Solution synthesis of epitaxial films of bismuth containing ferroelectric materials

Abstract

Methoxyethoxide complexes in 2-methoxyethanol were used to produce epitaxial thin films of SrBi₂Nb₂O₉, SrBi₂Ta₂O₉, BaBi₂Nb₂O₉, and BaBi₂Ta₂O₉ on [100] oriented single-crystals of SrTiO₃ and LaAlO₃. Films were prepared by spin coating substrates with alkoxide solutions and firing in air at 850 °C for 20 minutes. With the exception of BaBi₂Ta₂O₉ on LaAlO₃, all of the films were the desired c-axis oriented Aurivillius phase. Out-of-plane orientation was confirmed by θ-2θ scans which showed only [002/] reflections, and in-plane orientation was determined by phi-scans about the [105] plane. Lattice constants and full-width at half-maximum (fwhm) values for both in-plane and out-of-plane reflections are reported.     

Phase transition and electrical studies of wolframium doped SrBi2Ta2O9 ferroelectric ceramics

In this study, crystalline structure, dielectric and impedance properties of SrBi₂Ta₂O₉ (SBT) - based ferroelectric ceramics have been investigated with the substitution of wolframium/tungsten (W) onto the tantalum site. Wolframium doped SrBi₂(W _x Ta_{1 − x} )₂O₉ (0.0 ≤ x ≤ 0.20) ceramics were synthesized by solid state reaction method. The X-ray diffractogram analysis revealed that the substitution formed a single phase layered perovskite structure for the doping content up to x ≤ 0.05. The dielectric measurements as a function of temperature show an increase in Curie temperature (T _c ) over the composition range of x = 0.05 to 0.20. The W^{6 +} substitution in perovskite-like units results in a sharp dielectric anomaly at the ferroelectric phase transition. Furthermore, the dielectric constant at their respective Curie temperature increases with wolframium doping. Both enhanced Curie temperatures and dielectric constants at the Curie points indicate an increase in polarizability, which could be attributed to the increased “rattling space” due to the incorporation of the smaller tungsten cations. The dielectric loss reduces significantly with tungsten addition. AC impedance properties vis-à-vis wolframium content has also been studied.     

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.     

Structural and electrical properties of SrBi2VxNb2?xO9 ferroelectric ceramics: Effect of temperature and frequency

Aurivillius type bismuth layered materials have received a lot of attention because of their application in ferroelectric non-volatile random access memories. Among bismuth layer structured ferroelectric ceramics SrBi₂Ta₂O₉ (SBT)/SrBi₂Nb₂O₉ (SBN) are of great interest for researchers because of their fatigue resistance and less distorted structure. Recently vanadium substitution in SBN/SBT has shown interesting electric and dielectric properties. In the present work, processing conditions, microstructure and electrical studies of vanadium doped SBN ferroelectric ceramics have been performed. Samples of compositions SrBi₂V _x Nb_2-x O₉, x = 0.0, 0.1, 0.3, 0.5 were prepared by solid-state reaction technique using high purity oxides / carbonates. The samples were calcined at 700 °C and sintered at 800 °C. X-ray diffractograms show that a single phase layered perovskite structure is formed in all the samples. Effect of partial substitution of pentavalent niobium ion (0.68 ?) by smaller pentavalent vanadium ion (0.59 ?) at B site on the microstructure, Curie temperature, Dielectric constant, Dielectric loss and electrical conductivity have been investigated. Dielectric properties of SBVN have been investigated from room temperature to 500 °C and frequency of 100 Hz to 1 MHz. Dielectric constant values at their respective Curie points are observed to increase with increasing vanadium concentration. Curie temperature is observed to be maximum in x = 0.1 vanadium doped sample. Strong relaxor like dielectric relaxation at the transition temperatures have been observed. With increasing vanadium concentration the dielectric loss is observed to increase significantly. It is also observed that dielectric loss increases with increase in temperature. The variation of conductivities in these samples is also reported.     

EFFECT OF ALKALINE EARTH SUBSTITUTION ON ELECTRICAL PROPERTIES OF SrBi4Ti4O15 CERAMICS

ABSTRACT

Ferroelectric Sr_1–xCa_xBi₄Ti₄O₁₅ (SCBT-x x = 0.00, 0.20, 0.40, 0.50, 0.70, 0.90 and 1.00) ceramic samples were prepared using the conventional solid-state reaction. The Curie temperature (T_c) increases with Ca doping. The temperature dependence of dielectric loss (tan δ) shows two dielectric anomalies at x = 0.20 while only one dielectric loss peak is found in other cases. The remnant polarization (2P_r) and coercive field (E_c) of nondoped SrBi₄Ti₄O₁₅ are about 15.7 μC/cm² and 107 kV/cm, respectively. Small amount of Ca doping increases the 2P_r, the 2P_r reaches a maximum value of 17.6 μC/cm² and E_c is increased to 113 kV/cm when x = 0.20. The piezoelectric coefficient (d₃₃) shows the maximum values of 9.0 pC/N at x = 0 and decreases almost linearly with the increase in x.     

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.     

Co-Precipitation Method for the Preparation of Nanocrystalline Ferroelectric SrBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> Ceramics

A simple co-precipitation technique had been successfully applied for the preparation of pure ultrafine single phase SrBi₂Nb₂O₉. Ammonium hydroxide and ammonium oxalate were used to precipitate Sr^{2 +}, Bi³⁺ and Nb⁵⁺ cations simultaneously. No pyrochlore phase was found while heating powder at 850C and pure SrBi₂Nb₂O₉ (SBN) phase was formed as revealed by the X-ray diffraction (XRD) studies. Particle size and morphology was studied by transmission electron microscopy (TEM). The room temperature dielectric constant at 1 kHz is 100. The ferroelectric hysteresis loop parameters of these samples were also studied.     

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.     

Raman scattering in the aurivillius-layered ferroelectric SrBi2Ta2O9 – Bi3TiNbO9 thin films

Abstract

We have used Raman spectroscopy to investigate thin films of ferroelectric (SrBi₂Ta₂O₉)_x(Bi₃TiNbO₉)_1?x layered structures and to compare them with the corresponding bulk materials. Various compositions, with x ' 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0, were prepared by metal organic solution deposition method on Pt/TiO₂/SiO₂/Si substrates. A topographic micro-Raman study revealed very homogeneous films at each composition. The Raman spectrum of x ' 0.0 film shows bands around 170, 232, 337, 522, 608, 677 and 832 cm^?1, which indicates Bi₃TiNbO₉ formation. The evolution of the Raman bands with the inclusion of SBT material shows frequency shifts and a broadening of the bands due to the differences in mass between Sr and Bi in the A-sites, and Ta, Ti, and Nb in the B-sites A lower degree of crystallization was found in the films compared to the bulk due to the presence of stress in the films. Strong contributions from defects were also observed in the temperature-dependent Raman spectra.     

Influence of process conditions on the ferroelectric characteristics of SrBi2Ta2O9 films prepared by rf magnetron sputtering

Abstract

The effects of sputtering conditions on the SrBi₂Ta₂O₉ films deposited via a single-target RF-sputtering process were investigated in this study. It was found that the composition of targets significantly affected the phases and the composition of the deposited films. When the target contained high bismuth content, SrBi₂Ta₂O₉ and a secondary Bi₂O₃ phase were formed. When the bismuth content in the targets was insufficient, a pyrochlore phase was produced. SEM images revealed that the composition of the targets also affected the surface morphology of the obtained films. When the target-to-substrate distance was increased, bismuth oxide was formed, which resulted in an increase in the leakage current. By optimizing the deposition conditions, the ferroelectric properties of SrBi₂Ta₂O₉ films were improved.     

Preparation and characterization of SrBi2Ta2O9 thin films by low-oxygen-concentration annealing technique

SrBi₂Ta₂O₉ thin films were successfully prepared at a low annealing temperature using a low-oxygen-concentration annealing technique. It was possible to obtain a single perovskite phase at 600 °C in 0.7% oxygen concentration and fluorite phase was observed at 600 °C in 100% oxygen. In addition, the SrBi₂Ta₂O₉ thin films annealed at 650 °C in 0.7% oxygen were well crystallized and composed of dense crystal grains with a size of 70 nm. The remanent polarization and leakage current density of the SrBi₂Ta₂O₉ thin film obtained using this new technique were 7 μC/cm² and 3 × 10⁻⁹ A/cm² (at 5 V), respectively. The final remanent polarization after 10⁹ switching cycles was nearly constant. © 1999 Scripta Technica, Electr Eng Jpn, 129(4): 1–6, 1999     

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.     

Top electrode dependence of forming gas annealing effects on ferroelectric films

Abstract

The effects of forming gas annealing have been studied on PZT [Pb(Zr,Ti)O₃] and SBT (SrBi₂Ta₂O₉) samples with a variety of top electrode materials. It's been found that forming gas annealing causes changes in the remanent polarization, coercive field, and leakage current in both types of samples, and these changes depend strongly on the top electrode material. Among the 6 electrode materials that we have studied (Pt, Au, Ag, Cu, Ni, and In₂O₃), Pt tends to lead to the most severe degradation, while the oxide electrode tends to withstand better the forming gas anneal. To explain the results, a model has been proposed which is based on the catalytic activities of the top electrode to dissociate hydrogen molecules into hydrogen atoms, and the latter then migrate into PZT or SBT films to cause oxygen deficiency.     

MOCVD preparation of SBTN thin films from two organometallic sources bottles

Abstract

SrBi₂(Ta_0.7Nb_0.3)₂O₉ (SBTN) films were first prepared on (111)Pt/Ti/SiO₂/Si substrates by MOCVD from only two organometallic source bottles. Bi(CH₃)₃ and the mixture of Sr[Ta(O°C₂H₅)₆]₂ and Sr[Nb(O°C₂H₅)₆]₂ were used as source materials. High compositional reproducibility was obtained; the Nb/(Ta+Nb) ratio was the same as the mixing ratio of the source. Sr/(Ta+Nb) and Bi/(Ta+Nb) ratios can be controlled by the reactor pressure and the input gas flow rate ratio of the source gases. Almost single phase of SBTN was obtained for the film deposited at 500°C and the following heat-treated at 800°C in O₂ atmosphere. Pr and Ec values of 330 nm-thick SBTN film were 8.5 μC/cm² and 91 kV/cm, respectively and were larger than those of SrBi₂Ta₂O₉ film. There was no degradation after 5x10¹⁰ cycles polarization switching.     

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.     

Temperature dependence of the dielectric dispersion and ferroelectric properties of neodymium doped bismuth titanate ceramics

Nd-doped bismuth titanate Bi_{4 − x} Nd _x Ti₃O₁₂ ceramics (x = 0–1.0) were prepared by the solid state reaction method. The temperature dependence of the dielectric dispersion and ferroelectric properties were investigated. With the increase of the Nd substitution for Bi ion, the Curie temperature decreased and the corresponding dielectric constant peak broadened. In addition, the strong low-frequency dielectric dispersions were exhibited. The Nd doping decreases the temperature dependence of the ac conductivity and increases the temperature dependence of the remanent polarization, which is caused by the induced polarization by defects, such as bismuth and oxygen vacancies.     

Ferroelectric Pb5Ge3O11 MFMOS capacitor for one transistor memory applications

Abstract

The basic mechanism for an one transistor memory device has been studied. Many ferroelectric materials such PbZr_xTi_1?xO₃ (PZT), SrBi₂Ta₂O₉ (SBT), Pb₅Ge₃O₁₁ (PGO) etc. were analyzed for this application. Because of its low remanent polarization and low dielectric constant, the c-oriented Pb₅Ge₃O₁₁ thin film was selected for one-transistor memory applications. Pb₅Ge₃O₁₁ thin films have been prepared using MOCVD and RTP (Rapid Thermal Process) post-annealing. Lead bis-tetramethylheptadione [Pb(thd)₂] and germanium ethoxide [Ge(OC₂H₅)₄] were used as the precursors. The Pb₅Ge₃O₁₁thin films were deposited onto Ir/Ti/SiO₂/Si wafers to measure their compositions, phase formation, microstructure and ferroelectric properties. The extremely highly c-oriented Pb₅Ge₃O₁₁ thin films showed good ferroelectric and electrical properties. A 300 nm thick PGO thin film exhibited a square and saturated hysteresis loop with 2Pr of 3.98 μC/cm², 2Ec of 128 KV/cm at an applied voltage 5V, leakage current of 5.1×10^?7 A/cm² at 100 KV/cm, and dielectric constant of close to 36. The c-axis oriented Pb₅Ge₃O₁₁ thin film also exhibited very good retention properties. The experimental results showed that a Pb₅Ge₃O₁₁ MFMOS gate stack is suitable for one-transistor memory applications.     

Modeling of dynamic response of ferroelectric capacitors

Abstract

A simulation model of ferroelectric capacitors which describes both hysteresis loops under arbitrary voltage profile and time dependence of polarization change is developed based on the parallel-element model. In the model, a ferroelectric capacitor is assumed to consist of parallel capacitor elements with different coercive voltage and switching polarization. A new method of pulse measurement is designed to obtain the switching behavior of individual element. The measurement on a sol-gel SrBi₂Ta₂O₉ capacitor revealed that the switching time depended on the difference between the applied voltage and the coercive voltage of the capacitor element. The switching behavior is reproduced by inserting a nonlinear resistor in series with each capacitor in the model. All the parameters used in the model are determined from the measured data and no arbitrary fitting parameters are used.     

Structure and ferroelectric property of Nb-doped SrBi4Ti4O15 ceramics

Nb-doped SrBi₄Ti₄O₁₅ (SBT) was produced by conventional method. Structural and ferroelectric properties of SBT were examined as a function of niobium composition. Analyzing the structure futures of SBT by XRD, XPS and Raman spectrum, Nb⁵⁺ substituted Ti⁴⁺ to form NbO₆ octahedron and did not change the structure of SBT. The XRD patterns indicated the formation of the single phase of SBT for x = 0.01and 0.03 and secondary phase of Sr₃Ti₂O₇ appeared when x > 0.1. To compare the effect of Nb doping, the ferroelectric properties (hysteresis loop, piezoelectric coefficient) of Nb-doped SBT were measured. The SBT doped with x = 0.15 was found to exhibit higher remanent polarization with d ₃₃ = 17 pC/N.     

Thickness dependent morphology and electrical characteristics of SrBi2Ta2O9 deposited by metal organic decomposition

Abstract

The dependence of morphology of SrBi₂Ta₂O₉ (SBT) deposited by Metal Organic Decomposition (MOD) on film thickness and annealing temperature during the crystallization anneal was investigated. From Atomic Force Microscope (AFM) images of these films it can be seen that nucleation and grain growth strongly depends on SBT thickness which also affects the electrical characteristics of the correspondent Pt/SBT/Pt-capacitors. In this work results of a morphological study of SBT films with thicknesses between 40 and 110nm and annealing temperatures between 650°C and 725°C will be presented.