Fabrication,dielectric and ferroelectric properties of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> film with preferred orientation

Ba_0.6Sr_0.4TiO₃ films were fabricated by RF magnetron sputtering method. The X-ray diffraction (XRD) showed that the preferred orientation of films growing on platinum Si substrates can be tailored by sputtering pressure. The processing parameters such as sputtering pressure and substrate temperature were optimized to obtain a developed perovskite film with (110) preferred orientation. The polarization hysteresis loops and permittivity–voltage curves of the (110)-oriented film have been investigated,which demonstrated that the film is in ferroelectric phase at room temperature. Besides, it had excellent fatigue properties without polarization reduction after about 10¹⁰ switch cycles, and showed low leakage current (10⁻⁹–10⁻⁷ A/cm²) within an applied voltage of 5 V. Finally, the leakage current mechanism was studied.     

Electrical behavior of Y-doped Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> thin films

Ba_0.6Sr_0.4TiO₃ (BST) and 1.5 at% Y-doped Ba_0.6Sr_0.4TiO₃ (Y-BST) thin films have been deposited on single-crystal (100) oriented LaAlO₃ substrates using pulsed-laser deposition technique (PLD), respectively. X-ray diffraction (XRD) scanning revealed that the two kinds of films could be epitaxially grown in pure single-oriented perovskite phases, but Y-BST thin films showed an enhanced crystallization effect. The dielectric properties of the pure and Y-BST thin films were measured at 10 kHz and 300 K with a parallel-plate capacitor configuration. The results revealed that the addition of Y as an acceptor doping is very effective to increase dielectric tunability, and to reduce leakage current of BST thin films. The figure-of-merit (FOM) factor value increases from 17.32 for BST to 25.84 for Y-BST under an applied electric field of 300 kV/cm. The leakage current density of the BST thin films at a negative bias field of 300 kV/cm decreases from 2.45 × 10⁻⁴ A/cm² to 1.55 × 10⁻⁶ A/cm² by Y doping. The obtained results indicated that the Y-doped BST thin film is a promising candidate material for tunable microwave devices.     

Fabrication and characterization of epitaxial Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript>/LaNiO<Subscript>3 </Subscript>heterostructures

Epitaxial Ba0.6Sr0.4TiO3 (BST)/LaNiO3 (LNO) heterostructures were fabricated on LAO (100) substrates using pulsed laser deposition (PLD). Their structural properties were investigated by X-ray diffraction (XRD). The θ–2θ scans showed single crystalline BST and LNO layers with a (100) orientations perpendicular to the substrate plane. Phi scans (ϕ) on the (220) plane of BST layer indicated that the films have two in-plane orientations with respect to the substrate. The atomic force microscope (AFM) surface morphologies showed a smooth and crack-free surface with the average grain size of 55 nm and the root-mean-square (RMS) of 4.53 nm for BST films. Capacitance–voltage curves are measured. From the capacitance, a dielectric constant of 762, tunabilty of 82.81% and loss tangent of 0.032 are obtained. The current–voltage curve shows that the leakage current is 2.41 × 10⁻⁷ A/cm² under an applied voltage of 2 V.     

Electromagnetic properties of low-temperature-sintered (Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>)TiO<Subscript>3</Subscript>/NiCuZn composites

Dense (Ba_0.6Sr_0.4)TiO₃/Ni_0.37Cu_0.20Zn_0.43Fe_1.92O_3.88 (BST/NiCuZn) composites were prepared by the conventional solid-state reaction method and sintered at 1,050°C. The phase composition and surface morphology of the composites were investigated using XRD and SEM, respectively. The dielectric and magnetic properties of the composites were also reported. In low frequency range the dielectric properties of the BST/NiCuZn composites show Maxwell–Wagner relaxation. In high frequency range the BST/NiCuZn composites possess high dielectric constants and permeabilities, which can be used in high-frequency communications for capacitor-inductor integrating devices such as electromagnetic interference filters and antennas.     

Structural and dielectric properties of Bi doped Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ceramics

The dielectric properties of 0.1–15% mol bismuth doped Ba_0.6Sr_0.4TiO₃ (BST) ceramics have been investigated systematically. The solubility limit of bismuth is determined as about 10 mol% by means of both X-ray diffraction and scanning electron microscopy, which is further verified by the fact that the lattice constant of the samples above 10 mol% is almost invariable. The temperature dependence of the dielectric permittivity suggest that the ferroelectric behavior transit to relaxor ferroelectric type when impurity concentration reaches 5 mol%, and further to relaxor behavior for samples above 10 mol% Bi content, which is verified by the absence of a hysteresis loop. Thermal expansion results show differences between 5 and 10 mol% doped samples. Dielectric tunability at room temperature decreases with bismuth content increasing. The variation of properties was attributed to the impurity induced polar regions and former long-order structure.     

Characterization of Ba<Subscript>0.9</Subscript>Sr<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> prepared by low temperature chloride aqueous synthesis

Ba_0.9Sr_0.1TiO₃ powder was processed at 80°C by reacting Ti sol in aqueous solutions that contained BaCl₂, SrCl₂ and NaOH at atmospheric pressure. Well-crystallized, spherical, nanosizes powders were formed by this method. The powders were found to have a cubic structure, which was retained even after heating at 900°C. Sintering at 1400°C, led to the formation of a tetragonal structure with a secondary phase of Ba₆Ti₁₇O₄₀. Abrupt grain growth was observed at 1400°C. The electrical response of the sample sintered at 1400°C has three electrically different regions. Each region of the sample is represented by different RC element. Element 1 (R ₁ C ₁) is the most resistive and its capacitance ishigh (0.5 nFcm⁻¹) indicating a thin region, probably the grain boundary. Element 2 (R ₂ C ₂) shows a smaller resistance value compared to element 1. The capacitance value of element 2 is temperature-dependent and displays a Curie–Weiss behaviour, indicative of a ferroelectric material above T _c. The lower capacitance of C ₂ (15 pFcm⁻¹) indicates that it is a much thicker region than element 1 and can be assigned as a ferroelectric bulk region. Element 3 is probably an electrode effect.     

Dilution effects on X-ray photoelectron spectra of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> with SiO<Subscript>2</Subscript>

Diluted samples of La_0.8Sr_0.2MnO₃ with SiO₂ were prepared by calcination of the MCM-41 molecular sieve soaked in precursor solutions with various concentrations (0.1, 0.05 and 0.005 mol/l). The diluted samples from the 0.1, 0.05 and 0.005 mol/l solutions showed ferromagnetic behavior in temperature dependent magnetic susceptibility below 300, 250 and 100 K, respectively. The electron binding energy of the La 3d_5/2 main peak of the diluted samples from the 0.1, 0.05 and 0.005 mol/l solutions were 835.7, 836.0 and 837.4 eV, respectively, and were larger than that of La_0.8Sr_0.2MnO₃ bulk sample (834.2 eV). Reduction in intensity of the La 3d charge-transfer satellite was more pronounced for more diluted sample. The Mn 2p_3/2 main peak of all the diluted samples remained at 642.2 eV, which is larger by 0.6 eV than that of the bulk sample (641.6 eV). The charge-transfer peak energy in the optical absorption spectra was the same (2.3 eV) for all the diluted samples, and the energy was larger by 0.4 eV than the bulk one (1.9 eV). The dilution caused localization of charge carriers within the La_0.8Sr_0.2MnO₃ lattices isolated by the insulator. Suppression of charge flow between the isolated La_0.8Sr_0.2MnO₃ lattices resulted in the enlargement of the La 3d electron binding energy and the decrease of the La 3d charge-transfer satellite peak intensity, and also the lowering of the ferromagnetic ordering temperature. © Springer Science + Business Media, Inc.     

Fabrication of conductive SrRuO<Subscript>3</Subscript> thin film and Ba<Subscript>0.60</Subscript>Sr<Subscript>0.40</Subscript>TiO<Subscript>3</Subscript>/SrRuO<Subscript>3</Subscript> bilayer films on MgO substrate

Conductive SrRuO₃ (SRO) thin films have been grown on (100) MgO substrates by pulsed laser deposition (PLD) technique. Effects of oxygen pressure and deposition temperature on the orientation of SRO thin film were investigated. X-ray diffraction (XRD) θ/2θ patterns and the temperature dependent resistivity measurements indicated that oxygen pressure of 30 Pa and deposition temperature of 700 °C were the optimized deposition parameters. A parallel-plate capacitor structure was prepared with the SRO films deposited under optimized condition as an electrode layer and Ba_0.60Sr_0.40TiO₃ (BST) thin film as the dielectric layer. XRD Φ scans indicated a epitaxial relationship between BST and SRO on MgO substrate. The dielectric constant and loss tangent measured at 10 kHz and 300 K was 427 and 0.099 under 0 V bias, and 215 and 0.062 under 8 V bias, respectively. A tunability of 49.6% has been achieved with DC bias as low as 8 V. The C–V hysteresis curve and the P–E hysteresis loop suggested that the BST films epitaxially grown on SRO/MgO have ferroelectricity at room temperature. The induced ferroelectricity was believed to originate from the compressive strain between the epitaxial BST and SRO thin films. These results show the potential application of the BST/SRO heterostructures in microelectronic devices.     

Crystallization and electrical properties of Ba<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>TiO<Subscript>3</Subscript> thin films on SrRuO<Subscript>3</Subscript>/Pt hybrid bottom electrode

Ba_0.7Sr_0.3TiO₃ (BST) thin films were deposited on Pt and SrRuO₃(SRO)/Pt hybrid bottom electrodes by radio frequency magnetron sputtering. X-ray analysis indicated that both films were polycrystalline. Dielectric measurements showed that the films on SRO/Pt hybrid bottom electrode had lower dielectric constant and loss than the films on single Pt and the dielectric properties were frequency-independent. The leakage current density of Ba_0.7Sr_0.3TiO₃ thin films on hybrid bottom electrode was also lower. Leakage mechanism investigations showed that the contact between the electrode-film interfaces of thin films on SRO/Pt hybrid bottom electrode was ohmic. Based on the results, the effects of SRO/Pt hybrid bottom electrode on the crystallization and electrical properties of BST thin films were discussed.     

Effect of annealing on leakage current characteristics of Pt/Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript>/Pt thin-film capacitors

The effect of annealing on leakage current characteristics of Pt/Ba_0.6Sr_0.4TiO₃/Pt ferroelectric thin-film capacitors was investigated at the temperature range from 273 K to 393 K. The results show that the depletion layer width of the as-deposited BST film is about 3–5 times greater than that of the annealed film. For as-deposited samples, the Schottky barrier height increases with increasing temperature and voltage. However, for annealed samples, the Schottky barrier height linearly decreases with increasing voltage and is almost independent upon temperature.     

Effect of A-site dopant on the piezoresistive characteristics of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> ceramics

This letter reports the effect of the A-site doping (2, 4, and 6 mol% Bi and Li) on the piezoresistance phenomenon in La_0.8Sr_0.2MnO₃ (LSMO) polycrystalline ceramics. The fractional change in resistivity was found to be nominal for Li-modified samples but samples modified with 4 and 6 mol% Bi₂O₃ exhibited 1.8% and 2.3% fractional change in resistivity at 19.2 MPa which is significantly higher than that for pure LSMO. The enhancement in piezoresistive phenomenon is attributed to distortion of Mn–O bond due to substitution of smaller ion on to La-site. All the samples showed a sudden increase in resistivity with applied stress in the range of 0.5–2 MPa and the behavior was found to saturate as the magnitude of applied stress increases. Magnetic measurements as a function of field and temperature were conducted to confirm the A-site substitution.     

Investigation of Ba<Subscript>2-x</Subscript>Sr<Subscript>x</Subscript>TiO<Subscript>4</Subscript>: Structural aspects and dielectric properties

Investigation of solid solution of barium-strontium orthotitanates of the type, Ba_2-x Sr _x TiO₄ (0 ≤x≤ 2), show that pure phases exist only for the end members, Ba₂TiO₄ and Sr₂TiO₄, crystallizing in the β-K₂SO₄ and K₂NiF₄ structures, respectively. The intermediate compositions (till≥ 1) lead to a biphasic mixture of two Ba₂TiO₄-type phases (probably through a spinodal decomposition) with decreasing lattice parameters, indicating Sr-substitution in both the phases. Forx > 1, Sr₂TiO₄ along with a secondary phase is obtained. The dielectric constant and dielectric loss were found to decrease with Sr substitution till the nominal composition ofx = 1. However, pure Sr₂TiO₄ shows higher dielectric constant compared to the solid solution composition. Sr₂TiO₄ shows very high temperature stability of the dielectric constant.     

Electrical properties of thin Ba<Subscript>x</Subscript>Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> films on silicon dioxide substrates

We have studied the electrical properties of thin ferroelectric films of barium strontium titanate (Ba_xSr_1−x TiO₃) obtained on fused quartz (SiO₂) substrates by RF magnetron sputtering. Dependences of the tuning coefficient and dielectric loss tangent on the synthesis temperature and the film thickness are reported. The results are compared to analogous data for films grown on polycrystalline alumina substrates.     

Study on dielectric and tunable properties of Cr-doped Ba<Subscript>0</Subscript><Subscript>.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> thin films by rf sputtering

Ba_0.6Sr_0.4TiO₃ dielectric thin films doped by Cr(0, 1, 2.5, 5, 10 mol%) (BSTC) were prepared by radio frequency magnetron sputtering on Pt/Ti/SiO₂/Si substrates. The structure and morphology of the BSTC thin films were studied by atomic force microscopy and X-ray diffraction. The effect of Cr doping on the dielectric properties of BST thin films were analyzed. The results show that the dielectric loss of Cr doping BST thin films is lower than that undoped, and the tunability increased with Cr doping. The thin film doped with 5 mol% Cr has the best dielectric properties. The tunability, loss and figure of merit (FOM) at 1 MHz were 38.9%, 0.0183, and 21.3, respectively.     

Preparation of microwave dielectric,Sn<Subscript>0.2</Subscript>Zr<Subscript>0.8</Subscript>TiO<Subscript>4</Subscript>

A simple coprecipitation technique is described for the preparation of tin substituted zirconium titanate ceramic powders.     

Effects of sintering temperature on the properties of Mn/Y codoped Ba<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>TiO<Subscript>3</Subscript> ceramics for tunable application

(Ba_0.67Sr_0.33)_1?3x/2Y _x Ti_1?y/2Mn _y O₃ [BST(Mn + Y), x = 0.006, y = 0.005] ceramics were fabricated by using citrate–nitrate combustion derived powder. Microstructure and dielectric properties of the BST(Mn + Y) ceramic samples were investigated within the sintering temperature ranged from 1220 to 1300 °C. Sintering temperature has a great influence on the microstructure and electrical properties of the ceramic samples. The dielectric properties, ferroelectric properties, and tunability are enhanced by optimizing sintering temperature. The relatively high tunability of 40 % (1.5 kV/mm DC field, 10 kHz) was obtained, and relatively low dielectric loss, <0.0052 (at 10 kHz, 20 °C) was acquired for BST(Mn + Y) samples sintered at 1275 °C for 3 h. Both the low dielectric loss and enhanced tunable properties of BST(Mn + Y) are useful for tunable devices application.     

Impedance spectroscopy of Ba<Subscript>3</Subscript>Sr<Subscript>2</Subscript>DyTi<Subscript>3</Subscript>V<Subscript>7</Subscript>O<Subscript>30</Subscript> ceramic

Polycrystalline sample of Ba₃Sr₂DyTi₃V₇O₃₀ was prepared at 950°C using a high-temperature solid-state reaction technique. X-ray structural analysis indicated the formation of a single-phase orthorhombic structure with lattice parameters: a = 12·2719 (39) Å, b = 8·9715(39) Å and c = 19·7812(39) Å. Microstructural study showed densely packed uniform distribution of grains over the surface of the sample. The a.c. impedance plots were used as tools to analyse the electrical response of the sample as a function of frequency at different temperatures (30–500°C). These plots revealed the presence of grain boundary effect, from 200·C onwards. Complex impedance analysis showed non-Debye type of dielectric relaxation. The Nyquist plots showed the negative temperature coefficient of resistance character of Ba₃Sr₂DyTi₃V₇O₃₀. A hopping mechanism of electrical transport processes in the system is evident from the modulus analysis. The activation energy of the compound (calculated both from loss and modulus spectrum) is the same, and hence the relaxation process may be attributed to the same type of charge carrier.     

Electrical Conductivity and Complex Impedance Analysis of Ba<Subscript>2</Subscript>CrMo<Subscript>0.8</Subscript>W<Subscript>0.2</Subscript>O<Subscript>6</Subscript> Double Perovskite

Electrical properties of Ba ₂CrMo_0.8W_0.2O₆ double perovskite were investigated using admittance spectroscopy technique. According to impedance analysis, the material was modeled by an electrical equivalent circuit. Such analysis proves the presence of relaxation phenomenon in the compound. We also found that ac conductivity follows the Jonscher universal power law. Conduction process is found to be dominated by the thermally activated small polaron (SPH). The activation energy values, inferred from dc conductivity and from the temperature dependence of relaxation time, are closed to each other. Such result indicates that conduction process and relaxation phenomenon are related to the same defect.     

Microstructural characterisation by X-ray scattering of perovskite-type La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3±δ</Subscript> thin films prepared by a dip-coating process

The La_0.8Sr_0.2MnO₃ (LSM) cathode materials are widely used in solid oxide fuel cells (SOFCs) as electronic conductors. In such materials, the reduction of oxygen is located at the triple contact boundaries: air/cathode LSM/electrolyte which is generally Yttria Stabilised Zirconia (YSZ). In order to improve the chemical reactions at these air/cathode LSM/electrolyte interfaces, the triple phase boundary length has to be optimised. In this aim, we have first synthesised the La_0.8Sr_0.2MnO₃ phase by a sol–gel route and, second, LSM thin films have been deposited on various polished substrates by using a dip-coating process. The structure and microstructure of the resulting LSM thin layers have been investigated by using well suited complementary techniques such as X-ray reflectometry, grazing incidence small angle X-ray scattering, X-ray diffraction and scanning electronic microscopy. The structural and microstructural parameters of LSM thin films have been managed and studied as a function of synthesis parameters such as initial metallic salt concentration, time and temperature of annealing. The higher the metallic salt concentration, the higher the thickness of the film, the smaller the film density. The as-prepared layers are amorphous and the single crystallised perovskite form is obtained for low temperature heat treatments. Therefore, the annealed coatings are constituted by randomly oriented LSM nanocrystals, which organise in a more or less dense close-packed microstructure according to the initial metallic salt concentration.     

Synthesis of Ba<Subscript>3</Subscript>ZnNb<Subscript>2</Subscript>O<Subscript>9</Subscript>−Sr<Subscript>3</Subscript>ZnNb<Subscript>2</Subscript>O<Subscript>9</Subscript> solid solution and their dielectric properties

Oxides of the type, Ba_3-xSr_xZnNb₂O₉ (0 ≤x ≤3), were synthesized by the solid state route. Oxides calcined at 1000°C show single cubic phase for all the compositions. The cubic lattice parameter (a) decreases with increase in Sr concentration from 4.0938(2) forx = 0 to 4.0067(2) forx = 3. Scanning electron micrographs show maximum grain size for thex = 1 composition (∼ 2 μm) at 1200°C. Disks sintered at 1200°C show dielectric constant variation between 28 and 40 (at 500 kHz) for different values of x with the maximum dielectric constant atx = 1.