Preparation of Si-Added SrBi2Ta2O9 Ferroelectric Thin Films by RF Magnetron Sputtering

Si-added SrBi₂Ta₂O₉ (SBT) ferroelectric films were prepared by RF magnetron sputtering on a Pt/Ti/SiO₂/Si (100) structure. The films were deposited at temperatures below 100°C for surpressing Bi evaporation, and crystallized at 800°C in air. A typical composition was Sr_0.79Bi_2.37Ta_2.00Si_0.2O_x. The remanent polarization value (2Pr) of the Si-added SBT film was 16 μC/cm². The Si atom addition was found to be effective in improvement of the fatigue and leakage current of SBT ferroelectric films. The leakage current density was further improved by annealing in the high-pressure oxygen ambient at 7 atms.     

Ferroelectric SrBi2Ta2O9 thin films deposited by liquid injection MOCVD using novel bimetallic alkoxide precursor

Abstract

The ferroelectric SBT films were deposited on Pt/Ti/SiO₂/Si substrates by liquid injection metalorganic chemical vapor deposition (MOCVD) with single-mixture solution of Sr[Ta(OEt)₅(dmae)]₂ and Bi(C₆H₅)₃. The Sr/Ta and Bi/Ta ratio in SBT films depended on deposition temperature and mol ratio of precursor in the single-mixture solution. At the substrate temperature of 400°C, Sr/Ta and Bi/Ta ratio were close to 0.4 and 1 at precursor mol ratio of 0.5～1.0. As-deposited film was amorphous. However, after annealing at 750°C for 30 min in oxygen atmosphere, the diffraction patterns indicated polycrystalline SBT phase. The remanent polarization (Pr) and coercive field (Ec) of SBT film annealed at 750°C were 4.7 μC/cm²and 115.7 kV/cm at an applied voltage of 5 V, respectively. The SBT films annealed at 750°C showed practically no polarization fatigue up to 10¹⁰ switching cycles.     

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.     

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.     

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.     

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.     

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.     

Low temperature process and thin SBT films for ferroelectric memory devices

Abstract

At crystallization temperatures of about 800°C bismuth layered oxide SrBi₂Ta₂O₉ (SBT) deposited by MOD develops good ferroelectric properties for use in FeRAM devices. But scaling down the film thickness of SBT below 150 nm only shorts are measured at this crystallization temperture after top electrode deposition. Working Pt/SBT/Pt-capacitors are achieved by reducing the crystallization temperature. Also temperatures of 800°C are too high for integration of the SBT module in a stacked capacitor architecture for high density memory devices. Therefore, a process is needed to reduced the crystllization temperature of SBT, called ”Low Temperature Process“.

In this work the electric properties of spin-on processed SBT crystallized in a temperature window from 650°C up to 800°C are investigated. As shown by XRD, transtion of the nonferroelectric Fluorite phase to the Aurivillius phase takes place at approximately 625°C. Increasing the cystallization temperature gives better crystaallized SBT films with bigger SBT graains. However, film prosity is also increasing with temperature. Electrical results of stoichiometric variations of SBT are presented. SEM pictures show that cluster formation is correlated with less film porosity at lower temperatures.     

New top and bottom electrodes for SrBi2Ta2O9 ferroelectric capacitors

Abstract

SBT is a candidate as the ferroelectric material for large scale FeRAMs with the great advantages of less fatigue and better squareness in its P-E hysteresis curves, while SBT has the disadvantages of higher crystallization temperature that results in difficulties realizing a stacked structure cell and greater damage to its ferroelectric properties from forming gas annealing. This paper presents new top and bottom electrodes to eliminate these disadvantages for SBT. The remanent polarization decreases only slightly after forming gas annealing with the top electrodes of partially oxidized Ru. Ru-O top electrodes show no bubbles or peeling after forming gas. In order to achieve the stacked structure cell for SBT capacitors, a new diffusion barrier was developed. This new diffusion barrier withstands the high temperature annealing that is required to crystallize SBT films. With the new diffusion barrier hysteresis curves could be obtained with electrical connections through Si substrates.     

CHARACTERISTICS OF METAL-FERROELECTRIC-INSULATOR-SILICON DEVICES USING HFSION BUFFER LAYERS

ABSTRACT

In this work, metal-ferroelectric-insulator-silicon (MFIS) devices were fabricated using HfSiON as buffer layers and their electrical properties were studied. Ultra-thin HfSiON films were fabricated by electron-beam evaporation at room temperature and post-annealed using different parameters such as temperature, time in O₂. By annealing a 2 nm-thick HfSiON film at 800°C for 60s in O₂, a negligible hysteresis loop and small equivalent oxide thickness of 2.3 nm were obtained with a corresponding leakage current density of 6.8 × 10^{? 5} A/cm² at a voltage shifted from the flat band voltage by 1 V. In the fabrication of MFIS diodes, Sr_0.8Bi_2.2Ta₂O₉ (SBT) films with 400 nm thickness were formed by chemical solution deposition. For Pt/SBT (400 nm)/HfSiON(2 nm)/Si diodes, a memory window of 0.8 V in width was observed during double capacitance-voltage sweep between +5 and –5 V. At the same time, excellent data retention properties were observed. The high and low capacitances in the hysteresis loop were well distinguishable even after 24 h had elapsed.     

Defect Chemistry of SrBi2Ta2O9 and Ferroelectric Fatigue Endurance

The defect chemistry and charge transport properties of doped and undoped SrBi₂Ta₂O₉ (SBT) were studied by making 4-point dc equilibrium electrical conductivity, thermopower, ionic transport number, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) measurements. Results of high temperature equilibrium dc conductivity, thermoelectric power, and transport number measurements as a function of oxygen activity in the temperature range 650–725°C revealed that undoped SBT displays a broad centrally located plateau of ionic conductivity with an activation energy of mobility of 0.94 eV and a prominent upturn at high oxygen activity, caused by p-type conductivity. The effects of acceptor and donor dopants are consistent with a 1–2% net acceptor excess in the undoped compound. It has been observed that there is substantial (several percent) cation place exchange between the Sr²⁺ and Bi³⁺ in SBT. It is proposed that the net acceptor excess in undoped SBT consists of disordered Sr²⁺ substituting for Bi³⁺ in the fluorite-like bismuth oxide layers which are locally compensated by oxygen vacancies. The formation of the net donor excess by disordered Bi³⁺ substituting for Sr²⁺ in the perovskite-like layers does not manifest itself as n-type conductivity behavior, because the band gap is large and the mobility is highly thermally activated. The superior intrinsic ferroelectric fatigue endurance of SBT is attributed to the lack of mobile charged defects in the perovkite-like layers which create the ferroelectric response of the compound. The metallic bismuth presence on the surface of undoped SBT, as revealed by qualitative XPS measurements, is believed to result from long exposure to the highly reducing conditions in the XPS system.     

Low temperature growth of sol-gel SrBi2Ta2O9 thin films by low-pressure annealing

A new low-temperature processing method to prepare SrBi₂Ta₂O₉ thin films is proposed. These thin films were prepared on Pt/Ta/SiO₂/Si substrates by a sol-gel method, and their structural and electrical properties were investigated. Films were annealed before and after the top Pt electrode deposition. The first annealing was performed in a 760-Torr oxygen atmosphere at 600 °C for 30 min, and the second annealing was performed in a 5-Torr oxygen atmosphere at 600 °C for 30 min. The films were well crystallized and fine-grained after the second annealing. The electrical characteristics of the 200-nm-thick film obtained by this new process were as follows: remanent polarization, P_r = 8.5 μC/cm²; coercive field, E_c = 36 kV/cm; and leakage current density, I_L = 1 × 10⁻⁷ A/cm² (at 150 kV/cm). This process is very attractive for highly integrated ferroelectric nonvolatile memory applications. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 120(2): 27–33, 1997     

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.     

Preparation of PZT Thin Films by Liquid-Source MOCVD Using of Cyclohexane Solvent

Pb(Zr, Ti)O₃ thin films were grown on 8-inch Ir(111)/SiO₂/Si substrate by a MOCVD system aiming at application utilizing high-density ferroelectric memory (FRAM). Two types of solvents, THF and cyclohexane were used for liquid source delivery. It was found that the ferroelectric properties of the MOCVD-PZT films using cyclohexane solvent were better than them using THF solvent. By choosing cyclohexane as solvent, the MOCVD-PZT thin films showed strong ?111? preferred orientation and the Pt/PZT/Ir capacitors exhibited promising ferroelectric performances, for instance, large switching charge (Qsw) of 56.4 uC/cm².     

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.     

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.     

Distributed phase shifters using (Ba,Sr)TiO3 thin films on sapphire and glass substrates

Abstract

Sol-gel solutions were synthesized by using various alkoxides of polyhydric alcohol, carboxylate and stabilizer. Stability of modified sol-gel solution was good enough to keep its properties after at least three months although that of ordinary sol-gel solution is not good.

SBT films were fabricated on Pt(200nm)/Ti(20nm)SiO₂(500nm)/Si substrate at under 700°C by using modified sol-gel solution. Range of drying temperature was 200 to 400°C and that of RTA was 550 to 700°C. At high drying temperature, decrease of crystallinity for SBT films was observed accompanied by nucleation of Sr carbonate. On the other hand, SBT film dried at under 250°C and crystallized at 700°C shows high crystallinity of layer perovskite.

SBT film derived from conventional sol-gel solution used to show strong crystal orientation of c-axis. In case of modified sol-gel solution, RTA temperature and amount of added stabilizer influenced crystal orientation of film. So it was possible that to control crystal orientation of SBT films by adjust RTA condition and amount of stabilizer. Stability of sol-gel solution and property of SBT films were influenced by component of solvent, electric properties of SBT films especially I-V property were improved.

Using low temperature deposition process at 650°C, SBT films derived from modified sol-gel solution show superior ferroelectric properties to SBT thin films derived from conventional MOD solution.     

Comparison of sputtered SBTN and PLZT thin film capacitors for FRAM applications

Abstract

Thin films of the solid solution SrBi₂Ta₂O₉-SrBi₂Nb₂O₉ (SBTN) and Ca and Sr doped (Pb, La)(Zr, Ti)O₃ (PLZT) were prepared by conventional, single target, rf-magnetron sputtering. The films were deposited onto Pt coated substrates with a diameter of 6 inches. The electrical properties were characterized by hysteresis and pulsed field switching measurements. A ferroelectric performance comparison between two types of capacitors will be presented. The recent improvement in PLZT capacitor processing have greatly extended fatigue resistance beyond what is usually observed and reported for SBTN capacitors.     

Investigation on various insulator layers for MFIS capacitors

Abstract

Effects of insulator layers of Metal(Au)/Ferroelectrics(PZT)/Insulator/Si (MFIS) structure capacitors are investigated for non-destructive type non-volatile memory device applications. Various high dielectric oxide layers such as Al₂O₃, Ta₂O₅, TiO₂ and ZrO₂ were fabricated by reactive sputtering as insulating layers. The oxide insulators give significant impacts on the morphologies of PZT layer and the properties of capacitors. It is noted that the oxide layers with small thermal expansions (<6x10^–6/°C) coefficient caused cracks on PZT films during PZT crystallization annealing. The effects of insulators as a diffusion barrier are also comparatively studied using Auger electron spectroscopy. In addition, the characteristics of high dielectric solid solution, such as titanium oxide-zirconium oxide, are also studied.     

Preparation of Bi4Ti3O12 thin films by electron cyclotron resonance sputtering

Abstract

Ferroelectric Bi₄Ti₃O₁₂ thin films were deposited on Pt-coated oxidized Si substrate by electron cyclotron resonance (ECR) sputtering using ceramic targets. Crystal structure and dielectric properties of the films were investigated as functions of sputtering conditions such as substrate temperature and sputtering gas. Using a target with excess Bi content compared to stoichiometric composition was required to compensate Bi re-evaporation from the substrate and to obtain a perovskite single phase at 600°C. (117)-oriented films exhibited ferroelectric hysteresis loops. The remanent polarization and coercive field of the films were 9.8 μC/cm² and 180 kV/cm, respectively.