Ferroelectric and dielectric properties of sol-gel processed barium titanate ceramics and thin films

Ferroelectric and dielectric properties of barium titanate (BaTiO3) bulk ceramics and thin films have been investigated. The bulk ceramics and thin film samples have been prepared from barium acetate [Ba(CH3COO)2] and titanium(IV)isopropoxide [Ti(CH3)2CHO)4] precursors by sol-gel technique. The as-grown bulk powder and thin films were found to be amorphous, which crystallized to tetragonal phase after annealing at 700°C in air for one hour. The values of the spontaneous polarization (Ps), remanant polarization (Pr) and coercive field (Ec) of the bulk ceramics were found to be 19.0, 12.6 C cm–2 and 30 kVcm–1 respectively. In the case of the film, the values of Ps, Pr and Ec were respectively found to be 14.0, 3.2 Ccm–2 and 53 kVcm–1. The capacitance-voltage (C-V) characteristics of the film also showed polarization hysteresis. The values of the dielectric constant () of the bulk ceramic and thin film at 1 kHz were found to be 1235 and 370 respectively. Both the films and ceramics showed dielectric anomaly peaks at 125°C, showing ferroelectric to paraelectric phase transition.     

Electrical properties of sol-gel processed barium titanate films

The sol-gel technique has been used to prepare ferroelectric barium titanate (BaTiO₃) films. The electrical properties of the films have been investigated systematically. The room temperature dielectric constant (ε) and loss tangent (tanδ) at 1 kHz were respectively found to be 370 and 0.012. Both ε and tanδ showed anomaly peaks at 125°C. The room temperature remanant polarization (P_r) and coercive field (E_c) were found to be 3.2 μC/cm² and 30 kV/cm, respectively. The capacitance–voltage (C–V) and conductance–voltage (G–V) characteristics also showed hysteresis effect. The temperature variation of C–V and G–V characteristics also confirms the ferroelectric to paraelectric phase transition at 125°C.     

Europium incorporated barium titanate thin films for optical applications

BaTiO₃:Eu (BT:Eu) thin films were deposited onto quartz substrates by RF magnetron sputtering. The effect on structural, morphological, optical and photoluminescence (PL) properties in the films with different Eu concentrations (0–5 wt%) were investigated. The X-ray diffraction (XRD) pattern of the undoped BT thin film revealed a tetragonal (T) phase with orientations along (101) plane. From XRD pattern, the crystallinity of the films increased with increase in Eu concentration. The SEM images revealed that the films exhibited tetragonal shape, crack free and good adherence to the substrate. Atomic force microscopy studies showed an increase of grain growth with doping concentration. The rms roughness value increased with increase in Eu concentration and the film surface revealed positive skewness and high value of kurtosis which make them suitable for tribological applications. X-ray photoelectron spectroscopy revealed the presence of barium, titanium, europium and oxygen in BT:Eu film. An average transmittance of >80 % (in visible region) was observed for all the films. Optical band gap of Eu doped BT films decreased from 3.86 to 3.53 eV. Such films with optical properties such as high transparency, decrease in band gap and high refractive index are suitable for optoelectronic applications. PL properties showed a sharp line at 625 nm and a broad line at 552 nm due to europium (Eu³⁺) transitions. PL phenomena were observed, owing to the electronic structure of Eu³⁺ ions as well as BT nanocrystallites in the films. The sharp and intense red luminescence is useful for photoelectric devices and optical communications.     

Dielectric and microstructural properties of barium titanate hafnate thin films

Barium titanate hafnate (BaTi_1−xHf_xO₃, 0 ≤ x ≤ 0.25) thin films have been deposited by a chemical solution method on copper foil substrates. The films were crystallized at 900 °C and in a reducing atmosphere to prevent substrate oxidation. Perovskite phase formation was identified for each composition, accompanied by an increased pseudocubic lattice parameter. Temperature dependent dielectric measurements revealed a decreasing phase transition temperature and peak permittivity with increasing hafnium level. The decrease in permittivity resulted from grain size reduction with increasing hafnium content. Compositions containing 25 mol% barium hafnate display a deviation from Curie-Weiss behavior indicating the onset of relaxor behavior.     

Sol-gel synthesis and characterization of barium titanate powders

A simple aqueous sol-gel route has been refined to prepare yttrium-doped barium titanate powders. Thermal decomposition of the fabricated gel was studied by means of DTA/TGA measurements. The precursor gel was intermediate calcined at 600 °C, and the final synthesis products were characterized by IR spectroscopy, X-ray powder diffraction and scanning electron microscopy. The barium titanate obtained from the calcination of the gel at 1300 °C was a tetragonal phase, and showed a positive temperature coefficient of resistivity (PTCR) effect which depends on sample cooling rate during the final heat treatment.     

钛酸锶钡(BST)薄膜的介电性能研究

采用射频磁控溅射法制备了BaxSr1-xTiO2（简称BST）薄膜材料,研究了不同膜厚,晶粒尺寸的BST薄膜的介电系数温度特性（ε1-T),频率特性（ε-r-f),电压特性（εr-U)及损耗的温度特性（tgδ-T),频率特性（tgδ-f),找出了BST薄膜的非线性,损耗随尺度变化的规律。     

Hydrothermal processing of barium strontium titanate sol-gel composite thin films

Stoichiometric barium strontium titanate (BST) films of composition with thickness >2 μm have been fabricated on Si/SiO₂/Pt substrates by hydrothermal sol-gel composite processing. This film deposition technique involves the treatment of a spun-on sol-gel composite film, formed from a suspension of a powder in an aqueous BST sol-gel, at temperatures from 100–200°C at a pressure of 1–15 atm. An initial hydrolysis procedure eliminates dissolution of the dried sol-gel during the hydrothermal treatment. Glancing angle X-ray diffraction shows excellent crystallinity and stoichiometry in the BST films with no evidence of new phases created during processing. Scanning electron micrography and atomic force microscopy show densification of the film structure and the development of a bridging microstructure. Transmission electron micrography indicates that while much of the sol-gel derived matrix phase is amorphous a more crystalline interface occurs with the powder particles. The relative permittivity and loss tangent of the films are measured using a parallel plate capacitor technique in the frequency range 1–100 kHz. At 100 kHz relative permittivities of the films range from ɛ_r = 400–1200 and loss tangents lie in the range 0.05 < tan δ < 0.10, depending on the parameters of film preparation. The film structure and morphology and the electrical studies suggest that the microstructure of the films evolves by deposition of the sol-gel derived BST on the underlying powder, resulting in an electrically interconnected microstructure in which the sol-gel derived material bridges between the high permittivity powder particles.     

Dielectric properties of sol-gel derived barium strontium titanate thin films

Barium strontium titanate (Ba_xSr_1−xTiO₃) films were deposited by sol-gel technique on platinized silicon substrate for the composition range x = 0.0 to 1.0 in steps of 0.1. The as-deposited films were found to be amorphous. The films crystallize on annealing in air at 700 °C for 1 h. Dielectric constant (ε′) and loss tangent (tanδ) were measured in the temperature range − 180 °C to 150 °C in the frequency range 0.1 to 100 kHz. Both ε′ and tanδ show a small dispersion for all the compositions. This dispersion is more at the peak value than at room temperature. A comparison of the room temperature and peak value of the dielectric constant for various compositions are made with the reported values. Transition temperatures are reported for the entire composition range. All the compositions show a transition from ferroelectric to paraelectric phase except strontium titanate. Transition temperature shows a systematic decrease with increase in strontium content. The variation is at a rate of 3.4 °C/mol% of SrTiO₃. Curie constants are also reported for the entire composition range.     

Dielectric properties of lead zirconate titanate thin films seeded with barium strontium titanate nanoparticles

A low temperature synthetic method recently proposed by the authors was applied to the fabrication of lead zirconate titanate (PZT) thin films containing crystalline seeds of barium strontium titanate (BST) nanoparticles. PZT precursor and the BST particles were prepared with complex alkoxide methods. Precursor solution suspending the BST particles was spin-coated on Pt/Ti/SiO₂/Si substrate to film thickness of 500–800 nm at particle concentrations of 0–25.1 mol%, and annealed at various temperatures. Seeding of BST particles prevented the formation of pyrochlore phases, which appeared at temperatures above 400 °C in unseeded PZT films, and induced crystallization of PZT into perovskite structures at 420 °C, which was more than 100 °C below the crystallization temperature of the unseeded PZT films. Measurement of dielectric properties at 1 kHz showed that the 25.1 mol% BST-seeded PZT films annealed at 450 °C had a dielectric constant as high as 300 with a dissipation factor of 0.05. Leakage current density of the film was less than 1×10⁻⁶ A/cm² at applied electric field from 0 to 64 kV/cm.     

Diffusion properties of point defects in barium strontium titanate thin films

The relationship between the diffusion behavior of hydrogen and the electrical properties of (Ba, Sr)TiO3 (BST) thin-film capacitors was investigated using thermal desorption spectroscopy and secondary ion mass spectroscopy analyses. It has been clearly shown that the frequency dependence of the complex impedance profile of the BST thin-film capacitors could be successfully represented by two parallel resistor-capacitor (RC) electrical equivalent networks in series correlated with the distribution of the hydrogen, namely, the Pt/BST interface region with the influence of hydrogen and the BST bulk region without the influence of hydrogen. However, the I-V properties of the BST thin-film capacitors could be determined almost from the hydrogen atoms existing at the Pt/BST interface.     

Strength and toughness of barium titanate ceramics

The effect of processing variables on the mechanical and electrical properties of holmium-doped barium titanate ceramics with a positive temperature coefficient of resistance has been investigated. This paper contains details of the tests used to measure the mechanical properties of ceramics prepared using four compositional mixes. Two methods of measuring strength were used: diametral compression of disc samples and four-point bending of beam specimens. Fracture toughness was also evaluated using two methods: the failure of single edge-notched (SEN) beams under four-point loading and cracking from a surface indentation with a diamond pyramid indentor. Values of strength ranged from 18 to 82 MPa for the four materials when measured by the diametral compression test. This compared with a range of 35–79 MPa for the same materials tested in pure bending. Fracture toughness values ranged from 0.65 to 0.95 MPa m^1/2 for the SEN specimens and from 1 to 1.8 MPa m^1/2 using the indentation technique on the same samples.     

Electronic structure of nanograin barium titanate ceramics

The density of states and band structure of 20 nm barium titanate (BaTiO₃, BT) ceramics are investigated by first-principles calculation. The full potential linearized augmented plane wave (FLAPW) method is used and the exchange correlation effects are treated by the generalized gradient approximation (GGA). The results show that there is substantial hybridization between the Ti 3d and O 2p states in 20 nm BT ceramics and the interaction between barium and oxygen is typically ionic.     

PTCR ceramics produced from oxalate-derived barium titanate

BaTiO₃ powders with an average crystallite size from 68 to 2000 nm have been prepared by calcining barium titanyl oxalate at temperatures from 700 to 1150°C, and their morphology and recrystallization kinetics have been studied. The powders have been used to produce positive temperature coefficient of resistance (Ba,Ca,Pb)TiO₃ ceramics, and the microstructure and electrical properties of the ceramics have been investigated. The results indicate that improving the crystallinity of the barium titanate powder suppresses recrystallization in the ceramics, increases their resistivity, and has a significant effect on their resistance jump and electric strength. We have identified the optimal temperature range of barium titanyl oxalate calcination, which insures the highest electric strength of PTC thermistors with a resistance of 31 Ω. The corresponding crystallite size of the barium titanate powder is ?200 nm.     

Synthesis and properties of barium titanate stannate thin films by chemical solution deposition

Barium titanate stannate (BaTi_1−x Sn _x O₃, 0 ≤ x ≤ 0.25) thin films were deposited directly on copper foil substrates via a chelate chemical solution process. The films were subsequently crystallized in a reducing atmosphere such that substrate oxidation was avoided and that the 2-valent state of tin could be stabilized. Despite the stabilization of the low-melting temperature SnO oxidation state at high temperatures, the final grain size was smaller with increased tin incorporation similar to other B-site substituted BaTiO₃ films. Temperature and field-dependent dielectric measurements revealed a reduction in dielectric constant and dielectric tuning with increasing tin concentration. The reduction in permittivity with reduced grain size is consistent with the well-known trends for ceramic barium titanate and in combination with a defect-dipole model involving Sn acceptors, can be used to explain the experimental trends. Phase transition frequency dependence was studied and for compositions containing up to 25 mole percent tin. No phase transition dispersion was observed and thus no strong evidence of relaxor-like character. The phase transition became increasingly diffuse with deviation from Curie–Weiss behavior, but the observed transition temperatures agreed well with bulk reference data.     

Electrical and optical properties of chemical solution deposited barium hafnate titanate thin films

We have investigated the electrical and optical properties of Ba(Hf_xTi_1 − x)O₃ (x = 0, 0.1, 0.2, 0.3, 0.4) (BHT) thin films deposited on platinized silicon and fused quartz substrates. Analyses of the X-ray diffraction patterns reveal that with the increase in Hf contents there is a systematic increase of the lattice constants of BHT films. Irrespective of the measurement frequencies the dielectric constants was found to be systematically decreased, whereas their frequency dispersion was found to be reduced with increasing Hf contents. The leakage current data measured using a metal-insulator–metal configuration reveal that the Schottky emission is the dominant leakage current mechanism in these films. BHT films, deposited on transparent fused quartz substrates, were also characterized in terms of their optical properties. For this purpose the transmittance of the undoped as well as Hf doped barium titanate thin films was measured as a function of wavelength in the range of 290 nm to 800 nm. The transmission spectra were analysed to estimate the wavelength dependence of the refractive indices/extinction coefficients as well as the variation of optical band gap of these films. With the increase of Hf contents, a systematic increase of the band gap [from 3.65 eV (undoped film) to 4.15 eV (40 at.% Hf doped barium titanate film)] was observed. The reduction of the leakage current with increasing hafnium substitution is discussed on the basis of an increasing Schottky barrier height and due to a simultaneous increase in the band gap of the material.     

Preparation and optical properties of gold nanoparticles embedded in barium titanate thin films

High amount of gold nanoparticles was successfully incorporated into amorphous BaTiO₃ thin films by sol-gel process. Thiourea was applied to prevent Au ions from being reduced and aggregating as the effective stabilization agents. These films exhibited unique surface plasma resonance red-shifting and particular changes of surface plasma resonance intensity with the increase of heat-treating temperature, which could be attributed to the influence of BaTiO₃ ferroelectric domains. The films also exhibited superfast nonlinear optical response and larger third-order nonlinear susceptibility ⁽³⁾, which was attributed to hot electron contribution.     

Experimental investigations on barium titanate nanocomposite thin films as an opto-electronic humidity sensor

This article reports the synthesis and characterisation of Barium titanate (BaTiO₃) nanocomposite and its application as opto-electronic humidity sensor. Titanium tetrachloride and barium hydroxide were mixed in molar ratio 1?:?1 in deionised water under continuous stirring at room temperature. Later, sodium hydroxide solution was added to above solution with continuous stirring. Finally, BaTiO₃ gel was obtained. The synthesised nano-composite material was characterised using a scanning electron microscope, X-ray diffraction (XRD) and UV-Visible spectrophotometer. SEM image of the composite film shows that the film is porous having uniform grains. From XRD the minimum crystallite size of BaTiO₃ was found to be 8?nm using Debye–Scherer formula. UV-Visible absorption spectroscopy was used for optical characterisation of the film. It was found that the optical band gap of the composite material was 3.50?eV. Barium titanate thin film was deposited on the base of an equilateral prism using sol–gel spin coating process at 4000?rpm. The humidity sensing properties of the film was investigated at different angles of incidence. It was observed that the intensity of reflected light increased with an increase in relative humidity (%RH) in the range 5–95% at a particular angle of incidence. Sensing element has maximum sensitivity ～6?µW/%RH, which is quite significant for sensor fabrication purposes.     

Semiconducting ceramics produced using nanocrystalline barium titanate powder

Positive temperature coefficient of resistance ceramics of composition (Ba_0.89Ca_0.08Pb_0.03)TiO₃ + Y₂O₃ + MnO + SiO₂ have been produced using barium titanate powder with an average crystallite size of 125 nm prepared by calcining barium titanyl oxalate at 900°C. The effect of firing temperature on their microstructure and electrical properties has been studied. The results demonstrate that the ceramics possess semiconducting properties starting at a firing temperature of 1205–1215°C. The room-temperature resistivity of the ceramics has a minimum at t _firing ≈ 1245–1250°C. The samples sintered at 1250–1260°C have the largest positive temperature coefficient of resistance. The highest electric strength (360 V/mm at ρ_25°C = 290 Ω cm) is offered by the thermistor materials sintered at 1260°C, which is 60–70°C below the firing temperature of analogous ceramics produced by solid-state reaction.