Mn掺杂Pb(In_(1/2)Nb_(1/2))O_3-Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3单晶微米尺度压电阵列的制备与铁电畴结构研究

超声探头是高端医学超声诊疗设备的核心元件,由弛豫型铁电单晶制备的新型压电器件可显著提高其性能.由于高阵元密度阵列技术与微机电系统迅速发展,传统切割填充法刀缝过宽,难以降低阵元尺寸,无法提高阵元密度,更不利于高分辨率及高频率的应用需求.采用紫外光刻-深反应离子刻蚀工艺的微机械制备方法,可以降低缝宽、提升阵列密度.制备了基于新型、高性能弛豫铁电单晶—Mn离子掺杂0.3Pb(In_(1/2)Nb_(1/2))O_3-0.4Pb(Mg_(1/3)Nb_(2/3))O_3-0.3PbTiO_3 (Mn-PIMNT)的微米尺度压电阵列.研究了紫外光刻工艺参数、深反应离子刻蚀工艺参数对压电阵列形貌的影响规律,得到了不同沟道深度与不同压电阵元形状的形成机制以及Mn-PIMNT单晶的刻蚀速率与天线功率、偏置功率及刻蚀气体比例之间的关系规律.得到压电阵列阵元尺寸小于10μm,沟槽深度大于20μm,沟槽宽度小于5μm,侧壁角度高于87°.通过压电力显微镜研究了微米尺度压电阵元的铁电畴结构及电场效应调控.与传统切割填充法相比,本文的加工方法不存在刀缝过宽,可确保单晶晶向,促进了高频率压电单晶复合材料、高密度超声换能器阵列以及新型压电微机械系统的发展.     

Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3/CoFe_2O_4复合薄膜电学、磁学性能的研究

利用射频磁控溅射技术在LaNiO_3/SiO_2/Si基底上制备了Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3/CoFe_2O_4和Pb(Mg_(1/3)Nb_(2/3))O_3-Pb TiO_3/Co Fe_2O_4/Pb(Mg_(1/3)Nb_(2/3))O_3-PbTiO_3两种复合薄膜.我们采取了三种退火条件对复合薄膜进行退火处理,研究两种复合薄膜的晶体结构、电学和磁学性能.通过对两种复合薄膜的结构的分析,发现两步法退火后得到复合薄膜同时存在纯钙钛矿相和尖晶石相两种结构.铁电性能测试表明,两种复合薄膜均具有较好的铁电性能,其中三层复合薄膜的剩余极化强度Pr最大可以达到14.9μC/cm2,这要归因于多层复合薄膜内部的应力-应变效应和界面耦合效应.在电场强度为80 k V/cm的漏电流密度数量级仅10-5A/cm2,其导电机制在高电场区满足Schottky机制.介频性能测试表明:复合薄膜的介频特性较差,双层复合薄膜的介电性能较好,其介电常数εr为1078,其介电损耗tgδ较大,约为0.43.此外,对复合薄膜的磁滞回线测试表明:两种复合薄膜中均存在磁学性能,且双层结构复合薄膜的铁磁性能较大,其饱和磁化强度Ms为119 emu/cm3,剩余磁化强度Mr达到31.6 emu/cm3,矫顽场Hc为1360 Oe.以上测试结果表明,铁电有序和磁有序可以存在于钙钛矿-尖晶石结构当中,通过多层复合和合适退火方式可以增强其铁电和介电性能.     

Pb(Sc_(1/2)Nb_(1/2))O_3中有序-无序转变和铁电相变的Raman光谱研究

采用wolframite前驱物法制备了Pb(Sc1/2Nb1/2)O3陶瓷。通过调节陶瓷烧结工艺,获得了三种具有不同B位离子有序度的PSN陶瓷。测量了三种陶瓷样品在室温至160°C范围内的Raman光谱随温度变化。结果表明,随着温度的升高,三种不同B位有序度的陶瓷样品中,Raman光谱中位于530 cm-1的F2g模的峰位和半峰宽分别在100°C,85°C和80°C发生了突变,表明陶瓷分别在100°C,85°C和80°C三个温度点发生了铁电-顺电相变。上述结论得到了介电温度谱测量数据的支持。     

弛豫型铁电单晶0.67Pb(Mg_(1/3)Nb_(2/3))O_3-0.33PbTiO_3的拉曼散射研究

本文采用拉曼散射技术在温度从374到-196℃的范围内,研究了弛豫型铁电单晶0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3(PMNT)。观察了在不同温度下拉曼光谱的变化,经分析这些变化反映了该晶体经历了两个相变:第一个相变温度发生在120℃,从顺电立方相到铁电四方相的相变,780 cm-1处模式在VH偏振下的改变标志了这一相变;第二个相变温度发生在34℃,是从铁电四方相到铁电三方相的相变,软模的出现代表了这一相变。     

布里渊散射决定0.67Pb(Mg_(1/3)Nb_(2/3))O_3-0.33PbTiO_3单晶的弹性、压电和介电常数(英文)

我们报道了用高分辨布里渊散射,确定0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3单晶中的弹性、压电和介电常数.所有的实验数据都是在一块沿[001]方向的极化的单晶样品上获得的。我们实验中得到的这些常数的数值和以往超声共振技术获得的数值相似。我们还研究了压缩模和剪切模在(010)和(001)平面内的方向依赖性。TA1和TA2模式的强度对散射角度有很强列依赖性。在散射角度为45°~65°内,一个新的峰出现在~18 GHz附近。它可能与晶体中的微观不均匀性或者局域微结构相关。     

Structure instability-induced high dielectric properties in[001]-oriented 0.68Pb(Mg_(1/3)Nb_(2/3))O_3–0.33PbTiO_3 crystals

The structure evolution and origin of ultrahigh dielectric properties have been investigated in the low temperature range from 300 K to 5 K for [001]-oriented 0.68 Pb(Mg_(1/3)Nb_(2/3))O_3–0.33PbTiO_3(PMN–33 PT) crystal. The experimental results reveal that a short-range ordered monoclinic MAis the dominant phase at ambient temperature. As the temperature drops below 270 K, the MAtransforms into monoclinic MC, and the MCremains stable until 5 K. Although no phase transition occurs from 5 K to 245 K, polar nanoregions(PNRs) display visible changes. The instability of PNRs is suggested as responsible for the low temperature relaxation. The ultrahigh dielectric constant at room temperature is associated with the instability of local structure and phase transition. Our research provides an insight into the design of high-performance ferroelectric materials.     

Pb(Zr_(0.52)Ti_(0.48))O_3/YBa_2Cu_3O_(7-x)双层结构电学特性研究

该研究通过溶胶-凝胶结合PLD的方法,在LaAlO_3(LAO)基板上制备了具有良好的c轴取向的Pb(Zr_(0.52)Ti_(0.48))O_3/YBa_2Cu_3O_(7-x)(PZT/YBCO)双层薄膜。采用溅射法制备了Pt顶电极,在300K~50K温度范围内,对Pt/PZT/YBCO的电滞回线和J-V特性曲线进行研究,结果表明:300K时,Pt/PZT/YBCO的剩余极化强度约为22μC/cm~2,随着温度的降低,剩余极化强度基本保持不变同时矫顽场和临界导通电压(Vc)增大、漏电流减小,当YBCO进入超导态时,Vc随温度的变化规律发生改变。进一步研究了不同电压下Pt/PZT/YBCO的电流输运特性,当外加偏置电压较小时(临界导通电压以下),Pt/PZT/YBCO的电流输运特性主要符合欧姆导电机制,当外加偏置电压增大到临界导通电压以上时,电流输运特性主要符合肖特基发射机制。     

Magnetic properties of L1_0 FePt thin film influenced by recoverable strains stemmed from the polarization of Pb(Mg_(1/3)Nb_(2/3))O_3–PbTiO_3 substrate

The magnetic properties and magnetization reversible processes of L1_0 FePt(3 nm)/Pb(Mg_(1/3)Nb_(2/3))O_3–PbTiO_3(PMN–PT) heterostructure were investigated by using the phase field model. The simulation results show that the magnetic coercivities and magnetic domains evolution in the L1_0 FePt thin film are significantly influenced by the compressive strains stemming from the polarization of single crystal PMN–PT substrate under an applied electric field. It is found that the magnetic coercivities increase with increasing of the compressive strain. A large compressive strain is beneficial to aligning the magnetic moments along the out-of-plane direction and to the enhancement of perpendicular magnetic anisotropy. The variations of magnetic energy densities show that when compressive strains are different at the magnetization reversible processes, the magnetic anisotropy energies and the magnetic exchange energies firstly increase and then decrease, the negative demagnetization energy peaks appear at coercivities fields, and the magnetoelastic energies are invariable at large external magnetic field with the energy maximum appearing at coercivities fields. The variations of the magnetoelastic energies bring about the perpendicular magnetic anisotropy so that the magnetoelastic energy is lower at the large external magnetic fields, whereas the appearance of magnetoelastic energy peaks is due to the magnetization-altered direction from the normal direction of the plane of the L1_0 FePt thin film at coercivities fields.     

The Electric-Field Controllable Non-Volatile 35° Rotation of Magnetic Easy Axis in Magnetoelectric CoFeB/(001)-Cut Pb(Mg_(1/3)Nb_(2/3))O_3-25%PbTiO_3 Heterostructure

Using in situ electric-field-modulated anisotropic magnetoresistance measurement,a large reversible and nonvolatile in-plane rotation of magnetic easy axis of ~35° between the positive and negative electrical poling states is demonstrated in Co_(40)Fe_(40)B_(20)/(001)-cut Pb(Mg_(1/3)Nb_(2/3))O_3-0.25PbTiO_3(PMN-PT).The specific magnetoelectric coupling mechanism therein is experimentaiiy verified to be related to the synchronous in-plane strain rotation induced by 109° ferroelastic domain switching in the(001)-cut PMN-PT substrate.     

基于PbMg_(1/3)Nb_(2/3)O_3-PbTiO_3压电单晶的磁电复合薄膜材料研究进展

电子信息技术的迅速发展对磁电功能器件的微型化、智能化、多功能化以及灵敏度、可靠性、低功耗等都提出了更高的需求,传统的块体磁电功能材料已日渐不能满足上述需求,而层状磁电复合薄膜材料同时具有铁电性、铁磁性和磁电耦合等多种特性,因此能满足上述需求且有望应用于新一代磁电功能器件.层状磁电复合材料不仅具有非常丰富的物理现象和效应,而且在弱磁探测器、多态存储器、电写磁读存储器、电场可调低功耗滤波器、移相器、天线等微波器件中也具有广阔的应用前景,因而受到材料科学家和物理学家广泛的关注和研究.在层状磁电复合材料中,功能薄膜/铁电单晶异质结因其制备简单、结构设计和材料选择灵活以及电场调控方便和有效,最近十余年引起了越来越多的研究人员的兴趣.目前,以具有优异铁电和压电性能的(1-x)PbMg_(1/3)Nb_(2/3)O_3-PbTiO_3(PMN-PT)单晶作为衬底,构建功能薄膜/PMN-PT异质结已成为国内外多铁性复合薄膜材料研究领域的重要方向之一.相比于其他国家,我国科学家无论在发表的文章数量还是在文章被引用次数方面都处于领先地位,表明我国在功能薄膜/PMN-PT单晶异质结方面的研究卓有成效.迄今为止,研究人员已构建了锰氧化合物/PMN-PT、铁氧体/PMN-PT、铁磁金属/PMN-PT、稀磁半导体/PMN-PT、发光材料/PMN-PT、二维材料/PMN-PT、多层薄膜/PMN-PT、超导薄膜/PMN-PT等多种类型的异质结,在理论研究和实验方面都取得了丰富的研究成果.本文对基于PMN-PT压电单晶的磁电复合薄膜材料的研究进展进行了总结:简要介绍了与功能薄膜/PMN-PT异质结相关的研究论文发表现状;介绍了PMN-PT单晶在准同型相界附近的相图和应变特性;按照功能薄膜材料所属的体系对异质结进行了分类,并选取部分代表性的研究成果,介绍了材料的磁电性能和内涵的物理机制;最后就目前有待解决的问题和未来可能的应用方向进行了总结和展望.     

Pb(Zr_(0.4)Ti_(0.6))O_3电子结构的第一性原理研究

采用基于密度泛函理论的赝势平面波方法计算了Pb(Zr0.4Ti0.6)O3五层超晶胞的顺电相和铁电相的电子结构.由态密度、电子密度和能带结构的计算结果发现顺电相下钛氧八面体Ti-O6和锆氧八面体Zr-O6在铁电相中分裂为由1个O1离子和4个O2离子组成的金字塔结构Ti-O5和Zr-O5;与顺电相相比,铁电相中钛离子的3d电子和氧离子的2p电子存在更强的轨道杂化,这种杂化降低了离子间的短程排斥力,使得具有铁电性的四方结构更为稳定,而且钛离子与氧离子的相互作用对于铁电相Pb(Zr0.4Ti0.6)O3沿c轴自发极化的贡献大于锆离子与氧离子的相互作用;由电子密度的分布可推断立方结构的Pb-O键呈现离子键特征,而铁电相下Pb-O键则有较大的共价成分,铅离子与氧离子的这种轨道杂化对Pb(Zr0.4Ti0.6)O3的铁电性起重要作用.所得结果对深入理解Pb(Zr0.4Ti0.6)O3铁电性的微观机理具有参考价值.     

Orientation effects on the bandgap and dispersion behavior of 0.91Pb（Zn_（1/3）Nb_（2/3））O_3-0.09PbTiO_3 single crystals

0.91Pb(Zn_1/3Nb_2/3)O₃--0.09PbTiO₃ (PZN--9%PT) single crystals with different orientations are investigated by using a spectroscopic ellipsometer, and the refractive indices and the extinction coefficients are obtained. The Sellmeier dispersion equations for the refractive indices are obtained by the least square fitting, which can be used to calculate the refractive indices in a low absorption wavelength range. Average Sellmeier oscillator parameters E_o, $\lambda$_o, S_o, and E_d are calculated by fitting with the single-term oscillator equation, which are related directly to the electronic energy band structure. The optical energy bandgaps are obtained from the absorption coefficient spectra. Our results show that the optical properties of [001] and [111] poled crystals are very similar, but quite different from those of the [011] poled crystal.     

Ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramics under compressive stress

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN system were investigated. The ceramics with a formula (1−x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃ or (1−x)PZT–(x)PZN (x = 0.1–0.5) were prepared by a conventional mixed-oxide method. The ferroelectric properties under the compressive stress of the PZT–PZN ceramics were observed at the stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remnant polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelastic domain switching processes.     

钙钛矿锰氧化物La_(2/3)Sr_(1/3)Fe_xMn_(1-x)O_3的结构与磁性研究

本文利用溶胶-凝胶法制备了名义成分为La_(2/3)Sr_(1/3)Fe_xMn_(1-x)O_3(x=0.0,0.1,0.2,0.3,0.5)的系列样品,样品先后经过773,873,1073 K热处理,热处理时采用缓慢升温方式,X射线衍射分析表明,该系列样品均为单相钙钛矿结构,空间群为R3c,利用X'Pert HighScore Plus软件计算了样品的晶粒尺寸、晶格常数、晶胞体积及键长、键角,利用物理性能测量系统测量了样品的磁性,发现样品在10K的磁矩随掺杂量的增加而减小,但存在两个明显不同的变化区域:从x=0到x=0.2时,平均每个分子的磁矩从2.72μB迅速下降到0.33μB,居里温度从327 K下降到95 K,下降了232 K;而从x=0.2到x=0.5时,平均每个分子的磁矩从0.33μB缓慢下降到0.05μB,居里温度从95K下降到46K,只下降了49K,我们认为Fe与Mn离子磁矩反平行是样品磁矩随Fe掺杂量增加而下降的原因之一。     

The interface density dependence of the electrical properties of 0.9Pb(Sc_(0.5)Ta_(0.5))O_3–0.1PbTiO_3/0.55Pb(Sc_(0.5)Ta_(0.5))O_3–0.45PbTiO_3 multilayer thin films

The 0.9Pb(Sc0.5Ta0.5)O3–0.1PbTiO3/0.55Pb(Sc0.5Ta0.5)O3–0.45 PbTiO3 multilayer thin films((PSTT10/45)n, n = 1–6, 10) are deposited on SiO2/Si(100) substrates by radio frequency magnetron sputtering technique with La Ni O3 buffer and electrode layer, and the films are subsequently annealed by a two-step rapid thermal approach. It is found that the interfacial density of the film has an important influence on the electric property of the film. The electric property of the film increases and reaches its critical point with the increase of interface density, and then decreases with the further increase of the interface density. With an interfacial density of 16 μm-1, the film shows an optimized dielectric property(high dielectric constant, εr = 765, lowest dielectric loss, tan δ = 0.041, at 1 k Hz) and ferroelectric property(highest remnant polarization,2Pr = 36.9 μC/cm2, low coercive field, 2Ec = 71.9 k V/cm). The possible reason for the electric behavior of the film is the competition of the interface stress with the interface defect.     

铁电晶体Pb_xBa_(1-x)Nb_2O_6和掺Li,Na的Pb_xBa_(1-x)Nb_2O_6的结构和电弹张量的测定

用提拉法从熔体中生长出Pb_(0.37)Ba_(0.63)Nb_2O_6和Pb_(0.30)Ba_(0.533)Na_(0.306)Li_(0.028)Nb_2O_6 两种铁电单晶。用X射线衍射方法分析了两种单晶的结构,结果表明,室温时两种晶体都属于四方晶系点群4mm。测定晶格参数得PBN晶体的a=12.493A和c=3.98A;掺Li,Na的PBN晶体的a=12.493A和c=3.970A。测定了两种晶体全部各52个电弹张量的分量,结果表明PBN晶体具有优良的压电性,其中压电系数d_15=108×10~(-12)C/N。这种晶体很有希望用作与厚度切变模式有关的压电换能器材料。掺Li,Na的PBN晶体的介电常数显著降低,而铁电居里点有明显的提高。     

铁电单晶(K_xNa_(1-x))_(0.4)(Sr_yBa_(1-y))_(0.8)Nb_2O_6的光学性质和线性电光效应

本文介绍铁电单晶(K_xNa_(1-x))_(0.4)(Sr_yBa_(1-y))_(0.8)Nb_2O_6的光学性质和线性电光效应的测量。实验结果表明,这种晶体具有较大的光学双折射,透光范围由4000A到5.6μm。晶体具有低的线性电光调制的半波电压,其电光调制价值指数n_0~3·γ_c高达730×10~(-12)m/V,而激光损伤阈值为600MW/cm~2(4 pps),表明该晶体可作为较大功率激光调制使用的材料。     

Zn_3V_2O_8和Zn_2V_2O_7的电子结构与光学性能的第一性原理研究

基于密度泛函理论(DFT)的第一性原理平面波超软赝势方法,在零压下建立了α-Zn_3V_2O_8和α-Zn_2V_2O_7晶体模型,分别对模型进行了电子结构和光学性质的计算.实验结果表明:α-Zn_3V_2O_8和α-Zn_2V_2O_7都属于间接带隙,α-Zn_3V_2O_8的禁带宽度为2. 715 eV,α-Zn_2V_2O_7的禁带宽度为2. 540 eV;同时,α-Zn_3V_2O_8和α-Zn_2V_2O_7都具有很强的紫外-近紫外光吸收能力;反射光谱、吸收光谱及能量损失谱的差异,共同导致Zn_3V_2O_8的光学性能要优异于Zn_2V_2O_7.     

柔性Pb(Zr_(0.53)Ti_(0.47))O_3薄膜的高温铁电特性

随着柔性电子产品的迅速发展,具有优异铁电和压电性的Pb(Zr_(0.53)Ti_(0.47))O_3 (PZT)薄膜在柔性的非易失性存储器、传感器和制动器等器件中有广泛的应用前景.同时,由于外部环境越来越复杂,具有高温稳定特性的材料和器件受到越来越多的关注.本文在耐高温的二维层状氟晶云母衬底上,用脉冲激光沉积技术制备出外延的PZT薄膜,并通过机械剥离的方法,得到柔性的外延PZT薄膜.研究了Pt/PZT/SRO异质结的铁电和压电性及其高温特性,发现样品表现出优越的铁电性,剩余极化强度(P_r)高达65μC/cm~2,在弯曲104次后其铁电性基本保持不变,且样品在275℃高温时仍然保持良好的铁电性.本文为柔性PZT薄膜在航空航天器件中的应用提供了实验基础.