Fabrication and electrical properties of sol-gel-derived Ba0.8Sr0.2TiO3 ferroelectric films from a 0.05-M spin-on solution

Barium strontium titanate (Ba_0.8Sr_0.2TiO₃) films with good ferroelectricity have been obtained by a developed sol-gel processing, using a 0.05-M spin-on solution. X-ray diffraction and Raman spectroscopy investigations showed that the Ba_0.8Sr_0.2TiO₃ film exhibited a tetragonal structure at room temperature. Field-emission scanning electron microscopy measurements revealed that large columnar grains with the size of 100 to 200 nm in the film were formed from the highly dilute spin-on solution with layer-by-layer homoepitaxy. Electrical measurements for the prepared Ba_0.8Sr_0.2TiO₃ film showed a remnant polarization of 3.5 μC/cm², a coercive field of 53 kV/cm, two distinctive phase transitions, lower dissipation factor, and good insulating properties. These results indicate the sol-gel-derived Ba_0.8Sr_0.2TiO₃ film from a 0.05-M solution is suitable for uncooled infrared detector applications. Received: 19 August 1999 / Accepted: 11 October 1999 / Published online: 1 March 2000     

The Field Effect in a Metal–Ferroelectric–Semiconductor System of Multilayer Ferroelectric Films with Various Structure Types

The ability to grow the interfacial defect-poor Sr_0.5Ba_0.5Nb₂O₆ + Ba_0.2Sr_0.8TiO₃ and Ba_0.8Sr_0.2TiO₃ + Ba_0.4Sr_0.6TiO₃ ferroelectric films onto the doped silicon substrates is discussed. A study of piezo-response via the quasi-static method (using the electrode area of 0.07 mm²) reveals that heterostructures possess an initial polarized ferroelectric state with a spontaneous polarization vector perpendicular to the substrate at any type of Si conductivity. The polarized state is established to refer to two-dimension stresses in the ferroelectric, which is tunable through a preprepared Ba_xSr_{1 – x}TiO₃ onto a sublayer substrate as well as to a thickness of this sublayer. Polarization switching in Sr_0.5Ba_0.5Nb₂O₆/Si and Ba_0.8Sr_0.2TiO₃/Si heterostructures under the external field arises at only using the barium–strontium titanate sublayer predeposited onto silicon. A 15% decrease in switching polarization in Ba_0.8Sr_0.2TiO₃/Ba_0.4Sr_0.6TiO₃/Si structures is observed after 500 h.     

Vibrational spectroscopic studies on Ba0.8Sr0.2TiO3 thin films prepared by RF sputtering technique

Thin films of Ba_0.8Sr_0.2TiO₃ have been deposited on p-type Si substrate by radio frequency magnetron sputtering. Polycrystalline bulk Ba_0.8Sr_0.2TiO₃ sample has also been studied for comparison. X-ray diffraction patterns reveal that both the bulk sample and thin films are polycrystalline without any preferential orientation and belong to paraelectric cubic phase. We have compared the room temperature Raman and IR spectra of powder and thin films (both annealed and as-deposited) of Ba_0.8Sr_0.2TiO₃. The extra feature in the Raman spectrum for the annealed film has been explained as due to the presence of intergrain stresses from the submicron size grains in it.     

溶胶-凝胶法制备MgO/(Ba0.8Sr0.2)TiO3多层薄膜及其介电和漏电特性研究

采用改进的溶胶-凝胶方法在LaNiO₃/Si(100)衬底上制备了MgO/(Ba_{0.8Sr0.2)TiO3多层薄膜.实验结果表明，MgO层的引入改变了(Ba0.8}Sr_0.2)TiO₃的介电特性和漏电流行为，使薄膜的漏电 流降低了3个数量级，但介电常数也有相应降低.漏电流的显著降低是由MgO子层的高阻特性 以及微量Mg向(Ba_0.8关键词： 0.8Sr_0.2)TiO₃多层薄膜')" href="#">MgO/(Ba_0.8Sr_0.2)TiO₃多层薄膜 漏电流 介电常 数     

Preparation and characterisation of compositionally graded BaxSr1-xTiO3 thin films

Ba_xSr_1-xTiO₃ thin films with a compositional gradient of x=0.3 to 1 (in 0.1 mole fraction increments) were fabricated on Pt/Ti/SiO₂/Si substrates using a modified sol–gel technique. The graded film crystallised in a perovskite structure and consists of a uniform microstructure with comparatively larger grains. The room-temperature relative dielectric constant (ε_r) and dielectric loss (cosδ) at 100 kHz were found to be 305 and 0.03 respectively. Dielectric peaks were not observed in the temperature range from -20 °C to 120 °C. The dielectric constant and dielectric loss were almost independent of temperature. Polarisation–electric field measurements at room temperature revealed a saturated but slim hysteresis loop with a remanent polarisation (P_r) of 0.6 μC/cm² and a coercive field (E_c) of 2.4 kV/mm. The graded film behaves as a stack of Ba_xSr_1-xTiO₃ capacitors connected in series and hence the dielectric Curie peaks are removed. Received: 4 October 2001 / Accepted: 17 October 2001 / Published online: 23 January 2002     

Growth of Ba2−x Sr x NaNb5O15 thin film on La0.05Sr0.95TiO3 substrate by pulsed laser deposition

Ba_2−x Sr _x NaNb₅O₁₅ thin films were prepared on La_0.05Sr_0.95TiO₃ substrates by pulsed laser deposition. The structural and ferroelectric properties of the thin films depended on substrate temperature (T _sub) and Sr concentration. When T _sub was fixed at 700 °C, the Ba_2−x Sr _x NaNb₅O₁₅ (x = 0, 0.6, 1.0, and 1.4) thin films exhibited a high c-axis orientation. The thin films consisted of well-developed grains and exhibited a smooth surface. The c-axis-oriented Ba_0.6Sr_1.4NaNb₅O₁₅ thin film with the lowest Curie temperature also exhibited a high c-axis orientation and a P-E hysteresis loop with a high ferroelectricity at T _sub 650 °C. Thus, its remanent polarization (P _r) and coercive field (E _c) were 2P _r 24.9 μC/cm² and 2E _c 107 kV/cm, respectively. These values indicate that Ba_2−x Sr _x NaNb₅O₁₅ has ferroelectricity in the thin film form.     

Relaxation of polarized states in thin films of BST

The possibility of the local polarization of epitaxial Ba_0.8Sr_0.2TiO₃ thin film is studied by means of piezoresponse force microscopy. The existence of a local polarized state depends on the duration of the applied pulse. The kinetics of polarized states explaining the experiment is considered in the context of phenomenological theory.     

Effect of internal strain fields on the controllability of nanodimensional ferroelectric films in a plane capacitor

Nanodimensional ferroelectric heteroepitaxial Ba_0.8Sr_0.2TiO₃ films grown by the layer-by-layer mechanism on MgO(100) substrates are examined by the X-ray diffraction and transmission electron microscopy methods. It is established that, when the thickness of the film changes, the stress relaxation proceeds via generation of misfit dislocations at the film-substrate interface. There exists a critical thickness (≈40 nm) of the film below and above which the film possesses tensile and compression stresses, respectively. Examples of how the stresses influence the insulating properties of the films are given.     

发光二极管用红色荧光粉Sr0.8-xBaxEu0.2WO4的制备和性质研究

采用化学共沉淀法制备了不同Ba²⁺掺杂浓度、 不同煅烧温度的Sr_0.8-xBa_xEu_0.2WO₄红色荧光粉. 研究了样品的晶体取向和晶格 畸变对发光性质的影响, 实验结果表明: 合成的Sr_0.8-xBa_xEu_0.2WO₄红色荧光粉为四方相, 样品中Eu³⁺的⁵D₀–⁷F₂跃迁的红光能被近紫外光和蓝光有效激发. 适量的Ba²⁺离子取代部分的Sr²⁺提高了Sr_0.8Eu_0.2WO₄荧光粉的发光强度, Ba²⁺掺杂浓度的改变对基质的晶格参数、晶体对称性和发光性能影响较大, Ba²⁺的最佳掺杂量为30%.     

High-resolution transmission electron microscopy of heteroepitaxial barium strontium titanate films grown on MgO substrates

Nanoscale (5–100 nm) ferroelectric heteroepitaxial Ba_0.8Sr_0.2TiO₃ films on MgO(001) substrates were studied by methods of high-resolution transmission electron microscopy using Tecnai G² and FEI Titan 80–300 microscopes. Misfit dislocations resulting from stress relaxation in films and insignificant local misorientation of film regions (block structure) were detected. The heterostructure was numerically simulated, which allowed the detection of the formation of oxygen (substrate)-titanium (film) bonds or the oxygen (substrate)-barium (film) bond at the film-substrate interface.     

Polarization characteristics of graded thick Ba<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> films

The barium strontium titanate ceramics Ba_{1 − x} Sr _x TiO₃ with a spatially variable composition has been prepared according to the thick film technology (tape casting). The strontium content over the film thickness is varied from 0 to 30 mol %. The structure and polarization characteristics of the samples prepared have been investigated. It has been found that the polarization characteristics of multilayer structures are determined by the ratio between the thicknesses of layers with different compositions and by their properties. No shift of the hysteresis loops in the graded thick Ba_{1 − x} Sr _x TiO₃ ( _x = 0–0.3) films has been revealed. The results obtained have been analyzed in the framework of modern theoretical approaches.     

Critical concentrations in Ba-doped incipient ferroelectric SrTiO3

Temperature-induced variations of light refraction and dielectric permittivity in single-crystal Sr_1−x Ba_xTiO₃ (x=0.02, 0.05, 0.07, and 0.14), Sr_1−x Ca_xTiO₃ (x=0.014), and in nominally pure strontium titanate have been studied within the 17–300 K temperature range. The spontaneous polar contribution to the refractive index has been isolated. It was used to calculate the temperature and concentration dependences of the polarization autocorrelation function 〈P _s ^2〉 in the Sr_1−x Ba_xTiO₃ system. For x⩽0.07, the polarization P _s=〈P _s ² 〉^1/2 varies proportional to (x−x _g)^1/2, where x _g=0.0027 is the new critical concentration in Sr_1−x Ba_xTiO₃, below which short-range polar order vanishes. Fiz. Tverd. Tela (St. Petersburg) 39, 704–710 (April 1997)     

Effect of growth mechanisms on the deformation of a unit cell and polarization reversal in barium–strontium titanate heterostructures on magnesium oxide

The effect of a growth mechanism on the unit cell strain and the related change in the properties of single-crystal Ba_0.8Sr_0.2TiO₃ films grown on MgO substrates according to the Frank–van der Merwe and Volmer–Weber growth mechanisms is studied. The unit cell strain is shown to depend substantially on the film thickness and the growth mechanism. It is found that the same film–substrate pair can be used to vary stresses in the film from two-dimensional tensile to compressive stresses due to a change in the growth mechanism and the film thickness.     

Physical properties of Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> thin films

The behavior of material constants in ferroelectric Ba_0.8Sr_0.2TiO₃ thin films is studied depending on the misfit strain at room temperature in the context of nonlinear thermodynamic potential of the phenomenological theory. Some constants are found to undergo drastic changes with the alternating strain at the interfaces. The gathered results allow one to evaluate the material constants for a specific film and to outline the direction in searching the ways to synthesize films with the needed properties.     

Optical properties of the Ba0.8Sr0.2TiO3/(Bi0.82, Nd0.02)FeO3 superlattice

A Ba_0.8Sr_0.2TiO₃/(Bi_0.82, Nd_0.02)FeO₃ multilayer heteroepitaxial structure is prepared by successively depositing 20 Ba_0.8Sr_0.2TiO₃ and (Bi_0.82, Nd_0.02)FeO₃ layers, each 4 nm thick, using the method of rf sputtering. The layers grow on a single-crystal MgO substrate following the layer-by-layer mechanism. The structural perfection of the layers is examined by X-ray diffraction. The optical transmission is studied in the wavelength interval 200–1100 nm. The spectra are processed using a dispersion formula for the permittivity represented as a superposition of two oscillators with regard to relaxation. Such an approach allows us to separate direct and indirect transitions. The absorption edge of the superlattice for direct transitions is 80 nm wide and is estimated to be 3.78 eV.     

Structure and impedance spectroscopy of Pr1? x Sr x Fe0.8Co0.2O3? δ ( x =0.1, 0.2, 0.3) thin films grown by laser ablation

Polycrystalline samples of Pr_1−x Sr _x Fe_0.8Co_0.2 O_3−δ (x=0.1, 0.2, 0.3) (PSFC) were prepared by the combustion synthesis route at 1200°C. The structure of the polycrystalline powders was analysed with X-ray powder diffraction data. The X-ray diffraction (XRD) patterns were indexed as the orthoferrite similar to that of PrFeO₃ having a single-phase orthorhombic perovskite structure (Pbnm). Pr_1−x Sr _x Fe_0.8Co_0.2O_3−δ (x=0.1, 0.2, 0.3) films have been deposited on yttria-stabilized zirconia (YSZ) single-crystal substrates at 700°C by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell cathodes. The structure of the films was analysed by XRD, scanning electron microscopy (SEM) and atomic force microscopy (AFM). All films are polycrystalline with a marked texture and present pyramidal grains in the surface with different size distributions. Electrochemical impedance spectroscopy (EIS) measurements of PSFC/YSZ single crystal/PSFC test cells were conducted. The Pr_0.7Sr_0.3Fe_0.8Co_0.2O_3−δ film at 850°C presents a lower area specific resistance (ASR) value, 1.65 Ω cm², followed by the Pr_0.8Sr_0.2Fe_0.8Co_0.2O_3−δ (2.29 Ω cm² at 850°C) and the Pr_0.9Sr_0.1Fe_0.8Co_0.2O_3−δ films (5.45 Ω cm² at 850°C).     

Dielectric permittivity dynamics of Ba1−x SrxTiO3 epitaxial films (x=0.75): Microstructure and depolarization effects

Trilayer epitaxial heterostructures including metal oxide electrodes (SrRuO₃, 200 nm) and a sandwiched dielectric layer (Ba_0.25Sr_0.75TiO₃, 700 nm) were grown by laser ablation on (001)LaAlO₃ substrates. The maximum permittivity of the Ba_0.25Sr_0.75TiO₃ layer (?′/?₀≈3700) was obtained at T _M =160 K and an external electric field E≈10⁶ V/m. The ?′(T) dependence for the Ba_0.25Sr_0.75TiO₃ layer in the paraelectric phase is well fitted by the Curie-Weiss relation, with the Curie constant and the Weiss temperature differing only insignificantly from the corresponding bulk values. The change in the permittivity of the Ba_0.25Sr_0.75TiO₃ layer induced by the application of a ±2.5 V bias voltage to the electrodes reached as high as 85%. The electric-field dependence of the polarization retained clearly pronounced saturated hysteresis loops up to temperatures 10–15 K above T _M .     

Characteristics of Ba xSr 1–xTiO 3 thin films grown by pulsed laser ablation of rotating split targets of BaTiO 3 and SrTiO 3

We have grown heterostructures of Ba_xSr_1-xTiO₃(BST)/La_0.7Sr_0.3MnO₃(LSMO) on LaAlO₃(LAO) substrates by the pulsed laser deposition method. BST films with x=0.2,0.5,0.7 and 0.8 have been prepared using a novel rotating split-target arrangement. The lattice constant of the BST films is found to vary linearly with Ba/Sr ratio. An excellent cube-on-cube epitaxial relationship of (100)_BST||(100)_LSMO||(100)_LAO has also been obtained. Scanning electron microscopy studies have revealed smooth and crack-free BST films with a uniform grain size of about 100 nm. Dielectric measurements, made with patterned Au top electrodes and conducting LSMO bottom layers, have shown a maximum permittivity of approximately 280 at 5 kHz in BST films with x=0.7. P–E loop analyses of the Ba_0.7Sr_0.3TiO₃ and Ba_0.8Sr_0.2TiO₃ films have yielded remnant polarization values of 1.66 and 1.81C/cm², respectively. PACS 81.15Fg; 68.55Jk; 77.55+f     

Geometrical effects in nanodimensional epitaxial films of barium strontium titanate

The effect of the thickness of 6- to 950-nm-thick Ba_0.8Sr_0.2TiO₃ films epitaxially grown on (001)MgO on their ferroelectric properties is investigated. Raman scattering and X-ray diffraction data indicate a structural phase transition taking place at a film thickness of ≈70 nm, which changes drastically the lattice parameters of the film. Raman spectra taken of the films confirm that they are in the ferroelectric state and that their symmetry changes in going over a critical thickness, as revealed by a sharp displacement of the peaks corresponding to the A ₁(TO) and E(TO) components of the soft mode. At film thicknesses of <100 nm, the permittivity versus thickness dependence exhibits two peaks at thicknesses of ～18 and ～36 nm. Near the first peak, the dielectric nonlinearity is considerably higher than near the second one.     

Dielectric properties and magnetoelectric effect of (x)NiFe2O4+(1−x)Ba0.8Sr0.2TiO3 composites

Magnetoelectric composites of NiFe₂O₄ and Ba_0.8Sr_0.2TiO₃ were prepared using conventional double-sintering ceramic method. The phase formation of magnetoelectric composites was confirmed by XRD technique. Variation of dielectric constant and loss tangent at room temperature with frequency in the range 100 Hz-1 MHz has been studied. Also the variation of dielectric constant and loss tangent with temperature and composition at fixed frequencies of 1 kHz, 10 kHz, 100 kHz and 1 MHz is reported. The static value of the magnetoelectric conversion factor was measured as a function of intensity of the magnetic field. The ME voltage coefficient of about 430 μV/cm Oe was observed for 15% NiFe₂O₄+85% Ba_0.8Sr_0.2TiO₃ composite. All the samples show linear variation of magnetoelectric conversion in the presence of static magnetic field.