Residual stress and electrical properties of Pb(Zr0.52,Ti0.48)O3 thin films RF sputtered directly on Cu foils

Polycrystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films between 250 and 1000 nm thick were deposited on Cu foils via RF magnetron sputtering. Samples were crystallized ex situ between 550°C and 750°C in a low oxygen partial pressure atmosphere, pO₂, in order to avoid oxidation of the substrate. These were compared to films made on more common Pt/TiO_x/SiO₂/Si substrates also crystallized under low pO₂ conditions. The mismatch of the coefficients of thermal expansion for Cu and PZT caused large compressive residual stresses to develop in the films, whereas films on Pt‐Si experienced more moderate tensile stresses. Stress was measured using the sin²ψ method. In addition to mechanical implications, i.e., film cracking and delamination, the effect of residual stress on electrical properties is discussed. Dielectric constants of PZT were lower on Cu than on Pt/TiO_x/SiO₂/Si. This could be due either to a dead layer effect or to the residual stress imposed by the substrate. The remanent polarizations for films on Cu were between 18 and 41 μC/cm², while coercive fields were between 37 and 54kV/cm. Rayleigh analysis was used to describe the role of defects affecting domain wall mobility, as they act as pinning centers and decrease the extrinsic polarization response.     

Porosity‐dependent properties of Nb‐doped Pb(Zr,Ti)O3 ceramics

In the present work, it is shown how the controlled porosity can be exploited to obtain a compromise between a reduced permittivity down to a few hundreds and maintaining a high tunability level as in the dense material, to fulfill requirements for tunable applications. Nb‐doped Pb(Zr,Ti)O₃ ceramics with porosity in the range 5%‐30% have been prepared by direct sintering method. X‐ray diffraction analysis and Rietveld refinement indicated a co‐existence of tetragonal and monoclinic phases in the porous ceramics. Dielectric properties revealed a gradual reduction in permittivity when increasing the porosity level, while maintaining low dielectric losses below 3%. The ferroelectric switching behavior is also influenced by the porosity level: a continuous reduction in the saturation and remnant polarization is observed with increasing porosity. The nonlinear dielectric properties of all the investigated ceramics preserve a high level of tunability in comparison with one of the dense material, irrespective of the porosity level, while zero field permittivity was decreased below 1000. An optimum behavior is found for the ceramic sample with 25% porosity, which shows a high tunability, smaller losses, and moderate dielectric constant (ε ~600).     

Impact of Sr-doping on structural and electrical properties of Pb(Zr0.52Ti0.48)O3 thin films on RuO2 electrodes

In this paper, we investigated the impact of Sr-doping on the structural properties and electrical characteristics of lead zirconate titanate [Pb(Zr_0.52Ti_0.48)O₃, PZT] thin films deposited on RuO₂ electrodes by a sol-gel process and spin-coating technique. We used X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and field-emission transmission electron microscopy to explore the structural, morphological, chemical, and microstructural features, respectively, of these films as a function of the growth condition (strontium doping concentrations varied from 1, 3, and 5 mol%). The PZT thin film processed at the 3 mol% Sr exhibited the best electrical characteristics, including a low leakage current of 2.27×10⁻⁷ A/cm² at an electric field of 50 kV/cm, a large capacitance value of 2.74 μF/cm² at a frequency of 10 kHz, and a high remanent polarization of 37.95 μC/cm² at a frequency of 5 kHz. We attribute this behavior to the optimal amount of strontium in the PZT film forming a perovskite structure and a thicker interfacial layer at the PSZT film-RuO₂ electrode interface.     

Cr2O3掺杂Pb(Mn1/3Sb2/3)0.05Zr0.47Ti0.48O3压电陶瓷的性质

探讨了Cr2O3掺杂对锑锰锆钛酸铅Pb（Mn1/3Sb2/3）0.05Zr0.47Ti0.48O3（简称PMSZT）压电陶瓷性能影响.通过X射线衍射,电子顺磁共振以及扫描电镜分析了PMSZT＋z Cr2O3（z=0.2%～0.8%,质量分数）陶瓷的相组成,元素价态以及显微结构.结果表明：合成温度900℃保温2 h后,可以得到钙钛矿结构.随着Cr2O3掺杂量的增大,四方相的含量减少,准同相界向三方相移动.掺杂Cr2O3的质量分数为0.6%时：相对介电常数εr=1 650,介电损耗tanδ=0.006,压电常数d33=328 pC/N,机电耦合系数Kp=0.63,机械品质因数Qm=2 300,电性能优于Cr2O3掺杂量为0.2%,0.4%,0.8%的样品,但比未掺杂时的稍差.随着Cr2O3掺杂量的增加,PMSZT陶瓷的Curie温度降低,谐振频率变化率随温度变化由正变负.     

激励方式对锆钛酸铅钡锶压电陶瓷介电性能的影响

采用扎膜工艺和固相反应法制备了(Pb0.70Ba0.26Sr0.04)(Zr0.52Ti0.48)O3(PBSZT)压电陶瓷。通过扫描电子显微镜和X射线衍射表征PBSZT陶瓷的结构和物相组成,用电容介损测试仪表征压电陶瓷的介电性能与激励场强,通过自建电路集成直流电源、标准电容,在低频频率特性测试仪上得到偏场强度对压电陶瓷介电性能的影响关系。结果表明:压电陶瓷材料的介电性能随着加载的电场强度的增大先逐渐升高,而后出现拐点开始降低;在偏压电场中,自由电容CT随正向偏场强度的增加逐渐减小,但随着反向偏场强度的增加逐渐增大。tanδ则随着正、反偏场强度的增加均呈现上升;压电陶瓷的机电耦合系数kp与偏场强度的关系是以0点为界,随着负偏场增强,kp略显下降,反之,随正偏场增强,kp缓慢增大。因此,压电陶瓷应用时应避开强场损耗高点;并在环境中施加正向偏场,有助于抑制压电陶瓷性能衰减。     

Functional and structural effects of layer periodicity in chemical solution‐deposited Pb(Zr,Ti)O3 thin films

This work investigates the role of crystallization layers’ periodicity and thickness on functional response in chemical solution‐deposited lead zirconate titanate thin films, with periodic, alternating Zr and Ti gradients normal to the surface of the film. The films were processed with a range of layer periodicities and similar total film thickness, in order to relate the number of layers and compositional oscillations to structural and functional response changes. Trends of increased extrinsic contributions to the dielectric and ferroelectric responses are observed with increasing layer periodicity, but are counterpointed by simultaneous reduction in intrinsic contributions to the same. Transmission electron microscopy reveals in‐plane crystallographic discontinuity at individual crystallization interfaces. Samples with smaller periodicity, and thus thinner layers, potentially suffer from grain size refinement and subsequent reduction in domain size, thereby limiting extrinsic contributions to the response. The strong compositional oscillations in samples with larger periodicity result in deep fluctuations to the tetragonal side of the phase diagram, potentially reducing intrinsic contributions to the response. Conversely, piezoresponse force microscopy results suggest that large chemical oscillations in samples with larger periodicity also result in closer proximity to the morphotropic phase boundary, as evidenced by local acoustic softening at switching, signaling potential field‐induced phase transitions.     

(Pb,Sm)(Zr,Sn,Ti)O3 Multifunctional Ceramics with Large Electric‐Field‐Induced Strain and High‐Energy Storage Density

Recently, the progress of integrated electronics has led to a strong demand for materials and devices with multiple functions. In this study, we achieved Pb_0.985Sm_0.01 (Zr_0.64Sn_0.28Ti_0.08)O₃ (PSZST) multifunctional ceramics which showed simultaneously large electric‐field‐induced strain (0.63%) and high recoverable energy density (1.743 J/cm³) at room temperature. Moreover, the strain and recoverable energy density exhibited a slight frequency fluctuation in the frequency range of 1–10 Hz. Their variations were less than 8% and 1.3% and the values were all higher than 0.58% and 1.722 J/cm³, respectively. The large strain, high‐energy density, and their good frequency stability in a wide range indicate that the PSZST ceramic is quite promising for application in multifunctional devices.     

Microstructure and electric properties of Pr-doped Pb(Zr0.52Ti0.48)O3 ceramics

Improving the piezoelectric activity of lead zirconate titanate (PZT) ceramics is of great importance for practical applications. In this study, the influence of Pr³⁺ doping on the ferroelectric phase composition, microstructure, and electric properties on the A-site of (Pb_1-1.5xPr_x)(Zr_0.52Ti_0.48)O₃ is extensively investigated. A dense and fine microstructural sample is obtained with the introduction of Pr³⁺. The results show that the morphotropic phase boundary (MPB) moves to the rhombohedral phase region. The rhombohedral and tetragonal phases exhibit an ideal coexistence in the 4 mol.% Pr³⁺ doped (PPZT4) samples. Lead vacancy and the reduction of the potential energy barrier are considered to be the key mechanisms for donor doping, which is upheld by the Pr³⁺ doping. Combining the I-E hysteresis loops with the P-E hysteresis loops, it becomes apparent that both contribution maximums of the domain switching and residual polarisation are in PPZT4. Moreover, the thermal aging resistance of PZT is improved by doping, and the temperature stability is optimised from 83% in PZT to 96% in PPZT4. Hence, an appropriate amount of Pr³⁺ doping can effectively improve the piezoelectric activity of PZT ceramics in the MPB area and optimise the performance stability of the material under application temperatures.     

Ba(Zr0.3Ti0.7)O3薄膜的结构及性能

用溶胶-凝胶法分别在Pt/Ti/SiO2/Si和LaNiO3/Pt/Ti/SiO2/Si衬底上制备了锆钛酸钡[Ba(Zr0.3Ti0.7)O3,BZT]薄膜.相结构及介电性能研究表明:衬底和薄膜厚度对BZT薄膜性能具有显著影响.制备在LaNiO3/Pt/Ti/SiO2/Si衬底上的BZT薄膜具有(100)面的择优取向,其介电常数及介电损耗则随着薄膜厚度的增加而降低.对制备在Pt/Ti/SiO2/Si衬底上的BZT薄膜,在薄膜厚度低于500nm时,其介电常数随薄膜厚度增加而增加,大于500nm时又有所减小.     

湿化学方法制备Pb（ZrxTi1—x）O3陶瓷微粉的研究

以金属醇盐和硝酸盐为原料，按Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３＋５％（ｍａｓｓ０ＰｂＯ设计组成，采用改进的湿化学方法，严格控制共沉淀物生成，洗涤，分散液的选配及冷冻干燥条件；再经合理煅烧工艺，不需粉磨，制成化学组成均匀分布，不含有硬团聚体，具有单一钙钛矿晶相，高烧结活性的亚微米级Ｐｂ（ＺｒｘＴｉ１－ｘ）Ｏ３（ＰＺＴ）微粉。     

Enhanced and stable strain memory in Mn‐doped Pb(Mn1/3Sb2/3)O3–Pb(Zr,Ti)O3 ceramics realized by sesquipolar loading

The negative electric field, field cycling and frequency dependence of strain memory effect in poled and aged Mn‐doped Pb(Mn_1/3Sb_2/3)O₃–Pb(Zr,Ti)O₃ (PMS–PZT) piezoceramics under sesquipolar loading were investigated. The strain memory effect of Mn‐doped PMS–PZT is especially sensitive to the applied negative electric field. Maximum strain memory of 0.32% is achieved when the negative electric field is around negative coercive field of ~2.1 kV/mm, which can be ascribed to the partially depoled state with randomized domains. And this strain memory shows very good cycling stability, varying less than 5% up to 10⁴ cycles, while almost 40% degradation is found under bipolar signal. In addition, due to the stabilized defect dipoles, the strain memory exhibits stable characteristic over a broad frequency range from 0.01 Hz to 20 Hz. The results may shed new insights into designing the novel strain memory actuators where stable strain state could be realized after the removal of electric field.     

(Pb,La)(Zr,Sn,Ti)O3 陶瓷、锆锡钛酸铅镧/聚偏氟乙烯-三氟乙烯复合材料的介电性能

用固相烧结法,在1200℃烧结2．5h的条件下,制备了(Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3(PLZST)四方相陶瓷和陶瓷粉末,并将其与聚偏氟乙烯-三氟乙烯[polyvinylidene fluoride—trifluoroethylene,P(VDF-TrFE)]相复合制备了70％(体积分数)PLZST／P(VDF—TrFE)复合材料。用3～4MeV、剂量为60Mrad的电子束对PLZST陶瓷及其复合材料进行处理,测量其辐照前后的介电温谱,研究其弛豫性能的变化。结果表明：电子束辐照对PLZST陶瓷的介电温谱几乎没有影响,没有改变它的非弛豫特征;70％PLZST／P(VDF-TrFE)复合材料由于两相界面间的耦合作用产生微畴而具有弛豫特征,而辐照处理对P(VDF—TrFE)内部铁电宏畴的破坏使得其弛豫性能得到显改善,从而获得了一种良好的弛豫型复合材料。     

0.06BiYbO3-0.94Pb(Zr0.48Ti0.52)O3三元系压电陶瓷的氧化物掺杂改性研究

针对新一代声波测井仪器对其核心元件压电陶瓷兼具高居里温度、高压电系数以及高稳定性要求的迫切需求,本文采用传统的固相反应-无压烧结技术制备了一种0.06BiYbO₃-0.94Pb(Zr_0.48Ti_0.52)O₃(BY-PZT)三元系压电陶瓷,并研究了四种氧化物掺杂对其微观结构及电学性能的影响。由XRD和SEM表征可知所有样品均呈纯四方相钙钛矿结构,掺杂Cr₂O₃的样品平均晶粒尺寸最大。介电温谱和谐振频谱研究证实四种氧化物掺杂均能提高其介电性能的温度稳定性。掺杂La₂O₃的样品介电常数温度系数(Tk_ε)最低,掺杂MnO₂的样品机械品质因素(Q_m)最高,而掺杂CeO₂的样品抗热退极化性能最好。高温复阻抗(Cole-Cole图)分析表明,Cr₂O₃掺杂能够显著提高BY-PZT陶瓷的高温电阻率,陶瓷在高温下的电导行为主要由晶界响应控制。综合来看,掺杂La₂O₃的样品兼具高居里温度(T_C=397 ℃)和高压电系数(d₃₃=290 pC/N),并且在300 ℃退火4 h后d₃₃仍能保持在270 pC/N左右,有望在极限工作温度为300 ℃的高温压电器件中获得应用。     

Effect of pore size and porosity on piezoelectric and acoustic properties of Pb(Zr0.53Ti0.47)O3 ceramics

We studied the effect of porosity and pore morphology on the functional properties of Pb(Zr_0.53Ti_0.47)O₃ (PZT) ceramics for application in high frequency ultrasound transducers. By sintering a powder mixture of PZT and polymethylmetacrylate spherical particles (1.5 and 10?μm) at 1080°C, we prepared ceramics with ～30% porosity with interconnected micrometer sized pores and with predominantly ～8?μm spherical pores. The acoustic impedance was ～15?MRa for both samples, which was lower than for the dense PZT. The attenuation coefficient α (at 2.25?MHz) was higher for ceramics with ～8?μm pores (0.96?dB?mm^??1?MHz^??1), in comparison to the ceramic with smaller pores (0.56?dB?mm^??1?MHz^??1). The high α value enables the miniaturisation of the transducer, which is crucial for medical imaging probes. The dielectric and piezoelectric coefficients, polarisation, and strain response decreased with increased porosity and decreased pore/grain size. We suggest a possible role of pore/grain size on the switching behaviour.     

Direct-Write Fabrication of Pb(Nb,Zr,Ti)O3 Devices: Influence of Paste Rheology on Print Morphology and Component Properties

Lead niobium zirconate titanate (PNZT) pastes with tailored rheological properties have been developed for direct-write fabrication of thick-film capacitor elements in highly integrated, multifunctional electroceramic devices. Such pastes exhibited pseudoplastic behavior with a low shear apparent viscosity of roughly 1 × 10⁶ cP. On aging, the degree of shear thinning and the low shear apparent viscosity decreased. Pastes prepared from as-received powders attained printable, steady-state viscosities of ∼2 × 10⁵ cP after 50 days of aging. In contrast, pastes prepared from dispersant-coated powders showed no measurable rheological changes after 1 day of aging. Square elements were patterned on dense alumina substrates or Teflon sheets. Leveling behavior as a function of time for single line prints, and the resulting surface topographies of dried PNZT films were measured by laser profilometry. PNZT layers sintered at varying temperatures between 950° and 1050°C for 5 h in either air or a lead-rich atmosphere yielded porous microstructures as revealed by scanning electron microscopy (SEM). Such layers exhibited dielectric constants ( K ) of 1400–1570 at 1 kHz with dissipation factors ( D ) of less than 4.1%.     

High‐Energy Storage Performance in (Pb0.98La0.02)(Zr0.45Sn0.55)0.995O3 AFE Thick Films Fabricated via a Rolling Process

(Pb_0.98La_0.02)(Zr_0.45Sn_0.55)_0.995O₃ antiferroelectric (AFE) thick films with a thickness of about 85 μm were successfully fabricated via a rolling process using an improved sintering method, and all specimens showed high‐energy‐storage performance. The X‐ray diffraction, SEM pictures, and hysteresis loops confirmed that the sintering temperature had an important influence on the microstructures, dielectric properties and energy storage performance of AFE thick films. The grain size and the storage efficiency increased with the increasing sintering temperature, the energy storage performance was enlarged by the rolling process. As a result, a maximum recoverable energy density of 7.09 J/cm³ with an efficiency of 88% was achieved at room temperature, together with stable energy‐storage behavior, which was almost three times higher than that (2.43 J/cm³) of the bulk ceramics counterparts. The results demonstrated that the improved method was an effective way to improve the breakdown strength and energy storage performance of AFE thick films, and (Pb_0.98La_0.02)(Zr_0.45Sn_0.55)_0.995O₃ AFE thick films were a promising material for high‐power energy storage.     

Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

冲击波合成Pb(Zr0.95Ti0.05)O3粉体的结构和特性

采用Pb3O4，ZrO2和TiO2等氧化物为原料，Nb2O5为掺杂剂，利用柱面冲击波加载装置合成了Pb(Zr0.95Ti0．05)O3(PZT95／5)粉体。用X射线衍射、红外光谱、扫描电镜和热重-差热分析等多种测试手段对该粉体进行了表征，研究了冲击波技术对合成粉体的结构和性能的影响。结果表明：冲击波能合成钙钛矿型PZT95／5粉体，与固相法合成粉体相比，其晶体结构发生畸变，粉体活性提高。     

Combustion synthesis and electromagnetic properties of nanocrystalline Pb(Zr0.52Ti0.48)O3

The properties of nanocrystalline lead zirconate titanate [PZT, Pb(Zr_0.52Ti_0.48)O₃] thick films and pellets synthesized by self-propagating auto combustion route using sucrose as a fuel are reported. The X-ray diffraction reveals the formation of nanocrystalline tetragonal PZT having a particle size of 5.52 nm in thick films and 7.08 nm in bulk material. SEM images show the grain size of 300–400 nm with some agglomeration, as well as modified open grain boundaries and grain growth in the PZT thick film as compared to the bulk material. The DC electric resistivity of PZT shows semiconducting behavior. We also characterized the 8–18 GHz microwave insertion loss, absorption, complex permittivity, and microwave conductivity of synthesized materials. The real part of permittivity and dielectric loss were found to decrease with increasing frequency.     

Dielectric Properties of Pb(Fe2/3W1/3)O3–PbTiO3 Solid-Solution Ceramics

The dielectric properties of (1− x )Pb(Fe_2/3W_1/3)O₃· x PbTiO₃ solid solutions were investigated from 10² to 10⁶ Hz in the temperature range 150–600 K. The phase transition of Pb(Fe_2/3W_1/3)O₃ (PFW) was shifted by PbTiO₃ (PT) additions to higher temperatures at a rate of 6.3 K/mol% of PT. The temperature dependence of dielectric permittivity showed a sharper transition as the PT content increased. Dielectric measurements in a wide temperature range showed the presence of a second set of dielectric peaks at higher temperatures (350–600 K), besides the ferroelectric–paraelectric phase transition. This second set of peaks vanished when the samples were annealed in nitrogen. The activation energy values for the second relaxation varied between 0.50 and 0.63 eV, in agreement with the conduction activation energy determined for each sample. This relaxation is apparently related to electron holes.