The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.     

Bi-fluctuation in Na0.5Bi0.5TiO3 ferroelectric ceramics with abnormal relaxor behaviour

ABSTRACT

The existence of Bi-fluctuation dispersing in Na_0.5Bi_0.5TiO₃ (NBT) relaxor ferroelectric is hinted in other recent studies. However, this fluctuation has not been directly observed yet. We introduce the Bi-rich nano-regions with different sizes in a series of NBT ceramics by the slight excess of Bi³⁺ content. The crystal symmetries of the Bi-rich nano-regions and the NBT matrix are rhombohedral. The lattice parameters of the nano-regions are larger than those of the matrix in NBT ceramics, which were confirmed by the X-ray diffraction Rietveld refinement, TEM techniques and first-principles calculation. Also, the disorder-induced nano-regions appearing as Bi-fluctuation are associated with the complex phase transitions and the high-frequency relaxor behaviour of NBT suggested by the dielectric measurements and Raman spectra.     

Dielectric,ferroelectric and field-induced strain response of lead-free BaZrO3-modified Bi0.5Na0.5TiO3 ceramics

Lead-free piezoelectric ceramics (1 − x)Bi_0.5Na_0.5TiO₃–xBaZrO₃ (BNT–BZ100x, with x = 0–0.10) were prepared using a conventional solid-state reaction method. The crystal structure, microstructure, dielectric, ferroelectric, and piezoelectric properties of BNT–BZ100x ceramics were studied as functions of different BZ content. X-ray diffraction patterns revealed that the BZ completely diffused in the BNT lattice in the studied composition range. An appropriate amount of BZ addition improved the dielectric, ferroelectric, and piezoelectric properties of BNT ceramics. The remanent polarization (P_r) and piezoelectric constant (d₃₃) increased from 22 μC/cm² and 60 pC/N for pure BNT to 30 μC/cm² and 112 pC/N for x = 0.040, respectively. In addition, electric field-induced strain was enhanced to its maximum value (S_max = 0.40%) with normalized strain (d*₃₃ = S_max/E_max = 500 pm/V) at an applied electric field of 8 kV/mm for x = 0.055. The enhanced strain can be attributed to the coexistence of ferroelectric and relaxor ferroelectric phases.     

Relaxor properties of Nb-modified (Ba0.8Sr0.2)TiO3 ceramics

Nb-doped (Ba_0.8Sr_0.2)TiO₃ ceramics were prepared using conventional mixed-oxide processing technique. Permittivity and loss factor were investigated as a function of temperature for various frequencies of the measuring field. The obtained results confirmed the relaxor ferroelectric behaviour of the studied ceramics, i.e. a strong frequency dispersion of the permittivity maximum and a visible shift of its temperature with frequency. Analysis of real part of permittivity allowed us to determine the value of the freezing temperature characterising the relaxor ferroelectrics. The physical processes, responsible for the relaxor behaviour of the studied ceramics are discussed.     

Dielectric and structural relaxation phenomena in Na0.5Bi0.5TiO3 single crystal

Abstract

Dielectric permittivity studies of Na_0.5Bi_0.5TiO₃ single crystals in a broad range of frequency up to 10 MHz and temperature 300—823 K are reported. In this temperature range dielectric dispersion below 1 MHz has been found. The obtained data were fitted to the Cole-Cole relation. The mean relaxation time τ is strongly temperature dependent (0.04 ? 2.6 × 10^?5 s). A remarkable hysteresis effect in the values of τ on cooling and heating took place. The Δε(T) dependence (the maximal value of Δε ～ 400) is similar to the global ε′(T) response at low frequency. An isothermal structural transformation in Na_0.5Bi_0.5TiO₃ was observed by X-ray measurements. The order of the time in which the transformation takes place (～300 minutes) corresponds to the time in which the strongest time evolution of electric permittivity and time changes of dielectric dispersion were detected.     

Na0.25K0.25Bi0.5TiO3无铅压电陶瓷的介电特性研究

用固相反应法制备了Na0.25K0.25Bi0.5TiO3(NKBT50)陶瓷,研究了该陶瓷在室温至400℃温度范围内的介电性能.发现该陶瓷的介电温谱与烧结气氛、极化状态有关.在空气中烧结的未极化样品在70℃附近存在介电和损耗峰,而极化后及在氧气氛中烧结的样品并不存在该介电、损耗峰.分析认为70℃的介电和损耗峰与氧空位形成的缺陷偶极子的极化弛豫有关.热激电流显示,陶瓷的去极化温度为225℃,与此相对应的介电、损耗峰也与氧空位有关.     

Photoluminescence and electrical properties of Eu-doped (Na0.5Bi0.5)TiO3 ferroelectric single crystals

Eu³⁺-doped Na_0.5Bi_0.5TiO₃ (Eu:NBT) single crystals were grown by a top-seeded solution growth method. Photoluminescence emission and excitation spectra of Eu:NBT were investigated. The two transitions in ⁷F₀ → ⁵D₀ excitation spectra reveal that Eu³⁺ ions were incorporated into two adjacent crystallographic sites in NBT, i.e., Bi³⁺ and Na⁺ sites. The former has a symmetrical surrounding, while the later has a disordered environment, which was confirmed by decay curve measurements. The dielectric dispersion behavior was depressed and the piezoelectric and ferroelectric properties were improved after Eu doping.     

Influence of the dc and ac field intensity on electric permittivities of (Na0.5Bi0.5)0.88Ba0.12TiO3 ceramics

The electric permittivity measurements under different ac or dc field amplitudes on lead-free (Na_0.5Bi_0.5)_0.88Ba_0.12TiO₃ ceramics were performed. A significant increase or decrease in permittivities was observed with increasing ac or dc fields intensity, respectively. It was found that temperature T _m decreases or increases with increasing ac or dc fields, respectively. When ac field amplitude increased, stronger frequency relaxation around T _m and greater shift in T _m was observed. This was in opposite to the effect of dc field intensity. The obtained results were discussed in terms of polar region behaviour in external electric fields.     

(Bi0.5Na0.5)TiO3-Ba(Ti,Zr)O3 陶瓷的电性能研究

采用氧化固相法制备了(1-x)(Bi0.5Na0.5)TiO3-xBa(Ti0.95Zr0.05)O3(BNT-BZT)陶瓷,其中掺入量x的值分别为0,0.04,0.05,0.06,0.07.研究了BNT-BZT体系陶瓷的准同型相界以及陶瓷材料的微观结构和性能之间的关系,并探讨了陶瓷的介电性能和铁电等性能.通过探究Ba(Ti,Zr)O3(BZT)掺杂量对BNT 各性能的影响得出了当掺杂量x=0.05得到结构较为致密,介电,铁电性能较好的样本,对工业化研究和生产有重要的意义     

复合层状Bi7Ti4 NbO21铁电陶瓷的结构与介电和压电性能研究

制备了Bi7Ti4NbO21，Bi4Ti3O12及Nb掺杂Bi4Ti3O12(Nb-Bi4Ti3O12)层状结构铁电陶瓷材料．结合Nb-Bi4Ti3O12的介电温谱和退极化实验结果，研究了Bi7Ti4NbO21的晶体结构对其介电、压电性能的影响．高分辨透射电镜结果表明，在Bi7Ti4NbO21中，沿着c轴方向，(Bi2Ti3O10)^2-和(BiTiNbO7)^2-。两个类钙钛矿层分别与(Bi2O2)^2 层叠加堆积而成．这种晶体结构决定了Bi7Ti4NbO21的介电温谱在668℃和845℃出现介电双峰．结合极化样品的退化实验分析，说明材料在这两个温度附近发生了铁电一铁电相变、铁电一顺电相变，分别是(Bi2Ti3O10)^2-和(BiTiNbO7)^2-层状结构发生微观结构相变的结果．在退极化过程中，由于受热时钙钛矿层内空位引起的缺陷偶极子的定向排列受到破坏，引起材料部分退极化，表现为300℃热处理后Bi7Ti4NbO21的压电活性降低了10％，显示了室温下材料的压电性能来源于自发极化的固有电偶极子和缺陷偶极子的共同贡献．     

High-temperature impedance spectroscopy of BaFe0.5Nb0.5O3 ceramics doped with Bi0.5Na0.5TiO3

Bi_0.5Na_0.5TiO₃ (BNT)-doped BaFe_0.5Nb_0.5O₃ (BFN) ceramics were synthesized by a two-step solid-state reaction. Temperature dependence of dielectric properties measured at different frequencies was investigated over broad temperature and frequency ranges. Impedance spectroscopy and universal dielectric response were employed to study the relaxation behavior and conductivity mechanism of the ceramics in a frequency range from 40 Hz to 100 MHz and a temperature range from 300 K to 800 K. The complex plane impedance data revealed the bulk and grain boundary contributions toward conductivity processes in the form of semicircular arcs. The high-temperature conductivity of ceramics is attributable to thermally activated second ionized oxygen vacancy.     

Influence of lateral size on dielectric properties of ferroelectric thin films with structure transition zones

By taking into account structural transition zones near the lateral and thickness direction edges, this paper uses a modified transverse Ising model to study dielectric properties of a finite size ferroelectric thin film in the framework of the mean-field approximation. The results indicate that the influence of the lateral size on the dielectric susceptibility cannot be neglected and lateral structural transition zones could be a crucial factor that improves the mean susceptibility of the fixed size film.     

Transverse piezoelectric properties of Mn-doped Bi0.5Na0.5TiO3 thin films

Lead-free (Bi_0.5Na_0.5)(Ti_1-xMn_x)O₃ (BNTMn-x; x = 0, 0.0025, 0.0050, 0.0100) thin films were fabricated using a chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrate. The effect of Mn substitution on crystal structures, surface morphologies, and ferroelectric and transverse piezoelectric properties of BNTMn-x thin films was investigated. The 0.5 mol% Mn-doped (Bi_0.5Na_0.5)(Ti_0.995Mn_0.005)O₃ thin film exhibited a well-saturated ferroelectric P-E hysteresis loop at room temperature. A remnant polarization (P_r) of 16 μC/cm² was obtained for the BNTMn-0.0050 film at an applied electric field of 400 kV/cm. In addition, a 1.12-μm-thick BNTMn-0.0050 film was applied as a cantilever. The Pt/BNTMn-0.0050/Pt/TiO₂/SiO₂/Si unimorph cantilever exhibited a high transverse piezoelectric coefficient ($e_{31}^1$) of 2.43 C/m².     

Bi0．5Na0．5TiO3纳米晶的制备及其性能研究

采用凝胶自燃烧法合成Bi0.5Na0.5TiO3纳米粉体,并表征了粉体的晶相结构.测试表明应用凝胶自燃工艺合成的Bi0.5Na0.5TiO3粉体材料的粒子大小均匀,晶相单一,不需要经高温处理便能直接形成钙钛矿结构超细粉末.用所合成的粉末压片,1 125 ℃烧结2 h即可获得致密的烧结体,其相对密度为98.08%.用SEM观察烧结样品的平均粒径为2 μm.     

Enhanced electrical and ferroelectric properties in a multiferroic (BiFeO3/Bi0.5Na0.5TiO3)3/LaNiO3 superlattices structure

Artificial multiferroic superlattices (SL), consisting of BiFeO₃ (16 nm)/Bi_0.5Na_0.5TiO₃ (5 nm) (BFO/BNT SL), were grown on (001) SrTiO₃ single crystal by pulsed laser deposition method. The cross-sectional, surface morphology, and crystallographic structure of BFO/BNT SL and BFO single layer were investigated. It was found that the electrical, ferroelectric, and magnetic properties of BFO/BNT SL exhibit a remarkably enhancement compared with BFO single layer. The influence of BNT buffering layer, lattice strain, and interfaces interplay of the SL structure are supposed to benefit their ferroelectric and ferromagnetic properties. Our works suggested the BFO/BNT SL with an improved multiferroic characteristics have a promising application for the future informational storage devices.     

Dielectric properties and electrical conduction of La2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

La₂O₃ (2 wt%)-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (abbreviated as BNBT6) lead-free piezoelectric ceramics were synthesized by conventional solid-state reaction. X-ray diffraction (XRD) patterns indicated that La₂O₃ has diffused into the lattice of BNBT6 ceramics and formed a solid solution with a pure perovskite structure. Addition of La₂O₃ decreased the piezoelectric properties and electrical conductivity. It was used to study the electrical conductivity of the La₂O₃-doped BNBT6 lead-free piezoelectric ceramics combined with electrical modulus and impedance plots at the temperature range over 788–873 K. The values of activation energy derived from the electrical impedance and modulus were found to be 0.51 and 0.50 eV, respectively. The discrepancy between activation energy of relaxation frequency and the activation energy (0.25 eV) of dc electrical conductivity might have been due to a short-range migration or hopping of single ionized oxygen vacancy and a long-range migration or hopping of charge carriers over the whole disordered system, respectively.     

钛酸铋钠系铁电体的相变研究

研究了(Na0.5Bi0.5)TiO3,(Na0.5Bi0.5)(1-x)BaxTiO3和(Na0.5Bi0.5)(1-x)SrxTiO3陶瓷的介电温谱,确认了该系列材料在520℃以下的高、低温两种介电反常和存在于这一温度区间的巨大热滞现象.发现该类材料只存在对应于低温介电反常的介电损耗峰,而对于高温介电峰则无对应的损耗峰.同时,常温时材料的结构特征对于其介电温谱的特征影响较小,但施加偏置场却可明显改变材料的介电温谱特征:1)可使得材料的热滞现象几乎消失;2)适当偏置场下材料升降温介电曲线可与零偏场下介电 关键词： 钛酸铋钠 热滞 相变 极性微区