Ferroelectric and dielectric properties of sol-gel derived BaxSr1−xTiO3 thin films

Ferroelectric thin films of Ba_0.7Sr_0.3TiO₃, Ba_0.8Sr_0.2TiO₃, Ba_0.9Sr_0.1TiO₃ and BaTiO₃ were fabricated by a modified sol-gel technique on Pt/Ti/SiO₂/Si substrates. All the compositions crystallized in perovskite structure and consist of well-defined grains. As the value of x increases grain size of the Ba_xSr_1−xTiO₃ thin films increases while the dielectric permittivity decreases. Ba_0.7Sr_0.3TiO₃ composition possesses the highest dielectric permittivity of 748 (at 100 kHz). Hysteresis loops measured at room temperature for all compositions showed that BaTiO₃ has the largest remnant polarization of 4.8 μC/cm². The dielectric and ferroelectric properties of the sol-gel derived Ba_xSr_1−xTiO₃ thin films are strongly dependent on the Sr content and the grain size.     

Dielectric dispersion and tunability of sol-gel derived Ba x Sr1−x TiO3 thin films

Ba_0.5Sr_0.5TiO₃, Ba_0.6Sr_0.4TiO₃, Ba_0.7Sr_0.3TiO₃ and Ba_0.8Sr_0.2TiO₃ thin films were fabricated by a modified sol-gel technique on Pt(111)/Ti/SiO₂/Si(100) substrates. All Ba _x Sr_1–x TiO₃ films crystallized in the perovskite structure with a crack free microstructure and clear grain boundaries. Highest relative permittivity and dielectric tunability was observed in the Ba_0.7Sr_0.3TiO₃ thin film. Ba_0.7Sr_0.3TiO₃ and Ba_0.8Sr_0.2TiO₃ compositions demonstrated ferroelectric hysteresis loops indicating the presence of ferroelectricity at room temperature. The paraelectric compositions of Ba_0.5Sr_0.5TiO₃ and Ba_0.6Sr_0.4TiO₃ showed significant tunability with negligible loss tangent. The tunability of Ba_0.5Sr_0.5TiO₃ thin film decreased with the increase of frequency from 100 kHz to 100 MHz. As the frequency increases, especially above 10 MHz, the relative permittivity decreases while the loss tangent increases. Since Ba_0.5Sr_0.5TiO₃ thin film is paraelectric at room temperature, relaxation due to ferroelectric domains cannot occur. Therefore this behaviour has originated from the contact resistance and finite sheet resistance of both the bottom and top electrodes. To analyse the thin film capacitor, the parallel plate capacitor structure can be modeled based on an equivalent circuit, which contain electrode and contact resistance.     

Preparation and characterization of nano-sized Sr0.7Ca0.3TiO3 crystallines by low temperature aqueous synthesis method

Nano-sized calcium strontium titanate (Sr_0.7Ca_0.3TiO₃) particles were prepared by low temperature aqueous synthesis method at temperature as low as 90 °C and under ambient pressure. To improve the morphology and crystallinity of the particles, the hydrothermal treatment was used. The lattice structure, particle size, particle morphology, and hydroxyl defects of Sr_0.7Ca_0.3TiO₃ particles were investigated by using XRD, TEM, FE-SEM, TG and FT-IR measurements. The as-prepared particles with size about 100 nm were single cubic phase crystallines which consist of aggregates of small rounded nanocrystals about 10 nm in diameter. However, in as-prepared crystallines, a hydroxyl group was detected as a lattice defect. After the hydrothermal treatment, the hydroxyl groups in Sr_0.7Ca_0.3TiO₃ nanoparticles were partially released from the perovskite lattice. The morphology and crystallinity of the hydrothermally treated particles were observably improved.     

Synthesis and characterization of Ba0.7Sr0.3TiO3, BaZr0.3Ti0.7O3 thin film heterostructures

The paper presents synthesis of Ba_0.7Sr_0.3TiO₃ (BST), Ba_0.7Sr_0.3TiO₃ (BZT) thin films and BZT/BST heterostructures using modified Pechini method. The La_0.7Sr_0.3MnO₃ has been used as a conducting bottom layer to form metal ferroelectric metal capacitor. The thin films are spin coated on SiO₂/n-Si (100) substrates. The thin films thus deposited are characterized for crystal structure, morphology, dielectric and complex impedance properties. The results show that BZT/BST heterostructures show reduced loss tangent tan δ and useful value of figure of merit γ in RF range of frequencies. The results on dielectric properties could be analyzed in terms of the Maxwell–Wagner Model and contribution due to superlattice effects.     

Sol-gel synthesis of lead-free (K0.5Bi0.5)0.4Ba0.6TiO3 nanorods

A kind of lead-free ferroelectric nanorods, (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃, has been prepared by the sol-gel process. The phase formation, structure and morphological analyses of (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃ were investigated by XRD, FTIR, Raman and TEM. The results revealed that single-crystalline (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃ nanorods with width around 80 to 120 nm, and length around 200-300 nm were obtained by calcining dried gels at 800 °C for 2 h. Raman analysis of (K_0.5Bi_0.5)_0.4Ba_0.6TiO₃ nanorods indicated that A₁(TO₂) and E(TO) mode incorporated into one broad peak at around 285 cm^− 1, which can be attributed to the cation disorder (Bi, K, Ba) on the 12-fold coordinated A site of ABO₃ structure.     

Phase formation and dielectric properties of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> by slow injection sol–gel technique

A simple sol–gel process incorporating slow precursor injection technique was employed to synthesize homogeneous Ba_0.5Sr_0.5TiO₃ nano powders. The Ba_0.5Sr_0.5TiO₃ samples were subjected to calcination temperatures from 600 to 1,100 °C and sintering temperatures from 1,250 to 1,350 °C for the study of phase formation, crystallite size, particle distribution, and dielectric properties. Single phase Ba_0.5Sr_0.5TiO₃ with a cubic perovskite structure was successfully synthesized after calcination at 800 °C. The average size of the nano particles is 42 nm with a narrow size distribution, and a standard deviation of 10%. The highest values recorded within the investigated range for dielectric constant, and dielectric loss measured at 1 kHz are 1,164 and 0.063, respectively, for Ba_0.5Sr_0.5TiO₃ pellets calcined at 800 °C and sintered at 1,350 °C. Leakage current density measured at 5 V for the Ba_0.5Sr_0.5TiO₃ pellet was found to be 49.4 pA/cm².     

Calcium-doping for enhanced temperature stability of (Ba0.6Sr0.4)1−xCaxTiO3 thin film dielectric properties

Ternary (Ba_0.6Sr_0.4)_1−xCa_xTiO₃ (BSCT) (x = 0, 0.1, 0.2, 0.3 and 0.4) thin films with thickness of around 500 nm were prepared on Pt(111)/TiO₂/SiO₂/Si substrates by sol-gel methods. BSCT forms the complete solid solutions in a single cubic perovskite structure. The lattice constant, dielectric constant, tanδ and tunability of BSCT decrease, whereas the temperature stability of dielectric properties increases with increasing the Ca concentration. From 25 to 100 °C, the decrease of tunability is about 11% for BSCT with 40 at.% of Ca. BSCT thin films exhibit the comparable tunability, low loss and enhanced temperature stability.     

Studies on magnetic and magnetoelectric properties of the NiFe2O4–Ba0.7Sr0.3TiO3 composites

The magnetic and magnetoelectric properties of magnetoelectric (ME) composites consisting of with nickel ferrite (NiFe₂O₄) and barium strontium titanate (Ba_0.7Sr_0.3TiO₃) were investigated. The composites were prepared by standard double sintering ceramic method. The X-ray diffraction analysis was carried out to confirm the phases formed during sintering and also to calculate the lattice parameters. The hysteresis measurements were done to determine saturation magnetization (M_s), remenance magnetization (M_r) and coercivity (H_c) of the samples. The magnetoelectric voltage coefficient (dE/dH)_H was studied as a function of intensity of the magnetic field. The measured magnetoelectric (ME) response demonstrated strong dependence on the volume fraction of NiFe₂O₄ and the applied magnetic field. A large ME voltage coefficient of about 560 μVcm⁻¹Oe⁻¹ was observed for 15% NiFe₂O₄ + 85% Ba_0.7Sr_0.3TiO₃ composite.     

Ferroic metal-oxide films grown by polymer assisted deposition

Polymer assisted deposition is a versatile technique to grow simple and complex metal-oxide thin films. In this paper we report the structural and electrical properties of ferroic materials, namely La_0.67M_0.33MnO₃ (M = Sr and Ca) and Ba_1 − xSr_xTiO₃ (x = 0.3, 0.5, and 0.7) prepared using this process. The films were prepared on single crystalline LaAlO₃ substrates. The films were highly c-axis oriented and epitaxial in nature. The ferromagnetic La_0.67Sr_0.33MnO₃ and La_0.67Ca_0.33MnO₃ films show intrinsic transport properties with maximum magnetoresistance values (at applied field of 5 T) of − 50% and − 88%, respectively. The highest dielectric constant (∼ 1010) and tunability (∼ 69%) of Ba_1 − xSr_xTiO₃ film occurs at x = 0.3 for films, which is at the phase boundary of tetragonal and cubic.     

Dielectric and tunable properties of Pb0.25BaxSr0.75−xTiO3 thin films fabricated by a modified sol-gel method

A modified sol-gel method was used to fabricate (Pb_0.25Ba_x Sr_0.75−x)TiO₃ (PBST) thin films with x = 0.05,0.1,0.15 and 0.2 on Pt/TiO₂/SiO₂/Si substrate. The structure, surface morphology, dielectric and tunable properties of PBST thin films were investigated as a function of barium content (x). X-ray diffraction and scanning electron microscopy analysis showed that we could get pure PBST perovskite phase and relative fine density thin films with smooth surface. It was found that the crystal lattice constant, grain size, room temperature dielectric constant, dielectric loss and tunability of Ba solutionizing PST thin films increased with the increase in Ba content. For (Pb_0.25Ba_0.2Sr_0.55)TiO₃ thin film, it had the highest dielectric constant of 1390 and the largest tunability of 80.6%. The figure of merit parameter reached a maximal value of 28.9 corresponding to the (Pb_0.25Ba_0.05 Sr_0.7)TiO₃ thin film, whose dielectric constant, dielectric loss and tunability measured at 1 MHz were 627, 0.024 and 69.4%, respectively.     

The interaction of multifold polar orderings in Ba-doped Sr0.7Ca0.3TiO3

A series of polycrystalline Sr_0.7?xCa_0.3Ba_xTiO₃ (SCBT) (0.0 ≤ x ≤ 0.25) samples were synthesized through solid-state reaction method, and their microstructural, anti-ferroelectric (AFE), ferroelectric (FE), dielectric, and phase transition properties were investigated. With the incorporation of Ba²⁺ at Sr²⁺ site, the AFE polar phase (x = 0.0) has been sharply changed, experiencing AFE state, enhanced FE state, cooperative FE state, and normal FE state, owing to the competition and coupling interactions of different polar orderings in SCBT system. Note that excellent FE behavior has been found in the cooperative FE state. In addition, the critical region has been proposed in the T ? x phase diagram.     

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.     

Structure,chemical stability and electrical conductivity of perovskite La0.6Sr0.4M0.3Fe0.7O3−δ (M = Co,Ti) oxides

The perovskite La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) powders have been synthesized by the citrate gel method. The structural and chemical stability of the La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) oxides were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. The electrical conductivities of the sintered La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) ceramics were measured. The results demonstrate the chemical stability in H₂/helium (He) atmosphere of the La_0.6Sr_0.4Ti_0.3Fe_0.7O_3?δ oxide is improved significantly compared to that of the La_0.6Sr_0.4Co_0.3Fe_0.7O_3?δ oxide. The incorporation of Ti^3+/4+ ions in the perovskite structure can significantly stabilize the neighboring oxygen octahedral due to the stronger bonding strength, leading to the enhanced structural and chemical stability of the La_0.6Sr_0.4Ti_0.3Fe_0.7O_3?δ. In addition, the perovskite La_0.6Sr_0.4M_0.3Fe_0.7O_3?δ (M = Co, Ti) oxides possess much higher chemical stability in CO₂/He atmosphere than that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ oxide, in which the perovskite structure is destroyed completely in a flowing CO₂-containing atmosphere.     

High dielectric tunability of Ba0.6Sr0.4TiO3 thin film deposited by radio-frequency magnetron sputtering

In microwave tunable devices, one of the major challenges encountered is the simultaneous minimization of the material's dielectric loss and maximization of dielectric tunability. In this work, Ba_0.6Sr_0.4TiO₃ thin film with the thickness of 300 nm was deposited on Pt/SiO₂/Si substrates using radio-frequency magnetron sputtering technique, and its dielectric properties were investigated. Due to the high temperature annealing process at substrate temperature of 600 °C, well-crystallized Ba_0.6Sr_0.4TiO₃ film was deposited. The dielectric constant and dielectric loss of the film at 100 kHz are 300 and 0.033, respectively. Due to the good crystallinity of the Ba_0.6Sr_0.4TiO₃ films deposited by radio-frequency magnetron sputtering, high dielectric tunability up to 38.3% is achieved at a low voltage of 4.5 V.     

Morphologies and crystal structures of nano-sized Ba1−xSrxTiO3 primary particles prepared by flame spray pyrolysis

Nano-sized Ba_1−xSr_xTiO₃ (BST) powder was prepared by flame spray pyrolysis using “CA-assisted” spray solution. The effects of the mole ratios of Ba to Sr components on the mean sizes, morphologies, and crystal structures of the BST powder prepared by flame spray pyrolysis were investigated. The precursor powders obtained by flame spray pyrolysis had large size, fractured and hollow structures irrespective of the mole ratios of Ba to Sr components. The post-treated BST powders had slightly aggregated morphology of the primary particles with nanometer sizes. The slightly aggregated BST powders turned to nano-sized primary particles by a simple milling process. The milled BaTiO₃ particles post-treated at temperature of 1000 °C had spherical-like shape. On the other hand, the milled Ba_0.5Sr_0.5TiO₃ and SrTiO₃ particles had square shape. The mean sizes of the milled BaTiO₃, Ba_0.5Sr_0.5TiO₃ and SrTiO₃ particles were each 110, 32, and 48 nm. Phase pure BST powder was obtained at a post-treatment temperature of 1000 °C irrespective of the mole ratios of Ba to Sr components. The BaTiO₃ powder had tetragonal crystal structure. On the other hand, the BST except for the BaTiO₃ composition had cubic crystal structures at post-treatment temperature of 1000 °C. The mean crystallite sizes of the milled Ba_1−xSr_xTiO₃ primary particles were changed from 29 to 37 nm according to the mole ratios of Ba to Sr components.     

Effect of annealing time on microstructure and morphology of thin films by sputtering deposition with (Ba<Subscript>0.3</Subscript>Sr<Subscript>0.7</Subscript>)(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> target

The ceramic thin films have been fabricated by radio frequency (RF) magnetron sputtering technique on SiO₂ (110) substrates with (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ target, and then the thin films were annealed at 1,150 °C for different times at O₂ atmosphere. The microstructure and morphology of the thin films were investigated as a function of the annealing times using the X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy techniques. The results show that the microstructure, morphology, and crystallinity of the thin films can be affected by the annealing times significantly. The main phases of the samples are indexed to be Ba_0.5Sr_0.5Nb₂O₆ and Ba_0.27Sr_0.75Nb₂O_5.78, which are different from component of the (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ target due to the volatilization of ZnO. The crystalline quality of the thin films decreases when the annealing time is shorter or longer than 30 min, and the roughness and grain size of the thin films reaches a maximum value when the annealing time is 30 min.     

Enhanced dielectric and tunable properties of barium strontium titanate thin films through introducing Nd(Zn1/2Ti1/2)O3 and adjusting Ba/Sr

Ba_0.6Sr_0.4TiO₃ (BST) and 0.06Nd(Zn_1/2Ti_1/2)O₃–0.94Ba _x Sr_1?x TiO₃ (NZT–BST) thin films with x = 0.6, 0.7, 0.75, and 0.8 were fabricated on Pt/Ti/SiO₂/Si substrates by sol–gel method. The structures, surface morphology, dielectric, and ferroelectric properties, and thermal stability of BST and NZT–BST thin films were investigated as a function of NZT and Ba content. It was found that introducing NZT into BST decreased significantly dielectric loss, however, along with the tunability. On this basis, increasing Ba/Sr in NZT–BST thin films led to the simultaneous increase of dielectric constant and tunability of thin films. As a result, optimized dielectric and tunable properties were obtained for 0.06Nd(Zn_1/2Ti_1/2)O₃–0.94Ba_0.7Sr_0.3TiO₃ thin film with the highest FOM value of 43.22. It awakens us that, for reducing dielectric loss, introducing a certain amount of low permittivity oxides or non-ferroelectrics like NZT into weak ferroelectric perovskite tunable materials, not into paraelectric perovskite tunable materials, may obtain more excellent dielectric and tunable performances.     

Dielectric properties of sol–gel synthesized SrTiO3/(Ba0.7Sr0.3)TiO3 and SrTiO3/Ba(Zr0.3Ti0.7)O3 thin film heterostructures

The paper presents synthesis of Ba_0.7Sr_0.3TiO₃ (BST), BaZr_0.3Ti_0.7O₃ (BZT) and SrTiO₃ (ST) thin films and their heterostructures using modified Pechini method. The La_0.7Sr_0.3MnO₃ has been used as a conducting bottom layer to form metal ferroelectric metal capacitor. The thin films are spin coated on SiO₂/n-Si(100) substrates. The thin films thus deposited are characterized for crystal structure, morphology, dielectric, complex impedance and admittance properties. Deposition of surface layer ST is observed to reduce loss tangent tan δ of BST and BZT thin films, still maintaining equivalent magnitude of figure of merit γ. The results on dielectric properties are analyzed in terms of the Maxwell–Wagner model and Koop’s phenomenological theory.     

Optical and electrical properties of Ba1−x Sr x TiO3 nanopowders at different Sr2+ ion content

Barium strontium titanate (BST) Ba_1?x Sr _x TiO₃ nanopowders have been successfully synthesized using oxalate precursor route. The effect of Sr²⁺ ion content from 0.3 to 0.7 on the crystal structure, crystallite size, microstructure, electrical and optical properties was systematically studied. The results revealed that well crystalline single BST phase was formed by annealing the oxalate precursor at 1,000 °C for 2 h. The crystallite size of the BST powders was decreased with increasing the Sr²⁺ ion molar ratios. The crystallite size was decreased from 56.0 to 33.1 nm when the Sr²⁺ ion content increased from 0.3 to 0.7. Additionally, the lattice parameter (a), unit cell volume and X-ray density of BST ware decreased whereas the porosity, % were increased with Sr²⁺ ion concentration. The BST phase appeared as cubic-like structure. The spectrophotometer measurement results demonstrated that the room temperature band gap energy varied with the Sr²⁺ ion composition x. The band gap energy was shifted to low energy and it was decreased from 3.6 to 3.2 eV with increasing the Sr²⁺ ion content from 0.3 to 0.7. Moreover, the DC resistivity was enhanced with increasing the Sr²⁺ ion ratio. The dielectric response obtained for the stressed samples corresponds to a true resonance rather than a dispersion process with a characteristic frequency around 1 GHz at room temperature. However, the peaks commonly observed at GHz frequency were changed with varying the Sr²⁺ ion composition. The high imaginary components of dielectric permittivity for x = 0.3 was found at higher frequency region around 1.6 GHz compared with the samples with x values of 0.5 and 0.7 in which the frequency regions were around 1.25 and 1.15 GHz, respectively.     

Formation and electrical characterization of Ti-modified Sr0.3Ba0.7Nb2O6 ceramic system

Titanium modified Sr_0.3Ba_0.7Nb₂O₆ ceramic system has been studied in a wide range of compositions. As the sintering temperature exceeds the 1250 °C, the substitution of niobium by titanium induces liquid phase formation, which enhances the densities of the samples with compositions in the monophasic range. X-ray diffraction analysis shows a linear titanium incorporation into the Sr_0.3Ba_0.7Nb_2−yTi_yO_6−y/2 system up to a solubility limit 0.07 < y_m < 0.1, which it is also confirmed by the ferroelectric–paraelectric temperature transition. Both, the diffuse character of the system and the dielectric constant at room temperature increase as the Ti content increase. The dielectric constant (ɛ_r = 420) of the sample with a titanium content of 0.07 are two times higher than the reported for the SBN (30/70) system.