Structure and dielectric properties of Cu and (K,Na) doped SrBi2Nb2O9 ferroelectric ceramics

Ferroelectric ceramics, SrBi₂Nb₂O₉ (SBN), Sr_0.8Cu_0.2Bi₂Nb₂O₉ (SCBN) and Sr_0.8K_0.1Na_0.1Bi₂Nb₂O₉ (SKNBN) were prepared by a solid state reaction process. X-ray diffraction analysis shows that the alkali and Cu almost diffuse into the SBN lattice to form a solid solution during sintering and some slight secondary phases was detected. The effect of alkali and Cu on dielectric properties of the SBN ceramics was discussed. The dielectric loss factor of (K,Na) doped SBN ceramics degraded considerably to 0.01 and their frequency and temperature stabilities were enhanced. The dielectric constant was enhanced by approximately 60% and the Curie temperature (Tc) was also improved for Cu doped SrBi₂Nb₂O₉ ceramics.     

Dielectric and Piezoelectric Properties of Nonstoichiometric SrBi2Ta2O9 and SrBi2Nb2O9 Ceramics

Nonstoichiometric SrBi₂Ta₂O₉ (SBT) and SrBi₂Nb₂O₉ (SBN) ceramics were prepared by a solid state reaction method. X-ray diffraction analysis showed that single-phase of Bi-layered perovskite was obtained. With different Sr/Bi content ratios of SBT and SBN, Curie temperature (T_C), electromechanical factor (K_p) and mechanical quality factor (Q_m) were measured. T_C of SBN (SBT) rose from 414C (314C) to 494C (426C) when Sr/Bi content ratio was increased from 0.55/2.3 to 1.2/1.8. In the most Sr-deficient/Bi-excess ratio of 0.55/2.3, the maximum values of Q_m were obtained approximately 1013 and 3325 for SBT and SBN, respectively.     

Defect CHEMISTRY and Charge TRANSPORT in SrBi2Nb2O9

Equilibrium dc conductivity and thermopower measurements at 650–800°C on undoped and 1% acceptor-doped SrBi₂Nb₂O₉, SBN, indicate that the n-type conductivity is similar to that of a simple transition metal oxide that contains 1–2% donor excess. The donor content is attributed to the presence of Bi⁺³ on Sr⁺² sites in the perovskite-like layers of the structure. These centers arise from cation place exchange between these ions in the alternating layers of the crystal. This exchange is apparently not completely self-compensating, and there is local charge compensation in each layer. While the equilibrium conductivity of SrBi₂Ta₂O₉, SBT, is dominated by ionic conduction in the Bi layers, in SBN conduction by electrons in the perovskite-like layers prevails. The difference in behavior is attributed to the expected smaller band gap of the niobate. The electron mobility in SBN is extremely small, of the order of 10^–5 cm²/v · sec at 750°C, and is highly activated with an activation energy of about 1.6 eV. The resulting low mobility at ambient temperatures is proposed as the basis for the observed resistance to ferroelectric fatigue. Reports of metallic Bi on the surface of SBT and SBN by XPS analysis are shown to result from the highly reducing atmosphere of the XPS apparatus.     

Ionic Doping Effects in SrBi2Nb2O9 Ferroelectric Ceramics

Ionic doping effects of various ions in Bi-layered ferroelectric SrBi₂Nb₂O₉ (SBN) ceramics were studied. Un-doped and doped SBN ceramics with Ba²⁺, Pb²⁺, Ca²⁺, Bi³⁺, La³⁺, Ti⁴⁺, Mo⁶⁺, and W⁶⁺ ions were made with solid state reactions. Temperature dependent dielectric constants were measured. Ferroelectric transition temperature (T_C) decreased with Ba²⁺ and Pb²⁺ ions but increased with Ca²⁺ ion which substitutes the 12-coordinated Sr²⁺ site. T_C increased with Ti⁴⁺, Mo⁶⁺, and W⁶⁺ ions which substitute the 6-coordinated Nb⁵⁺ sites. With trivalent Bi³⁺ and La³⁺ ions, T_C increased with Bi³⁺ ion but much decreased with La³⁺ ion. These results showed that the ion size plays an important role in ferroelectricity of SBN ceramics.     

Polycrystalline SrBi2Ta0.8Nb1.2O9 thin films

Abstract

The growth, microstructure and micro-Raman properties of SrBi₂Tao_0.8Nb_1.2O₉ (SBTN) thin films deposited on Si(100) substrates using pulsed laser deposition (PLD) technique were studied at various substrate temperatures. Films were characterized using X-ray diffraction(XRD), atomic force microscopy(AFM), energy dispersive X-ray analysis (EDAX) and micro-Raman studies. AFM studies indicated that the average grain size of the films increased between 0.08 μm to 0.1 μm with the increasing growth temperatures. Micro-Raman studies of SBTN films revealed the fact that shifting of Raman modes corresponds to the BO₆ (where B' Ta/Nb) octahedral symmetry, to higher frequencies, is in accordance with the different masses of the B site atoms and the force constants involved due to Nb doping at Ta sites.     

Ferroelectric SrBi 2 Nb 2 O 9 Thin Films by Aqueous Chemical Solution Deposition

SrBi 2 Nb 2 O 9 (SBN) thin films on a Pt/Ti/SiO 2 /Si substrate were prepared by aqueous chemical solution deposition. The precursor solution was synthesized by means of an 'aqueous solution-gel method', starting with stable, inexpensive and easily available inorganic salts which are dissolved in an aqueous solution of chelating or coordinating ligands (acetates and citrates). Afterwards the synthesized precursor was spin-coated. However, problems arose as a consequence of insufficient 'wetting' of the substrate surface by the aqueous solution (poor film-substrate adhesion). Instead of improving surface adhesion by the addition of a surface-wetting reagent, a new strategy was developed: prior to spin-coating the platinum surface characteristics were modified using a UV/ozone technique. In this way the precursor solution was not chemically changed. Wetting/wettability was verified by means of contact angle measurements. A uniform, three-layer thin film with a total thickness of about 200 nm was obtained after thermal treatment, as could be verified using SEM and XRD.     

Preparation of SrBi2(Ta,Nb)2O9 thin films by rf sputtering for ferroelectric memory production

Abstract

Ferroelectric SrBi₂(Ta, Nb)₂O₉ (SBTN) thin films were prepared by rf magnetron sputtering utilizing a multi-chamber type production tool (ULVAC CERAUS ZX1000). Accurate and dynamic compositional control results in excellent ferroelectric performances such as large 2Pr up to 15μC/cm², fatigue free at least 10⁹ cycles as well as good uniformity and process repeatability. These results indicate that the SBTN sputtering process is promising for ferroelectric memory production.     

Studies on Laser Ablated SrBi 2 Ta 2 O 9 and Sr 0.8 Ca 0.2 Bi 2 Ta 2 O 9 Ferroelectric Thin Films

Ferroelectric thin films of SrBi 2 Ta 2 O 9 (SBT) and (Sr 0.8 Ca 0.2 )Bi 2 Ta 2 O 9 (SCBT) were grown on platinized silicon substrates by using pulsed laser deposition technique. The effect of annealing temperature on the structural and electrical properties of the films was studied. Films were grown at 200 mTorr oxygen pressure with a constant substrate temperature at 500°C and annealed at different temperatures ranging from 700-800 °C in an oxygen ambient. X-ray diffraction data showed that as-grown films were crystalline nature. Atomic force micrographs showed that the grain size and surface roughness increased with increase in annealing temperature. The SBT films annealed at 800 °C showed ferroelectric properties with remanent polarization of 9.1 w C/cm 2 and coercive field of nearly 72 kV/cm. Whereas the SCBT films showed maximum remanent polarization of 7.3 w C/cm 2 with higher coercive field of 86 kV/cm. The higher coercive field in case of SCBT is attributed to the higher electronegativity of partially substituted Ca at Sr site. The dielectric constant increased with increase in annealing temperature and was attributed to the higher grain size.     

Laser ablation preparation and property of bismuth-layer-structured SrBi2Ta2Ta2O9 and Bi4Ti3O12 ferroelectric thin films

Abstract

Bismuth-layer-structured ferroelectric thin films, SrBi₂Ta₂O₉ and Bi₄Ti₃O₁₂, have been prepared by laser ablation method on both Pt sheets and Si wafers at low temperatures of 400 ～ 500°C. These thin films have been characterized by XRD, XPS, AFM, C-V, D-E hysteresis and J-V measurement. SrBi₂Ta₂O₉ thin films have a good (105) preferential orientation, and Bi₄Ti₃O₁₂ thin films have (117) and c-axis orientation on these substrates. Ferroelectric film-SiO₂-Si structures show good C-V hysteresis curve owing to Si surface potential controlled by the D-E hysteresis. D-E hysteresis is obtained in Bi₄Ti₃O₁₂ thin film prepared on Pt sheet, and the remnant polarization and the coercive force are 7.5 μC/cm² and 72 kV/cm, respectively.     

Piezoelectric properties of SrBi2M2− xVxO9 (M = Nb and Ta) ceramics

Vanadium-substituted strontium bismuth tantalate, Sr_0.8Bi_2.2Ta_{2− x}V_xO₉ (SBTVx), and strontium bismuth niobate, SrBi₂Nb_{2− x}V_xO₉ (SBNVx), ceramics were synthesized by a low-temperature processing, and their dielectric, ferroelectric and piezoelectric properties were characterized. With the partial substitution of tantalum or niobium by vanadium cations, the single phase of the ABi₂M₂O₉-type structure was preserved and the sintering temperature was significantly decreased. For the SBNV ceramics, the T _c of 437^∘C for x = 0.0, the vanadium content hardly changed. On the other hand, the T _c of the SBTV ceramics increased from 408^∘C for the non-substituted SBTV to 414^∘C for x = 0.05 and then with the increasing vanadium content, the T _c decreased to 379^∘C for x = 0.20. The remanent polarizations, P _r, of SBTV and SBNV at room temperature were 4.9 and 5.4 μC/cm², respectively. All the obtained independent electromechanical coupling factors of the SBTV0.05 ceramics were as follows: k _p = 0.119, k ₃₁ = 0.073, k ₃₃ = 0.165, k ₁₅ = 0.051 and k _t = 0.134, and the SBNV0.05 ceramics were as follows: k _p = 0.074, k ₃₁ = 0.045, k ₃₃ = 0.175, k ₁₅ = 0.106 and k _t = 0.140. These coupling factors were higher than those of the non-substituted materials. From these results, the vanadium-substituted SBT and SBN-based materials can be expected to be lead-free piezoelectric resonator materials that can be prepared at low sintering temperatures.     

Growth and characterization of epitaxial SrBi2Ta2O9 films on (110) SrTiO3 substrates

Abstract

SrBi₂Ta₂O₉ (SBT) is an attractive material for nonvolatile ferroelectric memory applications. In this paper we report on the deposition of highly epitaxial and smooth SrBi₂Ta₂O₉ films on (110) SrTiO₃substrates. The films were grown by pulsed laser deposition at temperatures ranging from 600 to 800°C and at various laser fluences from a Bi-excess SBT target. The background oxygen pressure was maintained at 28 Pa during the film deposition. Structural characterization of the films was performed by x-ray diffraction. Atomic force microscopy was used to investigate morphology and growth of the films. The films grew with preferred (115) or (116) orientation. The roughness was of the order of unit cell height. The films display a growth pattern resulting in corrugated film morphology.     

Crystallization behavior and microwave dielectric characteristics of ZnO-(La, Nd)2O3-B2O3-based dielectrics

Crystallizable zinc borate glasses modified with different contents of La₂O₃ or Nd₂O₃ were investigated as a potential low loss dielectric with respect to their crystallization behavior and microwave dielectric characteristics. The glasses were admixed with Al₂O₃ filler and fired at 850°C for 30 min in air to prepare low temperature dielectrics. Crystallization behavior and microwave dielectric properties of the resulting samples strongly depended on the relative content of La₂O₃ or Nd₂O₃ in the glass. As a promising result, the composition of 0.15ZnO-0.25Nd₂O₃-0.6B₂O₃ exhibited k?～?6.5 and Q?～?1194 at the resonant frequency of 18.9 GHz. Near zero temperature coefficient of frequency (TCF) was obtained by additional modification of the composition with ～10 wt.% of TiO₂ filler. Crystallization kinetics of the samples was studied based on the differential thermal analysis (DTA) curves obtained with different heating rates. Correlation of the observed dielectric properties to the crystallization behavior is the main subject of this work.     

The sintering behavior and microwave dielectric properties of Mg4(Nb,Sb)2O9 ceramics

The sintering behavior, microstructure and microwave dielectric properties of Mg₄(Nb_2?x Sb _x )O₉ (0?≤?x?≤?2) solid solutions were investigated systematically by X-ray diffraction(XRD), scanning electron microscopy(SEM) and a network analyzer. The solid solutions of Mg₄(Nb_2?x Sb _x )O₉ was formed with x value being no more than 1.6. The dielectric constant (?) of the sintered ceramics decreased from 13.06 to 6.28 with Sb content x from 0 to 1.6. With a substitution of Sb⁵⁺ for Nb⁵⁺ (0.04?≤?x?≤?0.08), the sintering temperature of Mg₄Nb₂O₉ ceramics was decreased from 1400 to 1300 °C without degradation of the Qf values. The optimum microwave dielectric properties of ??～?12.26, Qf?～?168,450 GHz, and τ _f?～??56.4 ppm/°C were obtained in the composition of Mg₄(Nb_1.6Sb_0.4)O₉ sintered at 1300 °C.     

Low-temperature sintering and microwave dielectric properties of Mg4Nb2O9 ceramics

The effects of V₂O₅ and Li₂CO₃ on the sinterability and microwave dielectric properties of Mg₄Nb₂O₉ (MN) ceramics were investigated. With addition of 1.5wt% V₂O₅, the dielectric constant (?) and Q·? value of MN ceramics sintered at 1,000 °C are comparable to those of pure MN sintered at 1,400 °C. The good results are because of the enhancement of the density by liquid sintering at the lower temperatures. With the mixtures of V₂O₅ and Li₂CO₃, the sintering temperature of MN was further reduced to 925 °C at the expense of the quality factor (Q·?) value. Typically, ? of 13.7 and Q·? value of 78,000 GHz were obtained for the specimens with mixtures of 1.5wt% V₂O₅ and 1.5wt% Li₂CO₃ and sintered at 925 °C for 5 h.     

RELAXATIONAL PROPERTIES OF LAYERED FERROELECTRICS CaBi1.5 La0.5Nb2O9

ABSTRACT

CaBi_1.5La_0.5Nb₂O₉ ceramics were prepared by a conventional solid-state reaction method. Their structure and dielectric properties were investigated. X-ray diffraction analysis indicated that single phase layered perovskites were obtained. Dielectric studies demonstrated that CaBi_1.5La_0.5Nb₂O₉ is characteristic of relaxor ferroelectrics. The dielectric relaxation of CaBi_1.5La_0.5Nb₂O₉ was modeled using the Vögel-Fulcher relationship, and the dielectric relaxation in CaBi_1.5La_0.5Nb₂O₉ is found to be analogous to a spin glass with thermally activated polarization fluctuations above a static freezing temperature.     

Piezoelectric and dielectric characteristics of low temperature sintering Pb(Ni1/3Nb2/3)O3-Pb(Mn1/3Nb2/3)O3-Pb(Zr1/2Ti1/2)O3 ceramics for multilayer piezoelectric actuator

In this study, in order to develop the composition ceramics for multilayer piezoelectric actuator, PNN substituted PMN-PZT ceramics were fabricated using Li₂CO₃ and Na₂CO₃ as sintering aids, and their piezoelectric and dielectric characteristics were investigated. With the increase of the amount of PNN substitution, dielectric constant (εr), electromechanical coupling factor (k _p), and piezoelectric constant (d ₃₃) of specimens showed the maximum value at each sintering temperature, and crystal structure changed from tetragonal to rhombohedral. At the sintering temperature of 950^∘C, the density, εr, k _p, d ₃₃, Q_m and Tc of 12 mol% PNN substituted PMN-PNN-PZT composition ceramics showed the optimal values of 7.79 g/cm³, 1160, 0.599, 419pC/N, 894 and 332^∘C, respectively, for low loss multilayer piezoelectric actuator application.     

Integration of H2 barriers for ferroelectric memories based on SrBi2Ta2O9 (SBT)

Abstract

In this study, integration of an hydrogen barrier into a FeRAM process flow is investigated. It is reported in the literature that ferroelectric properties can be maintained after hydrogen annealing by using IrO_x as a top electrode [16][17][18]. Advantage of materials like IrO_x is less catalytic activity compared to Pt. However, we found that IrO_x is not a promising candidate for top electrode barrier. (Pt)/IrO_x/SBT/Pt capacitors are prone to shorting or exhibit high leakage. IrO_x films are very easily reduced by reducing ambient which will result in peeling off. Also, IrO_x films tend to oxidize Ti or TiN layers immediately. Therefore, other barrier materials or layer sequences like Ir/IrO_x have to be considered.

For protection of the entire capacitor an Encapsulation Barrier Layer (EBL) is required. In this study, LPCVD SiN is used. LPCVD SiN is a standard material in CMOS technology. Production tools are available and it is well known as hydrogen barrier. By modifying the deposition process and using a novel process sequence, no visual damage of the capacitors after SiN-deposition and FGA is seen. Also, no degradation of electrical properties after capacitor formation as well as after SiN-deposition and FGA is observed. However, after metal 1 and metal 2 processing, 2P_r values at 1.8V are reduced from 12μC/cm²to 2μC/cm². Polarization at 5.0V is not affected.     

Dielectric and piezoelectric properties of (K0.5Na0.5)(Nb0.97Sb0.03)O3 ceramics doped with Bi2O3

In this study, to develop the optimal composition of ceramics for low loss piezoelectric actuator and ultrasonic motor applications, (K_0.5Na_0.5)(Nb_0.97Sb_0.03)O₃?+?0.009 K_5.4Cu_1.3Ta₁₀O₂₉?+?0.1wt%Li₂CO₃?+?xwt%Bi₂O₃(x?=?0?~?0.9) lead-free piezoelectric ceramics with a fixed quantity of 0.009 K_5.4Cu_1.3Ta₁₀O₂₉ (abbreviated as KCT) were manufactured using the conventional solid-state solution processes. The effects of Bi₂O₃ addition on the dielectric and piezoelectric properties were then investigated. From the X-ray diffraction analysis result the specimens demonstrated orthorhombic symmetry when Bi₂O₃ was less 0.6?wt%, a pseudo-cubic phase appeared when Bi₂O₃ was 0.9?wt%. SEM images indicate that a small amount of Bi₂O₃ addition affect the microstructure. The piezoelectric properties of (K_0.5Na_0.5)(Nb_0.97Sb_0.03)O₃ ceramics were greatly improved by a certain amount of Bi₂O₃ addition. Excellent properties of density?=?4.54?g/cm³, relative densities?=?98.5?%, k _p?=?0.468, Q _m?=?1,715 and d ₃₃?=?183 pC/N were obtained with a composition of 0.3?wt% Bi₂O₃     

Effect of La3+ substitution on microwave dielectric properties of (Pb0.5Ca0.5)(Fe0.5Nb0.5)O3 ceramics

Microwave dielectric properties of the [(Pb_0.5Ca_0.5)_1?x La_2x/3](Fe_0.5Nb_0.5)O₃ and [(Pb_0.5Ca_0.5)_1?x La _x ](Fe_0.5Nb_0.5)O₃ ceramics were investigated as a function of La³⁺ content $ {\left( {0.0 \leqslant \times \leqslant 0.2} \right)} $ . A single perovskite phase was detected in [(Pb_0.5Ca_0.5)_1?x La_2x/3](Fe_0.5Nb_0.5)O₃, while Pb₃Nb₄O₁₃ were detected as a secondary phase in [(Pb_0.5Ca_0.5)_1?x La _x ](Fe_0.5Nb_0.5)O₃ beyond x?=?0.05 due to the excess of unbalanced charge. The amount of Pb₃Nb₄O₁₃ was proportional to the unbalanced charge. Qf value of [(Pb_0.5Ca_0.5)_1?x La_2x/3](Fe_0.5Nb_0.5)O₃ decreased remarkably with La³⁺ substitution due to the increase of oxygen vacancy. For [(Pb_0.5Ca_0.5)_1?x La _x ](Fe_0.5Nb_0.5)O₃ ceramics, dielectric constant and Qf value increased with La³⁺ content up to x?=?0.03 due to an increase of density and grain size. Temperature coefficient of resonant frequency (TCF) was depended on B-site bond valence in single perovskite phase.     

High energy storage,structure evolution and dielectric properties of complex perovskite solid solution (1-x) NaNbO3-xBi (Zn2/3Nb1/3) O3

Journal of Electroceramics - NaNbO3-based lead-free ceramics show great potential in energy storage and piezoelectric applications due to the antiferroelectric and ferroelectric features. However,...