Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

Compositional dependence of ferroelectric properties of highly c-axis oriented Bi4−xNdxTi3O12 film capacitors

Highly c-axis oriented neodymium-modified bismuth titanate (Bi_4−xNd_xTi₃O₁₂) films having a variety of neodymium (Nd) contents were successfully grown on Pt/TiO₂/SiO₂/Si(100) substrates using metal-organic sol decomposition. After systematically examining ferroelectric properties of the c-axis oriented Bi_4−xNd_xTi₃O₁₂ film capacitors as a function of the Nd-content, we concluded that the capacitor with x=0.85 had the largest remanent polarization. The Bi_3.15Nd_0.85Ti₃O₁₂ capacitor fabricated using a top Pt electrode showed well-saturated polarization-electric field (P-E) switching curves with the remanent polarization (P_r) of 51 μC/cm² and the coercive field (E_c) of 99 kV/cm at an applied voltage of 10 V. More importantly, the Pt/Bi_3.15Nd_0.85Ti₃O₁₂/Pt capacitor exhibited fatigue-free behavior up to 4.5×10¹⁰ read/write switching cycles at a frequency of 1 MHz. The capacitor also demonstrated an excellent charge-retaining ability and a strong resistance against the imprinting failure.     

Doping effect on the phase transition temperature in ferroelectric SrBi2−xNdxNb2O9 layer‐structured ceramics: a micro‐Raman scattering study

The temperature dependence of Raman spectra for SrBi_2−xNd_xNb₂O₉ ceramics (x from 0 to 0.2) has been studied in a wide temperature range from 80 to 873 K. It is found that the peak position of the A_1g[Nb] phonon mode at 207 cm^–1, which is directly associated with the distortion of NbO₆ octahedron, decreases with increasing Nd composition, while the A_1g[O] phonon mode at 835 cm^–1 increases. Moreover, both the peak position and intensity of the A_1g[Nb] phonon mode reveal strong anomalies around the ferroelectric to paraelectric phase transition temperature. It indicates that the phase transition temperature decreases from about 710 to 550 K with increasing Nd composition, which is due to the fact that the introduction of Nd ions in the Bi₂O₂ layers reduces the distortion extent of NbO₆ octahedron. Copyright © 2011 John Wiley & Sons, Ltd.     

La掺杂对Bi4Ti3O12薄膜铁电性能的影响

利用Sol-Gel法在Pt/Ti/SiO₂/Si衬底上制备出Bi₄Ti₃O₁₂和Bi_3.25La_0.75Ti₃O₁₂薄膜，研究了La掺杂对Bi₄Ti₃O₁₂薄膜的晶体结构、铁电性能和疲劳特性的影响，发现La掺杂没有改变Bi₄Ti₃O₁₂薄膜的基本晶体结构，并且提高了Bi₄Ti₃O₁₂铁电薄膜的剩余极化值和抗疲劳性能，对La掺杂改善Bi₄Ti₃O₁₂铁电薄膜性能的机理进行了讨论. 关键词： 铁电性能 4Ti₃O₁₂薄膜')" href="#">Bi₄Ti₃O₁₂薄膜 3.25La_0.75Ti₃O₁₂薄膜')" href="#">Bi_3.25La_0.75Ti₃O₁₂薄膜 sol-gel法 La掺杂     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

Cation disorder and structural studies on Bi4−x Nd x Ti3O12 (0.0≤x≤2.0)

Here we report the results of combined powder X-ray and neutron diffraction studies of Bi_4?x Nd _x Ti₃O₁₂ (0.0 ≤ x ≤ 2.0) compositions. The parent Bi₄Ti₃O₁₂ has an orthorhombic lattice (space group: B2cb) with unit cell parameters a = 5.4432(5) Å, b = 5.4099(5) Å and c = 32.821(2) Å, and V = 966.5(1) ų. This orthorhombic lattice is retained in all the studied compositions. The unit cell parameters gradually decrease with Nd³⁺ ion concentration with a discontinuity at x = 0.75. Orthorhombicity of the lattice decreases with increase in Nd³⁺ content in the lattice. The orthorhombic unit cell parameters for a representative Bi₂Nd₂Ti₃O₁₂ composition are: a = 5.3834(9), b = 5.3846(9) and c = 32.784(1) Å. The observed orthorhombic distortion at x = 2.0 is very small and thus the crystal structure apparently has a pseudo-tetragonal lattice. In addition, Nd³⁺ preferentially substitutes in the perovskite slab of the Aurivillius structure. The fraction of Nd³⁺ in the fluorite slab increases with increase in Nd³⁺ contents.     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

Electrical properties of neodymium doped CaBi4Ti4O15 ceramics

Neodymium doped bismuth layer structure ferroelectrics (BLSFs) ceramics CaBi_4−xNd_xTi₄O₁₅ (x=0, 0.25, 0.50, 0.75) were prepared by solid-state reaction method. X-ray diffraction pattern showed that single phase was formed when x=0-0.75. The refined lattice parameters showed that a (b) axes decrease at x=0.25 and increase with more Nd³⁺ dopant. The effects of Nd³⁺ doping on the dielectric and ferroelectric properties of CaBi₄Ti₄O₁₅ ceramics are studied. Nd³⁺ dopant decreased the Curie temperature linearly, and the dielectric loss, tan δ, as well. The remnant polarization of Nd³⁺ doped CaBi₄Ti₄O₁₅ ceramics was increased by 80% at x=0.25, while more Nd³⁺ dopant decreased the remnant polarization. CaBi_3.75Nd_0.25Ti₄O₁₅ ceramics had the largest piezoelectric constant d₃₃. The structure and properties of CaBi_4−xNd_xTi₄O₁₅ ceramics showed that Nd³⁺ may occupy different crystal locations when Nd³⁺ content x is less than 0.25 and more than 0.50.     

Table-like magnetocaloric effect involving the enhancement of refrigerant capacity in (AMn0.9Ti0.1O3)1−x/(AMn0.85Ti0.15O3)x composite

In this paper, a table-like magnetocaloric effect (MCE) is obtained in the (AMn_0.9Ti_0.1O₃)_1?x/(AMn_0.85Ti_0.15O₃)_x composite system. A flattening behaviour of the entropy change is investigated from the isothermal magnetic entropy change versus temperature curves ?S(T) of AMn_0.9Ti_0.1O₃ and AMn_0.85Ti_0.15O₃ (A = La_0.57Nd_0.1Pb_0.33) manganite materials. Both compounds exhibit nearly some large MCE, 5.2–4.85 J kg^?1 K^?1, under an applied field of 0–5 T, around their respective Curie temperature (T_C) ranged from 279 to 299 K. The temperature dependence of the isothermal magnetic entropy change ΔS(T) is calculated for (AMn_0.9Ti_0.1O₃)_1?x/(AMn_0.85Ti_0.15O₃)_x composite with 0 ≤ x ≤ 1. The optimum ΔS(T) of the composite with x = 0.495 approaches a nearly constant value of ～3.63 J kg^?1 K^?1 in a field change of 0–5 T in a wide temperature span over 15 K, resulting in large refrigerant capacity value of ～172.3 J kg^?1. The (AMn_0.9Ti_0.1O₃)_0.505/(AMn_0.85Ti_0.15O₃)_0.495 composite system indicates that this approach can be used to design magnetic refrigerant materials with enhanced magnetocaloric response in a magnetic refrigerator performing an Ericsson cycle near room temperature.     

Room‐Temperature Insulating Ferromagnetic (Ni,Co)1+2xTi1−xO3 Thin Films

Insulating uniaxial room‐temperature ferromagnets are a prerequisite for commonplace spin wave‐based devices, the obstacle in contemporary ferromagnets being the coupling of ferromagnetism with large conductivity. It is shown that the uniaxial A_{1 + 2x}Ti⁴⁺_{1 ? x}O₃ (ATO), A = Ni²⁺,Co²⁺, and 0.6 < x ≤ 1, thin films are electrically insulating ferromagnets already at room temperature. The octahedra network of the ATO and the corundum and ilmenite structures are the same yet different octahedra‐filling proved to be a route to switch from the antiferromagnetic to ferromagnetic regime. Octahedra can continuously be filled up to x = 1, or vacated (?0.24 < x < 0) in the ATO structure. TiO‐layers, which separate the ferromagnetic (Ni,Co)O‐layers and intermediate the antiferromagnetic coupling between the ferromagnetic layers in the NiTiO₃ and CoTiO₃ ilmenites, can continuously be replaced by (Ni,Co)O‐layers to convert the ATO‐films to ferromagnetic insulator with abundant direct cation interactions.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜的制备与特性研究

采用溶胶凝胶工艺在p-Si衬底上制备了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合铁电薄膜. 研究了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合薄膜的微观结构与生长行为、铁电性能和疲劳特性. 研究表明: Si衬底Bi₄Ti< 关键词： 2Ta₂O₉')" href="#">SrBi₂Ta₂O₉ 4Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 复合铁电薄膜 溶胶凝胶工艺     

Sr位Nd掺杂对SrBi$lt;sub$gt;2$lt;/sub$gt;Nb$lt;sub$gt;2$lt;/sub$gt;O$lt;sub$gt;9$lt;/sub$gt;性能的影响及机理研究

采用传统固相法制备了（Sr_1-3x/2A_x/2Nd_x）Bi₂Nb₂O₉（x=0,0.05,0.1和0.2）陶瓷,并系统研究了Nd离子取代Sr离子对SrBi₂Nb₂O₉性能的影响及其作用机理.研究结果表明：Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉的介电常数和介电损耗随温度变化的行为具有明显的离子松弛极化特征.Nd³⁺对Sr²⁺的部分取代,导致Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉剩余极化强度P_r稍有下降,但其压电系数d₃₃却有所增加,根据铁电热力学理论,这是Nd³⁺对Sr²⁺取代导致材料介电常数增大所致.Sr_1-3x/2A_x/2Nd_xBi₂Nb₂O₉的居里温度（T_C）没有随Nd含量的增加而变化,拉曼光谱技术分析表明这是其NbO₆八面体畸变程度没有发生变化所致.Nd³⁺取代Sr²⁺提高了材料的介电常数ε_r、压电系数d₃₃、机电耦合系数K_p,同时降低了机械品质因数Q_m,但是谐振频率温度系数C值没有改变. 关键词： 压电陶瓷 介电性能 压电性能 拉曼光谱     

Effect of Sr<Superscript>2+</Superscript> ion substitution with trivalent ions (Sc<Superscript>3+</Superscript>, In<Superscript>3+</Superscript>, La<Superscript>3+</Superscript>, Bi<Superscript>3+</Superscript>) on its ferroelectric instability in SrTiO<Subscript>3</Subscript>

The vibration frequencies of unstable ferroelectric and antiferrodistortion modes and the dependences of the energy on the ion displacement amplitude have been calculated within the generalized Gordon-Kim model for distortions along eigenvectors of these modes in the mixed compounds Sr_{1 − x} A _x Ti_{1 − x} /₄□ _x/4O₃ and Sr_{1 − y} A _2y /₃□ _y/3TiO₃ (A = Sc³⁺, In³⁺, La³⁺, Bi³⁺; □ is the vacancy). To compensate an excess positive charge, vacancies are introduced into the Ti⁴⁺ or Sr²⁺ site. Calculations have been performed in the “daverage” crystal approximation for impurity concentrations of 0.25 and 0.50. To this end, a set of 40 atomic superlattices with various orderings of heterovalent ions Sr²⁺ and impurity A ³⁺ has been considered. It has been found that each impurity type, independently of charge balance, induces ferroelectric instabilities in doped compounds. In the case of doping with In³⁺ and La³⁺ for concentration x = 0.25, the possibility of rotating the polarization vector has been shown.     

Magnetic and ferroelectric properties of exchange-frustrated multiferroics (Ni1 ? xTx)3V2O8 (T = Co, Mn, Zn)

The effect of the substitution of Co²⁺, Mn²⁺, and Zn²⁺ ions for Ni²⁺ ions on the magnetic, dielectric, and ferroelectric properties of vanadate single crystals (Ni_{1 − x} T _x )₃V₂O₈ has been analyzed. It has been found that the low-level (x ≤ 0.1) substitution of both magnetic and nonmagnetic ions stabilizes the ferroelectric state with a cycloidal magnetic structure. The existence region of this state is expanded to low temperatures down to 3 K for Zn²⁺ and below 1.8 K for Co²⁺ and Mn²⁺ owing to the suppression of a low-temperature weak ferromagnetic phase. At the same time, the ferroelectric phase disappears completely at large concentrations of Co and Mn. The effect of magnetic fields on the magnetic and ferroelectric states has been analyzed. It has been shown that the magnetic field along the c axis suppresses the ferroelectric state, whereas the magnetization along the antiferromagnetism axis (a axis) induces the reentrant phase transition from a paraelectric weak ferromagnetic structure to a ferroelectric structure. The corresponding H-T phase diagrams have been drawn.     

Synthesis, structural and electrical properties of La and Nb modified Bi4Ti3O12 ferroelectric ceramics

Polycrystalline ceramic samples of Bi_4−xLa_xTi₃O₁₂ (x=0.0, 0.5 and 1) and Bi_3.5La_0.5Ti_3−yNb_yO₁₂ (y=0.02 and 0.04) have been synthesized by standard high temperature solid state reaction method using high purity oxides and carbonates. The effect of lanthanum doping on Bi-site and Nb doping on Ti-site on the structural and electrical properties of Bi₄Ti₃O₁₂ powders was investigated by X-ray diffraction, scanning electron microscopy, dc conductivity and dielectric studies. A better agreement between the observed and calculated X-ray diffraction pattern was obtained by performing the Rietveld refinement with a structural model using the non-centrosymmetric space group Fmmm in all the cases. A better agreement between observed and calculated d-values also shows that the lattice parameters calculated using the Rietveld refinement analysis are better. The increase in lanthanum and niobium contents does not lead to any secondary phases. It is found that La³⁺ doping reduces the material grain size and changes its morphology from the plate-like form to a spherical staking like form. The substitution of Nb for Ti ions affected the degree of disorder and modified the dielectric properties leading to more resistive ceramic compounds. The shape and size of the grains are strongly influenced by the addition of niobium to the system. The activation energies of all the compounds were calculated by measuring their dc electrical conductivities. The frequency and temperature dependent dielectric behavior of all the compounds have also been studied and the results are discussed in detail. The substitution of La and Nb on the Bi and Ti sites decreased the T_c and improved the dielectric and ferroelectric behavior.     

Weak ferromagnetism in BiFeO<Subscript>3</Subscript>-based multiferroics

The magnetic properties of the Bi_{1 ? x} Ln _x FeO₃ (Ln is a rare-earth ion), Bi_{1 ? x} A _x FeO_{3 ? x/2} (A is an alkali earth ion), and BiFe_{1 ? x} Ti _x O_{3 + δ} solid solutions in magnetic fields up to 14 T have been studied. The concentration ranges of the existence of the ferroelectric phase described by the space group R3c have been determined. It is shown that the substitution of the rare-earth ions for the Bi³⁺ ions leads to a sharp decrease in the critical fields inducing the metamagnetic transition from a modulated antiferromagnetic state to a weakly ferromagnetic one; however, the modulated structure in the concentration range of the R3c phase is mainly retained. The substitution of the alkali earth ions (x ～ 0.1) for the bismuth ions leads to the total destruction of the modulated structure and to the implementation of the weakly ferromagnetic state within the R3c phase. A homogeneous weakly ferromagnetic state has been revealed when the Ti⁴⁺ ions (x = 0.1) are substituted for the Fe³⁺ ions in the ferroelectric R3c phase.     

Metalorganic chemical vapor deposited DyScO3 buffer layer in Pt/Bi3.25Nd0.75Ti3O12/DyScO3/Si metal–ferroelectric–insulator–semiconductor diodes

High-k DyScO₃ linear dielectric films were considered as a buffer layer for the metal-ferroelectric-insulator-semiconductor (MFIS) structures with Aurivillius Bi_3.25Nd_0.75Ti₃O₁₂ ferroelectric films. The DyScO₃ films on Si substrates were amorphous and dense with a smooth surface morphology, showing negligible CV hysteresis and low leakage current. The remnant polarization of ～20 μC/cm², dielectric constant ～400, and the loss tangent ～0.04 were obtained for the ferroelectric Bi_3.25Nd_0.75Ti₃O₁₂ film on Pt/TiO₂/SiO₂/Si substrates. The Pt/Bi_3.25Nd_0.75Ti₃O₁₂/DyScO₃/Si MFIS capacitors showed a large memory window of 4.0 V and excellent retention up to 1000 s, encouraging results for practical applications in nonvolatile RAM.     

Si基Bi4Ti3O12铁电薄膜的制备与特性研究

采用sol-gel工艺, 在分层快速退火的工艺条件下成功地制备了高质量Si基Bi_{4Ti3O12铁电薄膜. 研究了Si基Bi4Ti3O12薄膜的生长行为、铁电性能、C-V特性和疲劳特性. 研究表明: Si基Bi4Ti3O12薄膜具有随退火温度升高沿c轴择优生长的趋势; 退火温度通过影响薄膜的晶粒尺寸、生长取向和薄膜中载流子的浓度来改变Si基Bi关键词： sol-gel法 铁电薄膜 4Ti3O12')" href="#">Bi4Ti3O12 C-V特性}