SiO2对低温烧结压电陶瓷PMNNS的性能影响

在烧结温度为1020℃下,采用固相二步合成法制备了Pb(Ni1/3Nb2/3)0.05(Mn1/3Nb2/3)0.04(Mn1/3Sb2/3)0.01(Zr1/2Ti1/2)0.9O3(PMNNS)压电陶瓷,研究了加入不同掺杂量的SiO2对陶瓷的结构与机电性能的影响。结果表明:加入SiO2可以明显地降低烧结温度;而且当SiO2的掺杂量为0.1%时,陶瓷的性能最佳,其性能如下:d33=331 pC/N,tanδ=0.0041,kp=0.62,Qm=1326,εr=917。     

沿[001]c方向极化PZN-xPT单晶的声表面波性能

利用半波解法对三方相、四方相及准同型相界附近,沿[001]c方向极化(1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3晶体的声表面波传播特性进行了对比研究.结果表明,位于准同型相界附近的0.92Pb(Zn1/3 Nb2/3)O3-0.08PbTiO3晶体的声表面波性能明显优于三方相0.955Pb(Zn1/3Nb2/3)O3-0.045PbTiO3和四方相0.88Pb(Zn1/3Nb2/3)O3-0.12PbTiO3晶体.具有复杂工程畴结构的0.92Pb(Zn1/3Nb2/3)O3-0.08PbTiO3晶体声表面波机电耦合系数显著高于四方相晶体.同时0.92Pb(Zn1/3 Nb2/3)O3-0.08PbTiO3晶体具有相对较小的声表面波相速度和能流角.因此,该晶体适合制作机电性能优越的声表面波器件.     

PZT基反铁电材料研究进展

在综述Pb(Zr,Ti)O3(PZT)基反铁电材料的研制与性能研究进展的基础上,重点探讨了PZT95/5反铁电材料和在PZT基础上掺杂改性的Pb(Zr,Sn,Ti)O3(PZST),(Pb,La)(Zr,Sn,Ti)O3 (PLZST)反铁电材料.总结了利用La3+、Nb4+、Hf4+、Sr2+、Ba2+和Nd3+等离子对富锆PZT以及PZST粉体、陶瓷以及薄膜材料的掺杂取代改性研究.讨论了各类PZT基反铁电材料的铁电(FE)-反铁电(AFE)相变机理以及其场致应变性能.展望了PZT基反铁电材料今后研究与应用的发展方向.     

(La0.5Sr0.5)CoO3为电极的Pb(Zr0.4Ti0.6)O3和Pb(Zr0.2Ti0.8)O3铁电电容器结构及电学性能

分别采用磁控溅射法和溶胶-凝胶法(Sol-gel)制备了(La0.5Sr0.5)CoO3(LSCO)和Pb(Zr1-xTix)O3(PZT)薄膜,在Pt(111)/Ti/SiO2/Si基片上构架了LSCO/Pb(Zr0.4Ti0.6)O3(PZT(40/60))/LSCO和LSCO/Pb(Zr0.2Ti0.8)O3(PZT(20/80))/LSCO铁电电容器,研究了两种铁电电容器的结构和性能。XRD结构分析表明:两种四方相的不同Zr/Ti比例的PZT薄膜均为结晶良好的多晶钙钛矿结构。在5 V测试电压下,LSCO/PZT(40/60)/LSCO和LSCO/PZT(20/80)/LSCO两种铁电电容器的剩余极化强度(Pr)和矫顽场(Ec)分别为:28μC/cm2和1.2 V以及32μC/cm2和2 V。相对于PZT(40/60),PZT(20/80)具有较大的剩余极化强度和矫顽场,是由于其矩形度(c/a)较大。两种电容器都具有较好的脉宽依赖性和抗疲劳性。在5 V的测试电压下,LSCO/PZT(40/60)/LSCO电容器的漏电流密度为3.2×10-5A/cm2,LSCO/PZT(20/80)/LSCO电容器的漏电流密度为3.11×10-4A/cm2,经拟合分析发现:在0～5 V的范围内,两种电容器都满足欧姆导电机制。     

SrRuO3导电层对快速退火制备Pb(Zr,Ti)O3薄膜结构和性能的影响

采用溶胶-凝胶法在Pt/Ti/SiO2/Si基片上,制备了Pt/Pb(Zr,Ti)O3(PZT)/Pt和SrRuO3(SRO)/PZT/SrRuO3(SRO)异质结电容器,并研究了快速退火条件下SRO导电层对PZT结构和性能的影响.XRD测试表明,两种结构电容器中的PZT薄膜均为钙钛矿结构,SRO/PZT/SRO、Pt/PZT/Pt均具有较好的铁电性和脉宽依赖性,5 V电压下两电容器的剩余极化强度Pr和矫顽电压Vc分别为28.3 μC/cm2、1.2 V和17.4 μC/cm2、2.1 V.在经过1010次翻转后,SRO/PZT/SRO铁电电容器疲劳特性相对于Pt/PZT/Pt电容器有了较大的改善,但SRO导电层的引入也带来了漏电流增大的问题.     

含NiTi阻挡层的硅基(La0.5Sr0.5)CoO3/Pb(Zr0.4Ti0.6)O3/(La0.5Sr0.5)CoO3铁电电容器异质结

应用磁控溅射法制备的非晶NiTi薄膜作阻挡层,在Si (100)衬底上构造了(La0.5Sr0.5)CoO3/ Pb(Zr0.4Ti0.6)O3/(La0.5Sr0.5)CoO3(LSCO/PZT/LSCO)铁电电容器异质结,研究了Pb(Zr0.4Ti0.6)O3铁电薄膜的结构和物理性能.实验发现LSCO/PZT/LSCO铁电电容器具有良好的电学性能,在417kV/cm的驱动场强下,PZT铁电电容器具有较低的矫顽场强(125kV/cm)和较高的剩余极化强度(19.0μC/cm2),良好电容-电压特性(C-V)和保持特性,铁电电容器经过1010次反转后,极化强度没有明显下降,表明了非晶NiTi薄膜可以用作高密度硅基铁电存储器的扩散阻挡层.     

溶胶电泳沉积法制备PZT压电厚膜及其性能研究

采用溶胶-凝胶方法制备Pb(Zr0.52Ti0.48)O3(PZT)纳米粉末,将此粉末按一定比例加入到同成分PZT溶胶中,采用溶胶-电泳沉积技术在ITO玻璃衬底上制备PZT厚膜.采用X射线衍射分析、SEM及HP4294A阻抗分析仪等对PZT膜进行了微观结构和介电性能测试,研究了电泳电压、热处理温度及电泳时间对PZT膜结构及膜厚的影响,结果表明,在1V电压下进行电泳,600℃热处理20min,可以得到表面均匀平整的纯钙钛矿结构PZT膜,以(110)择优取向,通过控制电泳时间可有效控制膜的厚度.获得了膜厚为30μm、介电常数达到ε33T/ε0=781、介电损耗为tanδ=0.0083、剩余极化与矫顽电场强度分别为24.6μC/cm2与61.9kV/cm铁电性能较好的PZT膜材料.     

B位四价Sn4+, Zr4+取代对Ba(Zn1/3Nb2/3)O3系统微观结构的影响

采用传统的固相陶瓷烧结工艺,利用四价正离子Sn4+、Zr4+取代Ba(Zn1/3Nb2/3)O3陶瓷的B位Zn2+、Nb5+,研究其对Ba(Zn1/3Nb2/3)O3系统微观结构的影响.四价Sn4+、Zr4+取代B位Zn2+、Nb5+可以形成固溶体,系统的主晶相仍为立方相.系统晶格常数a随着Sn4+取代量的增加而呈线性增大,相同Sn4+取代量下随着烧结温度的增加,晶格常数a增大.BaZrO3(BZ)的加入可减少第二相的生成.Sn4+、Zr4+均可改善系统烧结特性,加快致密化形成.     

Pb0.92Sr0.08-xBax(Sb2/3Mn1/3)0.05Zr0.48Ti0.47O3的制备与性能研究

采用传统固相烧结法制备了Pb0.92Sr0.08-xBax(Sb2/3 Mn1/3)005Zr0.48Ti0.47O3(PSBSM-PZT)压电陶瓷样品.研究了不同Sr2+、Ba2+掺杂含量对样品的相结构、微观形貌、压电和介电性能的影响.结果显示:所有样品均为钙钛矿结构.而当x=0.02～0.06时,陶瓷样品组分位于准同型相界区(MPB).由于位于准同型相界区域的陶瓷样品对于电畴的转向具有促进作用,所以处于MPB区域的陶瓷样品具有较大的压电和介电性能,但同时由于电畴转向带来的较大内摩擦和结构损耗,从而提高了材料的机械损耗和介电损耗.当x=0.02时的陶瓷样品获得最佳的综合性能:d33=346 pC/N,kp=0.58,Qm=1217,εr=1724,tanδ=0.774;.     

弛豫铁电单晶的生长、性能及应用研究

弛豫铁电单晶因其具有优异的压电和热释电性能而成为下一代高性能压电换能器和红外热释电探测器用的多功能材料。利用坩埚下降法生长出了大尺寸、高质量的弛豫铁电单晶PMNT(Pb(Mg1/3Nb2/3)O3-xPbTiO3),以及高居里点PIMNT(xPb(In1/2Nb1/2)O3-yPb(Mg1/3Nb2/3)O3-zPbTiO3)单晶。系统研究了其组分诱导相变、电场诱导相变规律,以及相结构、畴结构对晶体高压电性能的影响。系统表征了PMNT单晶的力学、电学、压电、和热释电性能。系统研究了PMNT单晶及掺杂改性的PMNT单晶的结构和性能。利用弛豫铁电单晶PMNT及其复合材料制作了医用超声换能器,其性能相比于PZT陶瓷制作的换能器有大幅度提高;利用PMNT制作了压电能量收集器,实现了高能量密度的机械振动能量收集;利用Mn掺杂的PMNT单晶制作了热释电红外探测器,其电压响应率Rv(500 K,12.5 Hz,25℃)达到14540 V/W,比探测率D*(500 K,12.5 Hz,25℃)达到1.07×109 cmHz1/2W-1;利用PMNT单晶制作了低噪声、高灵敏度的交变弱磁传感器,探测性能达到1 pT.Hz-1/2。     

Pb过量对以Ti-Al为阻挡层的硅基铁电电容器极化翻转性能的影响

以射频磁控溅射法生长的La0.5Sr0.5CoO3( LSCO)为电极,采用溶胶-凝胶法在以Ti-Al为导电阻挡层的Si基片上生长了用不同Pb过量前驱体溶液(溶胶)制备的LSCO/Pb( Zro4Ti0.6)O3(PZT)/LSCO电容器,以此构造了Pt/LSCO/PZT/LSCO/Ti-Al/Si异质结.Pb过量对LSCO/PZT/LSCO电容器极化翻转性能的影响表明:不同Pb过量溶胶对电容器的极化翻转性能影响很大,其中Pb过量15;的溶胶制备的样品在550℃常规退火1h后相对具有较好的翻转性能.在5V的外加电场下,LSCO/PZT/LSCO电容器的矫顽电压和剩余极化强度分别为1.25V和24.6μC/cm2.疲劳和电阻率测试分析表明:在经过109翻转后,不同样品的抗疲劳性能均很好,而电阻率随前驱体溶液Pb过量的增加呈现下降的趋势.     

Stability and formation of pyrochlore phase in doped Sr0.8Bi2.3Ta2O9 thin films

Ferroelectric thin films of bismuth-containing layered perovskite Sr_0.8Bi_2.3Ta_2−xM_xO₉ (SBTM), where M is V, Ti, W, and Zr, have been prepared on Pt/Ti/SiO₂/Si substrates using the metal-organic decomposition method. The effect of the incorporated B-site cations on pyrochlore phase formation and microstructure evolution of SBTM films was investigated. The pyrochlore phase formation has been identified due to out-diffusion of titanium from underneath platinum layer to participate in the reaction with the films. Furthermore, the formation of pyrochlore phase in the SBTM films has been observed strongly dependent on the characteristics of incorporated M cation. The substitution of both W and V for Ta leads to the formation of pyrochlore phase at lower annealing temperature (750–800 °C). On the other hand, the addition of Zr can retard the formation of pyrochlore phase from 850 to 900 °C. A model based on the binding energy of octahedral structure is used to elucidate the formation and stability of the pyrochlore phase present in the SBT film.     

以TiO2粉体为钛源水热合成Pb(Zr0.52Ti0.48)O3晶粒机理

用水热法合成了Pb(Zr0.52Ti0.48)O3(PZT)超细晶粒.通过对合成粉晶体的物相与晶体形貌的表征和对生成物中TiO2残余量的测定,初步分析了PZT粉晶粒形成的机理.在反应初期,随着温度的升高,TiO2粒子逐渐溶解.进入溶液的钛氧基团与溶液中的羟基相作用发生羟基化反应,形成钛的氢氧化物.钛与锆的氢氧化物相互作用,形成生长基元,它们与pb2+离子一起在PZT晶核生长界面上叠合、脱水、结晶,从而使PZT晶粒长大.     

溅射制备不同厚度Pb(Zr0.52Ti0.48)O3薄膜结晶态的研究

研究了射频磁控溅射的Pb(Zr0.52Ti0.48)O3(PZT52/48)薄膜在退火晶化时,厚度对其结晶态及表面形貌的影响.首先利用Materials Studio软件对PZT分子进行了模拟,并模拟了X射线衍射(XRD)得到PZT的特征峰图;实验上,采用退火炉对不同厚度的PZT(52/48)薄膜进行了不同温度及时间的退火;接着采用XRD对各样片薄膜进行了结晶物相分析;采用FIB对部分样片薄膜表面形貌进行了观察.实验结果显示,薄膜的厚度及退火条件在一定程度上对其结晶态的影响是一致的;对于一定厚度的薄膜,合适且相同的退火(650 ℃)条件都可以使其形成单一的PZT(52/48)物相;二次退火对较厚薄膜结晶化有一定的作用,但随着溅射薄膜厚度的增加而累加了内应力,退火后形成有PZT(52/48)物相的较厚薄膜表面出现裂纹越明显.     

Role of oxygen vacancies in the coloration of 0.65Pb(Mg1/3Nb2/3)O3‐0.35PbTiO3 single crystals

The coloration and oxygen vacancies in 0.65Pb(Mg_1/3Nb_2/3)O₃‐0.35PbTiO₃ (PMN‐PT(65/35)) (starting composition) single crystals grown by a so‐called modified Bridgman technique were investigated in this paper. Light yellow and dark brown colored crystals were generally observed for the typical as‐grown PMN‐PT(65/35) single crystals. X‐ray diffraction results demonstrated that they were both of pure perovskite structure, but good electric properties were only obtained for the light yellow crystal. X‐ray photoelectron spectroscopy (XPS) was used to investigate the electronic structure of its components. The O 1s photoelectron spectra of the dark brown colored crystals located at the higher binding energy side, which meant the existence of the more oxygen vacancies. It accordingly led to the formation of the low valence cations associated with the coloration of the crystals, which is also testified by the obtained X‐ray photoelectron spectra of Ti and Nb. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bi1.65Zn1.0Nb1.5O7.225陶瓷和薄膜的结构和介电性能对比

以立方焦绿石Bi1.5Zn1.0Nb1.5O7(BZN)为配方基础,通过掺入过量10％的Bi2O3,形成Bi1.65Zn1.0Nb1.5O7.225非化学计量比分子式.采用固相反应法合成具有焦绿石立方结构的Bi1.65Zn1.0Nb1.5O7.225陶瓷,并采用脉冲激光沉积法在Pt/SiO2/Si(100)基片上制备其薄膜.对比研究了非化学计量比Bi1.5Zn1.0Nb1.5O7.225陶瓷和薄膜的结晶性能,微观形貌以及介电性能的差异.结果表明烧结的Bi1.65Zn1.0Nb1.5O7.225陶瓷和沉积的BZN薄膜都保持立方焦绿石单相结构,但是薄膜展现出较强的(222)晶面择优取向.陶瓷和薄膜的晶格常数,微观形貌都体现出差异.对比二者的介电特性后发现,Bi1.65Zn1.0Nb1.5O7.225薄膜的介电常数明显高于陶瓷的介电常数,这归因于薄膜和块体材料之间的差异,例如厚度,致密度,择优取向等.     

Structural Features of PLZT Films

Lead zirconate titanate (PZT) films doped with lanthanum, Pb(_1–х)La_х(Zr_0.48Ti_0.52) (х = 0, 0.02, 0.05, 0.08, or 0.01), have been investigated by electron microscopy and X-ray diffraction. Films were formed on Si–SiO₂–TiO₂–Pt substrates by chemical vapor deposition from a solution and annealed at temperatures T = 650 and 750°C. The main structural features of the films, differing them from undoped PZT films fabricated by the same method, have been established. It is found that doping with lanthanum delays the pyrochlore–perovskite transformation in the film bulk, i.e., in the regions distant from the film–substrate interface. The fraction of metastable pyrochlore phase increases with an increase in the La molar content in the films. The main reason for the delay is the deficit of lead in the intergranular perovskite space, especially in the upper part of the film. Annealing at T = 750°C reduces the content of pyrochlore phase but does not completely remove it, which was never observed for undoped PZT films. Doping with lanthanum leads to a change in the lattice period c and a tetragonal distortion of the perovskite lattice (c/a ratio). Hence, the [100] texture of the films obtained, in contrast to the typical [111] texture of PZT films, is due to the increase in the lattice mismatch between the film and platinum layer when lead atoms are replaced with lanthanum. Lattice distortions of “transrotational” character, whose value exceeds 160 deg/μm, are found to arise in growing crystals.