Degradation mechanisms of SrBi2Ta2O9 ferroelectric thin film capacitors during forming gas annealing

Abstract

The effects of annealing in forming gas (5% hydrogen, 95% nitrogen; FGA) are studied on spin coated SrBi₂Ta₂O₉ (SBT) thin films. SBT films on platinum bottom electrode are characterized with and without platinum top electrode by Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES), High Temperature X-Ray Diffraction (HT-XRD) and Secondary Ion Mass Spectrometry (SIMS).

High Temperature X-Ray Diffraction (HT-XRD) of blanket Ti/Pt/SBT films in forming gas revealed that the bismuth layered perovskite structure of the SBT is stable up to approx. 500°C. SIMS analysis of Pt/SBT/Pt samples annealed in deuterated forming gas (5% D₂, 95% N₂) showed that the hydrogen accumulates in the SBT layer and at the platinum interfaces next to the SBT. After FGA of blanket SBT films, tall platinum-bismuth whiskers are seen on the SBT surface.

Performing the FGA of the whole Pt/SBT/Pt/Ti stack, two different results are found. For the samples with a high temperature annealing (HTA) step in oxygen after top electrode patterning, top electrode peeling is observed after FGA. For the samples without a HTA step after top electrode patterning, no peeling is observed after FGA.     

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.     

Influence of Ti-content in the bottom electrodes on the ferroelectric properties of SrBi2Ta2O9 (SBT)

Abstract

Stress behavior, results of AES analysis and electrical properties of SBT in dependence of electrode structure and annealing conditions are discussed. Evidence for degradation of the electrical properties of SBT due to diffusion of Ti is presented.     

Glycolate tantalum based solutions for the sol-gel spin-coating deposition of SrBi2Ta2O9 thin films

Abstract

The reaction of tantalum ethoxide with a glycol solvent produces the interchange of the ethoxide groups with the glycol. As a result, a polymeric derivative is formed with a high resistance towards hydrolysis. Compounds of Sr(II) and Bi(II) can be added to this Ta-glycol sol, leading to strontium bismuth tantalate (SBT) precursor solutions stable in air. These solutions were spin-coated onto two substrates: Pt/TiO₂/SiO₂/(100)Si and Ti/Pt/Ti/SiO₂/(100)Si. Crystallisation of the SBT phase was carried out by a first formation of a fluorite phase that evolves to the layered perovskite at temperatures over 600°C. During crystallisation, a larger tendency to the formation of a substrate/film interface was observed in the films deposited onto Ti/Pt/Ti/SiO₂/(100)Si than onto Pt/TiO₂/SiO₂/(100)Si. A remanent polarisation of P_r5 μC/cm² and a coercive field of E_c <100 kV/cm were measured in the films on Pt/TiO₂/SiO₂/(100)Si. These films retain its remanent polarisation, P_r, up to 10⁵seconds and are fatigue-free up to 10⁹ cycles.     

Forming gas annealing effects on the microstructure and ferroelectricity of SrBi2Ta2O9 thin films prepared by metalorganic decomposition

Abstract

Ferroelectric SrBi₂Ta₂O₉(SBT) thin films prepared by metalorganic decomposition (MOD) method were annealed in forming gas (5% hydrogen + 95% nitrogen) at different temperatures for 60 min. SEM analysis results showed that an amount of columnar structures appeared on SBT surface when the annealing temperature was up to 450°C. When the annealing temperature raised up to 500°C, these columnar structures grew along one dimension and changed into wire structures. The EDX micro-area mapping analysis result showed that Bi was concentrated in the columnar or wire structures on SBT surface. The ferroelectric property analysis results showed that the hysteresis loops still existed after 5 min forming gas processing (350°C or 400°C), but when the annealing time was longer than 10 min, the resistance of the SBT samples became too low to measure the hysteresis loops.     

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 of SrBi2Ta2O9 ferroelectric thin film by rf magnetron sputtering

Abstract

SrBi₂Ta₂O₉ (SBT) thin films were deposited on 6-inch Pt/Ti/SiO₂/Si substrates by rf magnetron sputtering using a 12-inch ceramic SBT single target. It is found that several sputtering parameters such as argon (Ar) pressure and rf power were very effective to control the Bi content of SBT thin films which is essential for obtaining good ferroelectric properties.     

Low temperature preparation of ferroelectric SrBi2Ta2O9 thin films by a modified RF magnetron sputtering technique

Abstract

Bi–layered ferroelectric SrBi₂Ta₂O₉ (SBT) films were successfully prepared on Pt/Ti/SiO₂/Si substrates at 650°C by a modified rf magnetron sputtering technique. The SBT films annealed for 1 h in O₂ (760 torr) and again for 30 min in O₂ (5 torr) at 650°C show a average grain size of about 49 nm. The SBT films annealed at 65 0°C have a remanent polarization (P_r) of 6.0 μC/cm² and coercive field (E_c) of 36 kV/cm at an excitation voltage of 5 V. The films showed fatigue–free characteristics up to 4.0 × 10¹⁰ switching cycles under 5 V bipolar pulse. The retention characteristics of SBT films looked very promosing up to 1.0 × 10⁵ s.     

Atomic-scale microstructures of SrBi2Ta2O9 (SBT) ferroelectric thin films prepared by MOD and PLD for ferams applications

Abstract

In this work, the microstructural defects in SrBi₂Ta₂O₉ (SBT) ferroelectric thin films were investigated at the atomic-scale by high-resolution transmission electron microscopy (HRTEM). A stacking fault with an extra inserted Bi-O plane normal to the c-axis was observed in SBT film with 10mol% excess bismuth prepared by metalorganic deposition. Edge dislocations with an average space about 3nm were observed at the small misorientation angle (8.2°) tilt grain boundary of SBT film with (001)-orientation prepared by pulsed laser deposition. The Burgers vector b for the edge dislocation was determined to be 1/2[110]α₀, where α₀ is the parameter of SBT unit cell. Chemical compositions of grains and grain boundaries in SBT films annealed in forming gas at 450°C and 500°C for 60 minutes were analyzed by using energy dispersive spectra at the nano-scale. Effects of the microstructural defects and microchemistry of the grain boundaries on the leakage current of SBT films are briefly discussed.     

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.     

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.     

Effects of nitridation treatments for SBT/Ta2O5 stack gate capacitors

Abstract

In this study, effects of ICP nitride treatments on characteristics of ferroelectric gate stack capacitor were investigated for FET type ferroelectric memory applications. Pt/SBT(200nm)/Ta₂O₅(20nm)/ Nitride/Si (MeFINS) structure capacitors show wide ΔV (memory window) of 1.06V under ±3V operation, while Pt/SBT(200nm)/ Ta2O₅(20nm)/Si (MeFIS) capacitors without nitride treatments exhibit memory window of 0.60V. At the same time, an accumulation capacitance of the MeFINS structure device is higher than that of the MeFIS structure capacitor. This result implies that the ICP nitride treatment successfully suppresses a formation of low dielectric constant interfacial SiO_x layer and alleviates a series capacitance problem.     

Characterization of the CeO2 thin films for insulation layer and Pt/SrBi2Ta2O9/CeO2/Si MFISFET structure

Abstract

CeO₂ and SrBi₂Ta₂O₉ (SBT) thin films for MFISFET (metal-fcrroelectrics-insulator-semiconductor field effect transistor) were deposited by rf sputtering and pulsed laser deposition method, respectively. The effects of oxygen partial pressure during deposition for CeO₂ films were investigated. The oxygen partial pressure significantly affected the preferred orientation, grain size and electrical properties of CeO₂ films. The CeO₂ thin films with a (200) preferred orientation were deposited on Si(100) substrates at 600°C. The films deposited under the oxygen partial pressure of 50 % showed the best C-V characteristics among those under various conditions. The leakage current density of films showed order of the 10^?7～10^?8 A/cm² at 100 kV/cm. The SBT thin films on CeO₂/Si substrate showed dense microstructure of polycrystalline phase. From the C-V characteristics of MFIS structure composed of the SBT film annealed at 800°C, the memory window width was 0.9 V at ±5 V. The leakage current density of Pt/SBT/CeO₂/Si structure annealed at 800°C was 4×10^?7 A/cm² at 5 V.     

Effect of Oxygen Plasma on Growth, Structure and Ferroelectric Properties of SrBi2Ta2O9 Thin Films Formed by Pulsed Laser Ablation Technique

Growth of SrBi₂Ta₂O₉ (SBT) thin films has been carried out in the presence of O₂-plasma created by applying a potential at an auxiliary ring electrode placed near the substrate. Effect of plasma excitation potential and polarity, especially negative polarity, on the formation of a proper SBT phase at 700°C and in modifying crystallite orientation and microstructure of SBT films over (1 1 1) oriented Pt film coated over TiO₂/SiO₂/Si(1 0 0) substrates has been demonstrated. Preferred c-axis orientation of SBT films changes to (a–b) orientation with decrease in plasma excitation potential from –700 to –350 V and eliminates secondary Bi₂Pt phase formation even at 600°C Microstructural study show a 2-dimensional large flat c-oriented crystallites formed at –700 V change to small crystallites in conformity with the changed aspect ratio for crystallites in (a–b) plane parallel to film plane. Spectroscopic ellipsometric results are in agreement with the microstructural data. These affects are attributed to O₂-ion bombardment during film growth which reduces nucleation barrier for growth of crystallites in (a–b) plane. O₂-plasma sustains the cationic species formed by laser ablation, which along with O ₂ ⁺ ions, provide necessary activation energy and enhance the oxidation rates required for SBT phase formation even at 700°C. SBT films grown in O₂-plasma show enhancement in remnant polarization value from 1.2 to 6.6 C/cm² and display ferroelectric properties superior to those formed without plasma. Further O₂-plasma eliminates post deposition annealing step for observance of enhanced polarization values. This study shows O₂-plasma excitation potential could be exploited as a new process parameter in laser ablation growth of ferroelectric oxide thin films.     

Epitaxial structure SrBi2Ta2O9<116> /SrTiO3<011> /Ce0.12Zr0.88O2<001> /Si<001> for ferroelectric-gate FET memory

Abstract

Epitaxial thin film growth of SrBi₂Ta₂O₉/SrTiO₃/Ce_0.12Zr_0.88O₂ on Si was studied, and this epitaxial layer structure was applied to fabrication of ferroelectric-gate field effect transistors (FETs). The films were prepared by a pulsed laser deposition technique and epitaxial growth was identified by x-ray diffraction. The devices exhibited excellent electrical performances: Capacitance-voltage characteristic of a metal-ferroelectric-insulator-semiconductor (MFIS) diode showed a retention longer than 10 days and I_d-V_g characteristic of an MFIS-FET showed 1 day retention. It is proved that the crystalline quality of ferroelectric thin films is of great importance to develop integrated devices with high performance.     

Growth and characterization of non-c-axis-oriented SrBi2Ta2O9 epitaxial thin films on Si(100) substrates with SrRuO3 bottom electrodes

Abstract

We have successfully grown non-c-axis-oriented epitaxial ferroelectric SrBi₂Ta₂O₉ (SBT) films with (116) and (103) orientations on Si(100) substrates using epitaxial (110)- and (111)-oriented SrRuO₃ (SRO) bottom electrodes, respectively. The SRO orientations have been induced by coating the Si(100) substrates with epitaxial YSZ(100) and MgO(111)/ YSZ(100) buffer layers, respectively. All films were sequentially grown by pulsed laser deposition. Specific in-plane orientations of the epitaxial SBT films were found, which are in turn determined by specific in-plane orientations of the epitaxial SRO bottom electrodes. These include a diagonal rectangle-on-cube epitaxy of SRO(110) on YSZ(100) and a triangle-on-triangle epitaxy of SRO(111) on MgO(111).     

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.     

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.     

Improvement in microstructure of SBT thin films

Abstract

Various attempts to improve the microstructure of SBT thin films were carried out. One was to employ ultra-thin BT film as a top layer on the conventional SBT thin film. After optimization of the BT top layer thickness, a very smooth SBT surface was successfully achieved. Particularly, the insulation break down field was improved to more than 1.0 MV/cm. Next we used UV exposure during the baking process. By optimizing the UV assisted process, surface morphology was successfully improved with fine grain microstructure. The break down field was improved to more than 1.0 MV/cm. Also, these two process combinations successfully lead to more reliable SBT thin films. The break down field was drastically improved to more than 1.2 MV/cm.     

Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C