Effect of excess TiO2 on the phase evolution and densification of sol-gel derived (Ba,Sr)TiO3 powders

Nanoscaled (Ba_2/3Sr_1/3)Ti_{1 + x} O₃ powders have been prepared by sol-gel technique. Their phase evolution and densification behaviors have been studied by differential thermal analysis (DTA) and high temperature dilatometer, respectively. It is found the addition of 2 mol%-excess amount of TiO₂ lowers the activation energy required for the formation of the perovskite phase by about 130 kJ/mol and thus lowers the crystallization temperature of BST powders. However, the excess amount of TiO₂ makes the nano-powder difficult to sinter. Transmission electron microscopy reveals that a metastable nano-porous layer has formed on the surface of TiO₂-excess nanopowder and this may account for the slow densification rate.     

Lateral Epitaxial Growth of Ba0.6Sr0.4TiO3 Thin Films

We report a novel growth technique for epitaxial thin films by combination of selective heteroepitaxial growth and lateral homoepitaxial growth. Ba_0.6Sr_0.4TiO₃ (BST) thin films were deposited on the substrates having patterned SiO_x layers at 450°C using pulsed laser deposition. Post annealing was carried out thereafter for lateral epitaxial growth. The difference in the crystallization temperature of BST thin film on the amorphous masking layers and lattice-matched single crystalline substrate enables selective nucleation and heteroepitaxial growth from the regions of single crystalline substrates during the film deposition. Lateral homoepitaxial growth is expected from the crystallized BST thin film toward the amorphous BST on SiO_x during the post annealing process. In this paper, a study on the difference in nucleation and growth behavior of BST thin films on the amorphous masking layers and lattice-matched single crystal substrates is presented.     

Substrate effect on in-plane ferroelectric and dielectric properties of Ba0.7Sr0.3TiO3 thin films

Heteroepitaxial Ba_0.7Sr_0.3TiO₃ thin films were grown on (LaAlO₃)_0.3(Sr₂AlTaO₆)_0.35 (001) (LSAT) and SrTiO₃ (001) (STO) single crystal substrates using pulsed laser deposition (PLD). X-ray diffraction characterization revealed a good crystallinity and a pure perovskite structure for films grown on both LSAT and STO substrates. The in-plane ferroelectric and dielectric properties of the films were studied using interdigital electrodes (IDE). The film grown on LSAT substrate exhibited an enhanced in-plane ferroelectricity, including a well-defined P-E hysteresis loop with the remnant polarization P _r = 10.5 μC/cm² and a butterfly-shaped C-V curve. Nevertheless, only a slim hysteresis loop was observed in the film grown on STO substrate. Curie temperature T _c of the film grown on LSAT substrate was found to be ∼105^∘C, which is nearly 70^∘C higher than that of the bulk Ba_0.7Sr_0.3TiO₃ ceramics. T _c of the film grown on STO substrate has almost no change compared to the bulk Ba_0.7Sr_0.3TiO₃ ceramics. The dielectric tunabilities were found to be 64% and 52% at 1 MHz for the films grown on LSAT and STO substrates, respectively.     

Influence of anatase-rutile phase transformation on dielectric properties of sol-gel derived TiO2 thin films

The phase transformation behavior and resulting dielectric properties of sol-gel derived TiO₂ thin films were investigated. Thin films showed a typical behavior of mixture systems during the phase transformation; a kinetic investigation on the isothermal curve of pre-crystallized thin films revealed that the phase transformation was a first-order reaction with an Avrami time component of 1. Dielectric constants of TiO₂ thin films increased with the increasing amount of the rutile phase while the dielectric losses showed the opposite relationship. From a fitting process using the parallel mixing rule, dielectric constants of two end members of the mixture system were calculated to be 41.4 and 145.2 for the pure anatase and rutile phase thin films, respectively.     

Influence of Y and Mn alternately doped order on the microstructures and dielectric properties of Ba0.6Sr0.4TiO3 films

ABSTRACT

The influences of Y and Mn alternately doped order on the microstructures and dielectric properties of the Ba_0.6Sr_0.4TiO₃ (BST) films were reported in this paper. The Y and Mn alternately doped BST films were designed as YBST/MnBST/… and MnBST/YBST…multilayer films orderly expressed as (Y/Mn)_M and (Mn/Y)_M for short, and prepared on Pt/Ti/SiO₂/Si wafers by an improved sol-gel method, where Y and Mn represent yttrium doped BST layer and manganese doped BST layer, and M is cycle unit, respectively. The microstructures of the alternately doped BST films were observed by SEM and the capacitance-voltage curves at 100 kHz or 1 MHz were measured by a HP4284A LCR meter and the dielectric properties in the range of 1GHz were measured by an E4991A impedance analyzer. Compared to Y or Mn doped multilayer BST film, (Y/Mn)_M and (Mn/Y)_M show higher dielectric tunability and lower dielectric loss with higher dielectric constant. Moreover, (Y/Mn)_M show better dielectric properties than (Mn/Y)_M because (Y/Mn)_M show granular microstructures independent of M, while the (Mn/Y)_M show granular microstructures when M is 2 and add to a surface layer of columnar microstructures on the granular microstructures when M is 4. The related mechanisms were obtained in terms of the XRD phase structures, the cross-sectional SEM microstructures and the AFM morphologies.     

Structural and dielectric properties of epitaxial Ba0.6Sr0.4TiO3 thin films grown on Si substrates with thin SrO buffer layers

(100) epitaxial Ba_0.6Sr_0.4TiO₃ (BST) thin films were grown on Si substrates using a 9 nm thick SrO buffer layer. The phase shifter fabricated on BST films grown on a SrO buffered Si substrate showed a larger figure of merit (FOM) of 24.7°/dB as a result of improving the phase tuning while retaining an appropriate insertion loss compared to that (15.3°/dB) for the BST/MgO structure. This work demonstrates that a thin SrO buffer layer plays an important role in the successful integration of BST-based microwave tunable devices onto Si wafers.     

AC and DC conductivity studies in pulsed laser ablated (Ba,Sr)TiO3 thin films

Abstract

A comparison of the ac conductivity of laser ablated (Ba, Sr)TiO₃ thin films was made for films grown at different substrate temperatures. The ac conductivity was studied as a function of frequency and ambient temperature ranging from room temperature to 460°C. Conductivity results from ac and dc measurements were compared in their an respective Arrhenius plots revealing interesting coincidences. The value of the activation energies computed from the Arrhenius plot of à _ac with 1000/T ranged from 0.97 to 1.3 eV in the high temperature region to 0.36 to 0.54 eV in the low temperature region for different samples. The activation energies obtained from pure dc measurement for fields greater than 100 kV/cm across the samples were in the range of 1.06 to 1.32 eV for different samples. The similarity in results suggests a common origin in the de conduction process in the concerned temperature range and was attributed to ionic conduction resulting from oxygen vacancy motion which has been observed to be significant at high temperatures and high fields. For high temperature grown samples the value of activation energy computed from the Arrhenius plots was comparatively less than those grown at lower substrate temperatures. The difference was attributed to the microstructure and the effect of grain boundaries on the motion of oxygen vacancies leading to the conduction process.     

Iridium thin film as a bottom electrode for high dielectric (Ba,Sr)TiO3 capacitors

Abstract

We propose Ir thin films as new electrode materials for high dielectric BST capacitors. Ir was found to be superior to Pt in a number of aspects such as resistivity, adhesion and surface roughness. The Pt/BST/Ir/SiO₂/Si capacitors showed leakage currents as low as Pt/BST/Pt/SiO₂/Si ones, but higher capacitance resulted. For endurance properties with +5V unipolar pulse trains, the dielectric constant of BST films on Ir decreased by only 10% below its initial value after switching of 10⁹ cycles while that on Pt degraded by 30% after 10⁸ cycles. Ir bottom electrode effects on BST film properties were well explained by the formation of IrO₂ phases on the surface of Ir electrodes.     

Characterization of Ba(Zr0.05 Ti0.95)O3 thin film prepared by sol-gel process

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin film (∼330 nm) was grown on Pt/Ti/SiO₂/Si(100) substrate by a simple sol-gel process. The microstructure and the surface morphology of BZT thin film were studied by X-ray diffraction and atomic force microscopy. The optical properties of BZT thin film were obtained by spectroscopic ellipsometry. The optical bandgap was found to be 3.74 eV of direct-transition type. Ferroelectric and dielectric properties of BZT thin film were also discussed. The electrical measurements were conducted on BZT films in metal-ferroelectric-metal (MFM) capacitor configuration. The results showed the film exhibited good ferroelectrity with remanent polarization and coercive electric field of 3.54 μC/cm² and 95.5 kV/cm, respectively. At 10 kHz, the dielectric constant and dielectric loss of the film are 201 and 0.029, respectively.     

Optical properties of RF-sputtered Ba0.65Sr0.35TiO3 thin films

Ba_0.65Sr_0.35TiO₃ (BST) thin films have been prepared by radio frequency magnetron sputtering on fused quartz at different substrate temperatures. Optical constants (refractive index n, extinction coefficient k) were determined from the optical transmittance spectra using the envelope method. The dispersion relationship of the refractive index vs. substrate temperature was also investigated. The refractive index of BST thin films increased from 1.778 to 1.961 (at λ?=?650 nm) as deposited temperature increases from 560°C to 650°C. The extinction coefficient of as-deposited BST thin films increased with the increase of the oxygen-to-argon ratio, which was due to the change of the film stoichiometry, structure, and texture of BST thin films. The oxygen-to-argon ratio also affected the fluorescence spectra. The fluorescence peaks intensity was greatly increased, apparent frequency shift was detected, and the linewidth became narrow as the ratio of oxygen to argon increased from 1:4 to 1:1. The fluorescence spectra also indicated the band transition of BST thin films was an indirect gap transition.     

Preparation and electrical properties of Ni/(Ba,Sr)TiO3 PTC composite with low resistivity

Ni/ (Ba,Sr)TiO₃ PTC composite of low resistivity was fabricated by a solid state route. A mildly reducing sintering atmosphere was employed to avoid the oxidation of nickel. Metallic nickel is the main chemical state after sintering in the mildly reducing sintering atmosphere. With the increase in nickel amount, the room-temperature resistivity declines and the PTC effect worsens. The quantum mechanical tunneling effect at the Ni–(Ba_,Sr)TiO₃ interface is presumably the prime factor in the deterioration of the PTC effect. PbO–B₂O₃–ZnO–SiO₂ glass was added to modify the interface between nickel and (Ba,Sr)TiO₃ ceramics. The intergranular phase introduced by the glass has an amorphous structure and exists at the interfaces and triple junctions of (Ba,Sr)TiO₃ grains and nickel grains. No obvious diffusion occurs at the interface between crystalline (Ba,Sr)TiO₃ grain and the intergranular phase. Also the added-glass improves the distribution of metal phase. The proper glass addition screens interfacial electron tunneling effect and improves the composite electrical properties. An abundance of the intergranular phase due to excess glass will, however, result in high room-temperature resistivity. The influences of nickel amount and glass amount on the microstructure evolution and electrical properties were analyzed.     

Electrical properties of TiO2 thin films prepared by the sol-gel method

A TiO₂ thin film was prepared by the sol-gel method using a metal alkoxide [Ti(O-i-Pr)₄ tetrasopropoxy titanium: TIPT]. The crystalline form of the film depends on the preparation conditions and the heat treatment temperature. When the ratio (γ) of H₂O to TIPT is 7, the crystalline phase is formed at 400°C; when γ = 2 it is formed at 500°C. The anatase crystal structure was obtained for both γ = 2 and γ = 7. The electrical conductivity of the TiO₂ film increased with the heat treatment temperature.     

Hysteresis analysis in capacitance-voltage characteristics of Pt/(Ba,Sr)TiO3/Pt structures

Abstract

Capacitance-Voltage (C-V) characteristics of Pt/(Ba, Sr)TiO₃/Pt MIM capacitor were investigated. Hysteresis observed in the C-V characteristics of BST films was analyzed. The dependence of the C-V characteristics on the sweeping direction of applied voltage indicates that the hysteresis is caused by the interface trap charge between the BST film and the Pt electrode. A new method was proposed to characterize the interface traps from the hysteresis of C-V characteristics of MIM capacitor. The trapped electron density near the lower interface of the BST thin films was constant (～ 3 × 10¹²cm^?2) for all the film thickness ranging from 500 Å to 2000 Å, which suggests that the hysteresis is not caused by the bulk property of the BST film but caused by the interfacial property.     

Structure and properties of sol-gel processed (Pb,La)TiO3 ferroelectric thin films

Abstract

The influence of heat treatment and substrate materials on PLT thin films by sol-gel processing has been researched. Epitaxial growth PLT thin films with perovskite-type structure on sapphire, SrTiO₃ and MgO single crystal substrates have been prepared. The epitaxial relations are (100)PLT28/(100)SrTiO₃, (111)PLT28//(0001)sapphire and (100)PLT14//(100)MgO. The PLT polycrystal thin films with perovskite-type structure on Si single crystal and quartz glass substrates have been prepared. The remanent polarization Pr and the coercive field Ec of PLT15 ceramic thin films are 7.7 μc/cm² and 34 kv/cm at 4 KHz respectively. The optical transmittance of PLT28 ceramic thin films within the wavelength range of λ = 500–1000 nm is approximately 80%.     

Frequency and Voltage Dependent Dielectric Properties of Ni-doped Ba0.6Sr0.4TiO3 Thin Films

Highly (100) preferred undoped and 1–5% Ni-doped Ba_1–xSr_xTiO₃ (BST) thin films were deposited onto MgO (100) single crystal substrate at 750°C using pulsed laser deposition. BST thin film-based interdigital capacitors (IDC) were prepared by standard photolithography process. The microwave properties of BST films were measured at 10 GHz. Ni-doped BST films showed better dielectric properties by exhibiting improved dielectric Q while retaining an appropriate capacitance tuning compared to undoped BST films. 1% Ni-doped BST film showed the maximum figure of merit of 2896.1. It is suggested that 1 mol% Ni doped BST film is an effective candidate for high performance tunable device applications.     

Investigation on the electrical characteristics of sol-gel derived Pb1.05(Zr0.53Ti0.47)O3 thin films

Abstract

Lead zirconate titanate (PZT) thin films with composition Zr/Ti ～ 0.53/0.47 were deposited by the sol-gel technique. The films were characterized in terms of its polarization relaxation, fatigue and imprint characteristics. We have found that the polarization relaxation is due to the presence of a depolarization field which increases dramatically with the rise in temperature. Improved fatigue performance was observed when the film was fatigued with higher frequency. The direction of imprint depends on the state of polarization. With the increase in net polarization, the trapped charge density at the film-electrode interface increases which leads to imprint characteristics. Also the imprint increases considerably with the rise in temperature. Finally, we have made an attempt to correlate simultaneously fatigue, polarization relaxation, and imprint characteristics with the presence of mobile charge defects (viz. V_o) and defect dipoles (viz. V_Pb – V_o) in the film.     

Contribution of dielectric and metallic losses in RF/microwave tunable varactors using (Ba,Sr)TiO3 thin films

Abstract

Recently, there has been significant interest in use of (Ba,Sr)TiO₃ (BST) thin films for tunable high frequency (RF and microwave) components. In a previous work we have shown that BST thin films grown by metalorganic chemical vapor deposition (MOCVD) exhibit films very low losses (as low as 0.003–0.004) and tunabilities over 50% at low operation voltages.

In order to integrate BST thin films in tunable devices, the objectives of this work are : (i) study the effect of bottom and top electrode on the performance of thin film based capacitors, (ii) correlate low frequency (10 kHz) and high frequency (45 MHz - 1 GHz) measurements, (iii) separate the contribution of dielectric losses and metallic losses at both low and high frequency and finally (iv) show the potential usefulness of series capacitors structures.     

Investigation of the effects of milling ceramic targets on the optical and electrical properties of BST thin films deposited by RF sputtering

Abstract

The RF sputtering method was utilized to deposit thin films of Ba_1-xSr_xTiO₃ (BST). The targets utilized in these experiments were prepared from ceramic powders with different particle size. The goal of this work is to examine whether the particle size distribution of the target can affect the properties of the thin films fabricated by the sputtering method. The Atomic Force Microscope (AFM) was used to examine the grain size in the thin films. The composition of the thin films and the bulk materials were examined by Fourier Transform Infrared (FTIR) spectroscopy. The dielectric properties of the thin films were measured and compared to its bulk counterparts. It was found that on lattice matched electrodes of SrRuO₃ on LaAlO₃ substrates, the thin films deposited from ceramic targets manufactured from ball-milled powders had finer grain size than those deposited from targets made from unmilled powders. However, this phenomenon was not observed in the case of polycrystalline films deposited on platinized silicon wafers.     

Pulsed Laser Deposition of Ba0.6Sr0.4TiO3 Thin Films and Their Optical Properties

ABSTRACT

Barium strontium titanate [Ba_0.6Sr_0.4TiO₃ or BST (60/40)] thin films were deposited on MgO (100) substrates using pulsed laser deposition. X-ray diffraction (XRD) measurements revealed that the BST thin films had epitaxially grown on the MgO (100) substrates. The surface morphology of the thin films was observed using an atomic force microscope and the grain size was found to be about 100–150 nm. The surface roughness was around 4.9 nm for a 250 nm thick film. The optical transmittance of the BST thin film was measured using a transmission mode ellipsometer. The BST/MgO configuration was highly transparent in the visible region. The optical band gap energy of the BST film, calculated by applying the Tauc relation, was 3.56 eV. Optical waveguide characteristics of the BST (60/40) thin film were determined using a prism coupler. The electro-optic (E-O) properties were measured at 632.8 nm wavelength using a phase modulation detection method. The BST film exhibited a predominately quadratic E-O behavior and the quadratic E-O coefficient was found to be 0.58 × 10^{? 17} m²/V².     

Preparation of sol-gel-derived Ca1−x Sr x ZrO3 perovskite dielectric thin films

The sol-gel wet chemical synthesis of dielectric thin films of perovskite Ca_1−x Sr _x ZrO₃ has been studied in detail using different techniques. To the best of our knowledge, it is the first time in the literature to systemically study the properties of Ca_1−x Sr _x ZrO₃ dielectric thin films in the whole solid solution composition range. Based on X-ray diffraction (XRD), Flourier transform infrared (FT-IR) reflectivity spectroscopy and atomic force microscope (AFM) data, the mechanisms of Ca_1−x Sr _x ZrO₃ phase transformation and crystallinity have been investigated. The results show that the film annealed at 550 °C is amorphous with existing of carbonates, while the carbonates and other organics are decomposed at 600 °C and above, and the film is crystallized into the perovskite phase with increasing annealing temperature. The values of dielectric constant in a range of 16–30 for Ca_1−x Sr _x ZrO₃ thin films have been obtained. Measured dielectric properties show that those films exhibit stable dielectric properties nearly independent on the applied electrical field and frequency at room temperature. Based on above data, it can be concluded that Ca_1−x Sr _x ZrO₃ thin films are a promising candidate system for the high-k microelectronic devices application.