pyrolysis (CNA-USP), is developed to synthesize nanoparticles of electrolyte material for solid oxide fuel cell applications. In CNA-USP, carbon nanoparticles are added in a precursor solution. First, Gd_0.1Ce_0.9O_1.95 (GDC) particles were synthesized from an aqueous solution of Ce(NO₃)₃ 6H₂O and Gd(NO₃)₃ 6H₂O by using the CNA-USP method. The resulting synthesized GDC particles were agglomerated, porous, primary particles on the order of 10 nm in diameter. EDX images revealed uniform distributions of Ce, Gd, and O in these porous particles. Then, these agglomerated, porous submicron GDC particles were ground into primary nanoparticles by ball milling for 24 h. The average diameter of the ground GDC nanoparticles was about double of their average crystallite size.

Copyright 2014 American Association for Aerosol Research     

Fabrication and Electrical Properties of Lead Zirconate Titanate Thick Films on Si Substrate by Using Lanthanum Nickelate Buffer Layer

Lead zirconate titanate PbZr_0.53Ti_0.47O₃ (PZT) thick films have been deposited on silicon substrate by modified metallorganic decomposition process. Crack-free PZT films of 8 μm thickness can be obtained by using lanthanum nickelate LaNiO₃ (LNO) as buffer layer. The greater LNO thickness, the greater thickness of crack-free PZT can be obtained. The X-ray diffraction measurements show the films exhibit a single perovskite phase with (110) preferred orientation. SEM measurements showed the PZT thick films have a columnar structure with grain size about 60–200 nm. The thickness dependence of ferroelectric, dielectric, and piezoelectric properties of PZT thick films have been characterized over the thickness range of 1–8 μm. For PZT with thickness of 8 μm, P _r and E _c are 30 μC/cm² and 35 kV/cm, and dielectric constant and dielectric loss are 1030 and 0.031, respectively. The piezoelectric coefficient ( d ₃₃) of PZT with 8 μm thickness is obtained to be 77 pm/V. PZT thick films on LNO-coated Si substrate are potential for MEMS applications.     

Processing and electromechanical properties of lead zirconate titanate thick films by electrophoretic deposition

Electrophoretic deposition (EPD) was used for the fabrication of piezoelectric [lead zirconate titanate (PZT)] thick films on alumina substrates. The EPD was performed in constant current mode from an ethanol based suspension consisting of PZT and PbO particles. The influence of addition of ethyl cellulose (EC) and sintering temperature on the thickness, density, homogeneity and functional response of PZT thick films is studied. Results show that the highest electromechanical performance is obtained for the PZT thick films sintered at 900 or 950°C, with a thickness coupling factor k_t of 50%. The addition of EC influenced the thickness of the PZT thick films but had only minor effect on the porosity content for sintering temperatures over 900°C. Moreover, elastic constants of the thick films based on the suspension with EC were lower, which leads to lower acoustic impedance (15?MRa) while maintaining high (k_t) value. In this last case, a better acoustic matching can be expected with propagation media such as water or biological tissues for ultrasound medical imaging applications.     

Low temperature sintering of PZT powders coated with Pb5Ge3O11 by sol–Gel method

Low temperature sintering of PZT powders was investigated using Pb₅Ge₃O₁₁(PGO) as a sintering aid. PZT powders with 150 nm particle size were coated with PGO which was prepared from precursor solutions of Ge(OiPr)₄ and Pb(NO₃)₂ by sol–gel method. 1 wt% PGO-added PZT powders were densified at 750°C for 2 h to sintered bodies with the relative density of approximately 95%. An addition of PGO improved the sinterability of PZT powders with a reduction of sintering temperature by about 300°C. Dielectric and piezoelectric properties of PGO-added PZT ceramics sintered at ≦950°C were superior to those without PGO additives. However, a higher sintering temperature above 1000°C deteriorated the dielectric and piezoelectric properties of PGO-added PZT ceramics. This may be attributed to the change of microstructure involving the formation of solid solution between PZT and PGO. The 1 wt% PGO-added PZT bodies sintered at 750°C exhibited an electromechanical coupling factor, Kp, of about 56%.     

Electrophoretic deposition of Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thick film on Pt wire

0.2PbNi_1/3Nb_2/3–0.8Pb(Zr,Ti)O₃ (PNN–PZT) thick films were deposited on Pt wire with the diameter of 50 μm by electrophoretic deposition (EPD) method. The EPD deposition times on the microstructures of PNN–PZT thick films were investigated. By optimizing the EPD process, the Pt wire can be uniformly wrapped with the PNN–PZT powders. During the sintering process, the as-deposited PNN–PZT/Pt wires were buried in the mixed powders of PbCO₃ and ZrO₂, and then sintered in the optimal temperature to get a dense microstructure. The piezoelectric properties of the thick films were characterized by scanning force microscopy (SFM) method. The results show that the PNN–PZT thick films prepared by EPD method have good piezoelectricity.     

Effect of high energy ball milling on strengthening of Cu-ZrO2 nanocomposites

In this paper, copper matrix nanocomposites reinforced by 5 and 10?wt% ZrO₂ particles were produced by mechanical milling technique at different milling times. The produced nanocomposite powders were investigated by X-ray diffraction technique and transmission electron microscopy. The effect of high energy ball milling on the morphology, microstructure and microhardness of the produced composites has been investigated. After that cold compaction was applied to the prepared powders under a pressure of 700?MPa and sintered at 950?°C for 2?h in hydrogen atmosphere. The results showed that increasing milling time improves microhardness of the prepared nanocomposites. The microhardness of Cu-10%ZrO₂ after 20?h milling is 3.76 times larger than pure Cu. This improvement is attributed firstly to the presence of ZrO₂ nanoparticles in addition to the improvement coming from the grain refinement and crystallite size reduction occurred due to mechanical alloying. So, in spite of the crystallite size of Cu-10%ZrO₂ nanocomposite is reduced to 10.75?nm compared to 105.5?nm for pure Cu, the presence of ZrO₂ nanoparticles plays a major role on mechanical properties improvement.     

Processing Conditions and Aging Effect on the Morphology of PZT Electrospun Nanofibers, and Dielectric Properties of the Resulting 3–3 PZT/Polymer Composite

Lead zirconate titanate (PZT) nanofibers are obtained by electrospinning a sol–gel based solution and polyvinyl pyrrolidone (PVP) polymer, and by subsequent sintering of the electrospun precursor fibers. The average diameter of the precursor PZT/PVP green fibers has increased with the aging of the precursor solution along with an increase in the viscosity. Bead-free uniform green PZT/PVP fibers were collected at about an ∼230 nm average fiber diameter using a 28 wt% PVP ratio solution with a viscosity of 290 mPa. Shrinkage of 40% was recorded on the fiber diameter after sintering. The X-ray diffraction pattern of the annealed PZT fibers exhibits no preferred orientation and a perovskite phase. Preparation of 3–3 nanocomposites by the infusion of polyvinylester into the nanofiber mat facilitates successful handling of the fragile mats and enables measurements of the dielectric properties. The dielectric constant of the PZT/polyvinylester nanocomposite of about 10% fiber volume fraction was found to be fairly stable and vary from 72 to 62 within the measurement range. The dielectric loss of the composite is below 0.08 at low frequencies and reaches a stable value of 0.04 for most of the measured frequencies.     

Effects of pore shape and porosity on the properties of porous PZT 95/5 ceramics

Porous lead zirconate titanate (PZT 95/5) ferroelectric ceramics were prepared by sintering compacts consisting of PZT and pore formers. The piezoelectric, dielectric and ferroelectric properties of porous PZT ceramics were investigated as a function of pore shape and porosity. Piezoelectric coefficient (d₃₃), dielectric constant (ɛ₃₃) and remnant polarization (P_r) decreased with an increase in porosity, and the porous PZT ceramics with spherical pores exhibited better properties than that with irregular pores. Furthermore, the electrical conductivities of PZT ceramics were investigated to explain the phenomena that porous PZT ceramics exhibited lower dielectric loss (tan δ) than dense PZT ceramics in the temperature range from 250 to 500 °C.