低相变场细电滞回线(Pb,La)(Zr,Sn,Ti)O_3反铁电陶瓷的研究

对远离反铁电-铁电准同型相界的(Pb,La)(Zr,Sn,Ti)O3反铁电组分进行Ba2+掺杂,制备出了细电滞回线、低相变电场的反铁电陶瓷,反铁电-铁电相变电场仅为1.5kV/mm,电场回滞减小到0.2kV/mm,并且极化强度和应变量随电场增大几乎呈线性变化,可通过调节电场大小得到不同的应变量,有利于开辟这类材料新的应用领域。     

脉冲电场诱导的相变研究

反铁电陶瓷材料在电场诱导下发生反铁电-铁电相变.为了研究快速电场诱导相变,诱导电场选择高压脉冲电源产生的脉冲电场.反铁电陶瓷选用Pb(Zr,Sn,Ti)O3相图中位于反铁电-铁电相界附近,正向相变电场小于40kV/cm的锆锡钛酸铅.脉冲电源输出波形为2.7 μs电压脉冲,测量陶瓷样品两端的电压波形与所通过的电流波形,作出正向半周期的"脉冲电滞回线".可以看到反铁电陶瓷在脉冲电场诱导下发生了相变.     

铅基(Pb,La)(Zr,Ti)O_3反铁电厚膜微驱动结构的特性测试

采用金属醇盐为前驱体的溶胶-凝胶工艺,实现了PLZT反铁电厚膜晶圆级的制备。基于铅锆反铁电材料的相变应变效应和快速响应特性,结合微纳兼容制造关键技术,研制出具有大应变、快响应、低驱动特性的硅基(Pb,La)(Zr,Ti)O3反铁电厚膜微悬臂梁构件。3种激励模式的测试结果表明,定频模式下梁的最大位移和速率相对于扫频模式下高出数倍,且定频模式(Square)更有利于激发反铁电材料相变,使得微悬臂梁驱动构件产生更大的应变和更快的响应速度,为大行程驱动位移和快速响应新型微执行构件的设计提供一种新的技术途径。     

掺铌Pb(Zr,Sn,Ti)O3反铁电-铁电转换电场的研究

研究了掺铌PZST反铁电陶瓷中组份和温度对诱导反铁电－铁电相变转换电场的影响,测定了Pb0.99Nb0.02((Zr0.80Sn0.20)1-yTiy)0.98O3系中正向转换电场EF与组份y(Ti)的关系和电极化前后的反铁电／铁电相界。实验测量结果显示,某组份y(Ti)的反映电－铁电转换强度大小取决于该组份与铁电／铁电相界组份的差距。在Pb0.99Nb0.02((Zr0.80Sn0.20)1-yTiy)0.98O3系中随着试样温度升高,反向转换电场EB保持不变,正向转换电场EF和电滞△E降低。这一现象表明温度有助于降低反铁电－铁电相变的应能使得电场诱导反铁电－铁电相变容易进行,因此可以采用加热电极化方法来降低极化电场强度。     

PbZrO3晶体反铁电相至电场感应铁电相相变的研究

仔细研究了电场感应PbZrO3铁电相的晶体结构。在PbZrO3处于反铁电相时，各离子位移方向与极轴垂直。在外电场感应下，Pb离子沿极轴方向有相同方向0．17A的位移，从而使晶体呈现铁电相特征，发生反铁电-铁电相变。此铁电相称之为电场感应铁电相（EFI，Electric—Field—Induced）。通过结构对称性分析，确定EFI铁电相的对称性是C2mm（G2v），用极矢量Ps作为序参量来描述相变时对称性的变化是合适的。     

原位XRD测试PLZT铁电陶瓷的电致畴变

通过传统固相法合成了四方相结构、晶粒平均尺寸1~2μm且化学组成约为Pb0.93La0.07(Zr0.52,Ti0.48)O3的铁电陶瓷试样。利用自制的电加载装置与常规XRD测试仪器联用,在不同外加直流电场作用下实现了陶瓷试样的原位XRD测试,通过分析(002)和(200)的相对峰强变化,计算了90°畴转向率,并与非原位XRD测试得到的数据进行比较,初步分析了外加电场卸载前后铁电陶瓷的电致畴变行为。结果表明,高达7%的a畴在电场卸载瞬间会发生回转。     

钙钛矿型Pb基反铁电储能材料研究进展

反铁电材料在发生场致反铁电-铁电相变过程中伴随着巨大应变和能量的储存和释放,故在高密度储能器件和机电换能器上极具应用潜力。综述了具有钙钛矿结构的Pb基反铁电体结构特点与性能调控,特别是Pb(Zr,Ti)O3(PZT)基反铁电储能材料的研究进展与存在问题。重点讨论了几类典型元素掺杂Pb基反铁电薄膜材料研究的最新进展。简要介绍了适应无铅化要求、环境友好的无铅钙钛矿型反铁电-铁电相变材料。最后对当前钙钛矿型Pb基反铁电材料研究与应用中尚需深入探究的问题进行了总结。     

快速退火工艺条件下温度对Bi4Ti3O12铁电薄膜微观结构与性能的影响

采用快速退火工艺在Pt/Ti/SiO2/p-Si衬底上制备了Bi4Ti3O12铁电薄膜.研究了退火温度对薄膜微观结构、铁电特性及介电性能的影响.研究表明:退火温度对Si基Bi4Ti3O12铁电薄膜晶相结构的影响显著,对晶粒尺寸和表面形貌的影响较小,但退火温度超过800℃后会出现焦绿石等杂相;低于750℃时,薄膜的剩余极化随退火温度升高而增大,高于750℃时却有所减小,但矫顽电场随退火温度升高而逐渐降低;退火温度对薄膜的漏电流密度有一定的影响,薄膜的漏电流密度在200kV/cm极化电场作用下低于3×10-9A/cm2,750℃时的剩余极化和矫顽电场分别为11μC/cm2和77kV/cm,具有较好的铁电和介电性能.     

电场诱导PZST陶瓷反铁电-铁电相变

研究了ＰＺＳＴ陶瓷电场诱导反铁电－铁电相变。当外加电场大于相变临界参数ＥＡＦＥ－ＦＥ时,样品由反铁电态诱导为铁电态,并在宏观性能上产生突变：极化强度和纵向应变分别由零跃变到大约３０μＣ／ｃｍ＾２和０．３％,介电常数下降５０％。利用直流偏压原位Ｘ射线衍射表征为相变时晶格结构的变化,结果表明,伴随着相变的发生,晶格结构由反铁电四方相转变为铁电三方相。     

原子氧处理减小多晶PZT-PMN薄膜漏电流的实验研究

漏电流是铁电薄膜应用过程中的关键问题。本文通过磁控溅射法制备了结晶性能良好的铌镁锆钛酸铅(PZT-PMN)铁电薄膜,并在室温下用原子氧对其进行处理,研究了原子氧对PZT-PMN薄膜表层微观结构和漏电流的影响。实验结果表明:经原子氧处理后的PZT-PMN薄膜,①表面粗糙度下降且有非晶层形成;②表层有大量的氧原子进入;③漏电流密度减小了大约一个数量级,外加电压为2.5 V时,未处理样品的漏电流密度为3×10-5A/cm2,处理样品的漏电流密度降为4.5×10-6A/cm2。原子氧对PZT-PMN薄膜内部晶界、缺陷的钝化是薄膜漏电流减小的原因。     

Direct current electric field adjustable phase transformation behavior in (Pb,La)(Zr,Ti)O3 antiferroelectric thick films

(Pb,La)(Zr,Ti)O₃ antiferroelectric 1.4 μm-thick films have been prepared on Pt (111)/Ti/SiO₂/Si(100) substrates by sol–gel process. The structures and dielectric properties of the antiferroelectric thick films were investigated. The films displayed pure perovskite structure with (100)-preferred orientation. The surface of the films was smooth, compact and uniform. The antiferroelectric (AFE) characterization have been demonstrated by P (polarization)-E (electric field) and C(capacitance)-V (DC bias) curves. The AFE–ferroelectric (FE) and FE-to-paraelectric (PE) phase transition were also investigated as coupling functions of temperature and direct current electric field. With the applied field increased, the temperature of AFE-to-FE phase transition decreased and the FE-to-PE phase shifted to high temperature. The AFE-to-FE phase transition was adjustable by direct current electric field. (Pb,La) (Zr,Ti) O₃ antiferroelectric films have broad application prospects in microelectromechanical systems because of the phase transition.     

Polarization-electric field relations of ferroelectric/antiferroelectric layered ceramics in Pb(Nb, Zr, Sn, Ti)O3 system

Ferroelectric/antiferroelectric bi-layer ceramics with different ferroelectric and antiferroelectric phase thickness ratio (FE/AFE thickness ratio) in Pb(Nb, Zr, Sn, Ti)O₃ system were prepared and characterized. With increasing the maximum external electric field from 0 to 40 kV/cm, polarization-electric field relation was always ferroelectric-like or underwent an antiferroelectric-ferroelectric transition, depending on the FE/AFE thickness ratio. All layered ceramics showed ferroelectric-like hysteresis loops with maximum external electric field of 40 kV/cm, and much higher remanent polarizations were attained than those of the ferroelectric/antiferroelectric heterostructures reported previously.     

Effect of compositional variations on electrical properties in phase switching (Pb,La)(Zr,Ti,Sn)O3 thin and thick films

The composition-dependent electrical properties in (Pb,La)(Zr,Ti,Sn)O₃ antiferroelectric-ferroelectric phase switching thin and thick films have been systematically studied and compared with bulk ceramics. The films were deposited on Pt-buffered silicon substrates by a sol-gel method. The results show that the dependence of low-field dielectric properties on compositions in the films is similar to that in bulk ceramics but the variation of high field properties (polarization or hysteresis loops) is quite different, which may be attributed to the special mechanical boundary condition of the films. While all the films with compositions in the antiferroelectric tetragonal region in the phase diagram demonstrate the existence of remanent polarization in the hysteresis loops, the films with zero remanent polarization can be obtained in the antiferroelectric orthorhombic region. This is because the films are under high tensile stress due to the thermal mismatch between the film and substrate, which tends to stabilize the ferroelectric phase and causes the retention of ferroelectric phase for the films in the antiferroelectric tetragonal region because of their relatively small free energy difference between the antiferroelectric phase and ferroelectric phase.     

Field-induced strain of (Pb, La)(Zr, Ti)O3 epitaxial films grown by metal organic chemical vapor deposition

Two micrometers thick (Pb, La)(Zr, Ti)O₃ [PLZT] films with wide composition range were epitaxially grown on (1 0 0)SrRuO₃ bottom electrode layers epitaxially grown (1 0 0) SrTiO₃ substrates by metal organic chemical vapor deposition. Constituent phase of the films were found to be almost the same with the reported phase diagram for the sintered body except for the wider coexistence region of tetragonal and rhombohedral phases. The change of the measured field-induced strain with the electric field was almost respond to the square of the polarization of the films except the negative strain region, but the magnitude was different. This is due to the increase of the electrostatic coefficient of the film with increasing the La/(Pb + La) ratio. As a results, field induced strain of the PLZT film was found to be controlled by adjusting the composition of PLZT films.     

The characteristics of (Pb,La)(Zr,Sn,Ti)O<Subscript>3</Subscript> ceramics synthesized by coprecipitation method compared to conventional mixed oxide method

The relaxor antiferroelectric (Pb,La)(Zr,Sn,Ti)O₃ powders were synthesized by conventional mixed oxide method and coprecipitation method. The XRD patterns show that pure perovskite phase formation temperature was 700 °C for the coprecipitation method and that was 1,100 °C for the conventional mixed oxide method. Effect of the methods on sintering behavior and microstructures of the ceramics has been investigated by SEM. Both the samples exhibit typical antiferroelectric double hysteresis loops with maximum polarization of 18.2 μC/cm², forward-switching field of 6.2 kV/mm by conventional mixed oxide method, and 33.1 μC/cm², 4.3 kV/mm by coprecipitation method, respectively.     

Effect of the orientation on the ferroelectric-antiferroelectric behavior of sol-gel deposited (Pb,Nb)(Zr,Sn,Ti)O3 thin films

The (Pb,Nb)(Zr,Sn,Ti)O₃ (PNZST) antiferroelectric thin films were prepared on two different substrates by sol-gel methods. Films derived on the LNO/Pt/Ti/SiO₂/Si substrates showed a strong (100) preferred orientation. The dependence of electrical properties derived on the Pt/Ti/SiO₂/Si and LNO/Pt/Ti/SiO₂/Si substrates have been studied, with the emphasis placed on field-induced phase switching from the antiferroectric to the ferroelectric state. The PNZST thin films deposition on two kinds of substrates show different phase transition behavior and associated properties such as antiferroelectric (AFE) to ferrroelectric (FE) switching field E_AFE-FE, FE to AFE switching field E_FE-AFE and the hysteresis ΔE=E_AFE-FE−E_FE-AFE.     

Structure and electrical properties of (111)-oriented Pb(Mg1/3Nb2/3)O3-PbZrO3-PbTiO3 thin film for ultra-high-frequency transducer applications

Ternary lead magnesium niobate-lead zirconate titanate system 0.4Pb(Mg(1/3)Nb(2/3))O(3)-0.25PbZrO(3)-0.35PbTiO(3) (40PMN-25PZ-35PT) thin film with a thickness of 1.5 μm was grown on Pt(111)/Ti/SiO(2)/Si substrate via chemical solution deposition. X-ray diffraction and transmission electron microscopy results suggested the film obtained was highly (111)-oriented. The remanent polarization and coercive electric field of the film were found to be 25.5 μC/cm(2) and 51 kV/cm, respectively. In addition, at 1 kHz, the dielectric constant was measured to be 1960 and the dielectric loss 0.036. The film was observed to undergo a diffuse ferroelectric-to-paraelectric phase transition at around 209°C. The leakage current appeared to depend on the voltage polarity. If the Au electrode was biased positively, the leakage current was dominated by the Schottky emission mechanism. When the Pt electrode was biased positively, the conduction current curve showed an ohmic behavior at a low electric field and space-charge-limited current characteristics at a high electric field.     

A study on the electrical properties of Pb(Zr, Ti)O3 thin films crystallized by the electrical resistive heating of Pt thin film

The electrical properties of Pb(Zr, Ti)O₃ thin films annealed by Pt thin film heater were investigated. By the thin film heater, we successfully crystallized Pb(Zr, Ti)O₃ thin films at a high temperature above 750 °C in a few seconds. The thin film heater has some advantages, such as a low thermal budget, little Pb-loss and enhanced surface morphology compared with the conventional furnace because it has a fast heating rate. The electrical properties of the Pb(Zr, Ti)O₃ thin film crystallized by thin film heater improved considerably comparing to those crystallized in conventional furnace. The remanent polarization, breakdown field, and leakage current density measured to be 22.7 μC/cm², 853 kV/cm, and 6.93 × 10⁻⁷ A/cm², respectively.     

溶胶-凝胶法制备Bi0.975La0.025Fe0.975Ni0.025O3铁电薄膜的结构及物理性能

采用溶胶-凝胶法在Pt/Ti/SiO_2/Si(111)衬底上制备了Bi_(0.975)La_(0.025)Fe_(0.975)Ni_(0.025)O_3(BLFNO)铁电薄膜。利用X射线衍射(XRD)、原子力显微镜(AFM)及其压电模式(PFM)对薄膜的晶体结构、表面形貌以及铁电畴结构进行了研究。研究发现,BLFNO为结晶良好的钙钛矿结构多晶薄膜,且薄膜表面颗粒生长均匀。PFM测试图显示铁电薄膜在自发极化下的铁电畴结构清晰,铁电电容器具有良好的铁电性能。应用铁电测试仪对Pt/BLFNO/Pt电容器进行测量,得到了饱和性良好的电滞回线。在828kV/cm的外加电场下,Pt/BLFNO/Pt电容器的剩余极化强度为74.3μC/cm~2,表明La、Ni的共掺杂没有明显抑制铁电电容器的剩余极化强度,铁电电容器具有良好的铁电性能。漏电流研究结果表明,La、Ni元素的共掺杂有效降低了薄膜的漏电流密度,在277.8kV/cm外加电场下漏电流密度在10-4 A/cm2量级,明显小于纯BFO薄膜的漏电流密度。正半支漏电流曲线满足SCLC导电机制,对于负半支曲线,当电场强度大于22.2kV/cm时,同样遵循SCLC导电机制;但是,当电场强度小于22.2kV/cm时,曲线斜率约为4.8,表明参与导电贡献的电子数较多,归因于极浅陷阱俘获的电子在外加电场作用下参与了导电行为。室温下磁滞回线测试结果表明BLFNO薄膜具有反铁磁性质。