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.     

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.     

Improvement in the electrical properties of ferroelectric SrBi2Ta2O9 capacitors by electron beam irradiation on precursor films

Abstract

Ferroelectric SrBi₂Ta₂O₉ (SBT) capacitors were fabricated by the Electron-Beam-Induced Patterning process and their electrical properties were evaluated in detail. In this process, the dose of an electron beam irradiated on precursor films had a great influence on the electrical properties of the SBT capacitors. The appropriate electron dose significantly improved the electrical properties of the SBT capacitors although the excess electron dose made severe deterioration in the properties. The SBT capacitors fabricated with the optimum electron dose, 1.5 mC/cm² for Sr:Bi:Ta = 0.8:2.2:2.0 solutions, exhibited excellent ferroelectric properties: a remanent polarization of 11.5 μC/cm², a coercive field of 40 kV/cm, a leakage current of 8×10^?8 A/cm²@ 1V and fatigue-free up to 1010 cycles. It seems that such improvements were caused by the adjustment of Bi contents in the films and the modification or the decompositon of precursors before heat treatment by electron beam irradiation.     

Effects of bi2o3 buffer layer on ferroelectric properties of srbi2ta2o9 thin films by liquid-delivery mocvd

Abstract

Ferroelectric SrBi₂Ta₂O₉ thin films were deposited on the Bi₂O₃ buffered Pt/Ti/SiO₂/Si substrates using liquid-delivery metalorganic chemical vapor deposition. SBT films with 5nm thick-Bi₂O₃ buffer layer on Pt bottom electrode showed stronger (115) orientation than those without Bi₂O₃ buffer layer after annealing at 750°C. The value of the remanent polarization of SBT films with Bi₂O₃ buffer layer were improved significantly in comparison with those for the films without Bi₂O₃ buffer layer. The remanent polarization(2Pr) and coercive field(Ec) of SBT films without and with Bi₂O₃buffer layer annealed at 750°C were 11.9, 20.8 μ C/cm2 and 57, 37.8kV/cm at an applied voltage of 5 V, respectively.     

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.     

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.     

Preparation of BST thin films on Pt electrode on Si wafer with down-flow LSMCVD reactor

Abstract

A novel type of down-flow LSMCVD (Liquid Source Mist CVD) reactor was developed to prepare a high dielectric BST thin film on Pt electrode on Si wafer. Barium acetate [Ba (OOCCH₃)₂], strontium acetate [Sr (OOCCH₃)₂], and titanium isoproxide [Ti (OC₃H₇ ⁱ )₄] were used as metal sources. Metal sources were dissolved in acetic acid, 1-butanol, or 2-methoxyethanol. BST [Ba/(Ba + Sr) = 0.7] film annealed on Pt/Ti/SiO₂/Si above 650°C was polycrystalline. BST film has a (110) preferred orientation with increasing temperature. Surface roughness of BST film and grain size increased with increasing temperature. The metal-oxygen bond was formed at 650°C as shown in the spectra of FTIR. The depth profiles of elements of BST thin films indicated a uniform composition throughout the film. BST films annealed at 750°C showed a dielectric constant and a tanδ of 390 (thickness: 150 nm) and 0.06 at a frequency of 100 kHz, respectively. The behavior of capacitance of the BST film with bias voltage showed paraelectric property. BST film annealed at 750°C had the leakage current density of 3.2 (μA/cm²) at a bias voltage of 2V.     

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.     

Enhanced ferroelectric properties of multilayer SBT-BTN thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉ – (Bi₄Ti₃)_1-xNb_xO₁₂ (SBT-BTN) multilayer thin films with various stacking periodicity have been synthesized on Ir/Ti/SiO₂/Si substrates by metal organic chemical vapor deposition technique (MOCVD). Tributylbismuth [Bi(C₄H₉)₃], strontium-bis[tantal(pentane-ethoxy)(2-methoxyethoxide)] [Sr[Ta(OEt)₅(OC₂H₄OMe)]₂], titanium bis(isopropoxy)bis(1-methoxy-2-methyl-2-propoxide) [Ti(OiPr)₂(mmp)₂] and niobium-ethoxide [Nb(OC₂H₅)₅] were selected as precursors. X-ray diffraction patterns show that the multilayer films annealed at 800°C consisted of a fully formed perovskite phase with polycrystalline structure. The remanent polarization (2·P_r) and coercive field strength (E_c) were 16.2 μC/cm² and 230 kV/cm, respectively, values which are much higher compared to pure SBT film (2·P_r = 6.4 μC/cm², E_c = 154 kV/cm).     

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.     

Fabrication of MFIS diodes using sol-gel derived SBT films and LaAlO3 buffer layers

Abstract

We demonstrate the ferroelectric behavior of Sr_0.8Bi_2.2Ta₂O₉ (SBT) films grown on Si(100) substrates by using lanthanum aluminate (LaAlO₃) buffer layers. LaAlO₃ films were prepared by vacuum evaporation method. Then, they were subjected to ex situ dry N₂ annealing in a rapid thermal annealing (RTA) furnace. From the capacitance-voltage (C-V) measurement, the dielectric constant of LaAlO₃ was estimated to be 20～25. On these substrates, SBT films (210nm) were deposited by sol-gel method and they were characterized by XRD analysis after annealing under various conditions. It was found from C-V characteristics that the memory window of an SBT film annealed at 750°C for 30min in O₂ atmosphere was about 3.0V for the voltage sweep of ±10V. It was also found from the retention measurement that the capacitance values of the SBT film annealed at 750°C did not change over 12hours. It is concluded from these results that the SBT/LaAlO₃/Si(100) structure is one of the most promising structures for realizing MFISFETs (metal-ferroelectric-insulator-semiconductor field-effect-transistors).     

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.     

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     

Preparation of SrBi 2 Ta 2 O 9 Ferroelectric Thin Films by RF Magnetron Sputtering

Ferroelectric SrBi 2 Ta 2 O 9 (SBT) thin films were deposited by RF magnetron sputtering on a Pt/Ti/SiO 2 /Si(100) structure. The deposition temperature of the film was varied from RT (room temperature) to 600C. It was found that the SBT films were crystallized at temperatures between 500C and 600C, which was much lower than the annealing temperature (700C to 800C) of the RT-deposited film. The maximum remnant polarization value (2Pr) of the SBT film was 15 w C/cm 2 , which was deposited at 575C.     

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.     

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     

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.     

Chemical Processing and Properties of (Sr,Ca) 2 (Nb,Ta) 2 O 7 Thin Films

Ca-doped Sr 2 (Nb,Ta) 2 O 7 thin films have been synthesized by the chemical solution deposition. Homogeneous and stable (Sr,Ca) 2 (Nb,Ta) 2 O 7 precursor solutions were prepared by optimizing the reaction of starting metal alkoxides in ethanol with a key additive of 2-ethoxyethanol. The improvement of ferroelectric properties of the Sr 2 (Nb,Ta) 2 O 7 based films were achieved through the Ca substitution into Sr 2 (Nb 0.3 Ta 0.7 ) 2 O 7 as well as the optimization of heating conditions. The crystallization temperature of the layered perovskite (Sr 0.9 Ca 0.1 ) 2 (Nb 0.3 Ta 0.7 ) 2 O 7 thin films on Pt/Ir/Ti/SiO 2 /Si substrates was found to be above 750C. (Sr 0.9 Ca 0.1 ) 2 (Nb 0.3 Ta 0.7 ) 2 O 7 thin films crystallized at 750C exhibited P r of 0.51 w C/cm 2 and E c of 69 kV/cm.     

PREPARATION AND PROPERTIES OF LITHIUM-DOPED K0.5Na0.5NbO3 THIN FILMS BY CHEMICAL SOLUTION DEPOSITION

ABSTRACT

Lithium-doped K_0.5Na_0.5NbO₃ (KLNN) films were fabricated by chemical solution deposition on Pt/TiO₂/SiO₂/Si substrates. Homogeneous and stable precursor solutions were prepared by controlling the reaction of starting metal alkoxides. Perovskite KLNN single-phase thin films were successfully synthesized on Pt/TiO _x /SiO₂/Si substrates. The 0.75-μ m-thick KLNN film annealed at 650°C exhibited ferroelectric polarization hysteresis loops at ?250°C. The loop at room temperature was round, indicating the film contained leakage components. The dielectric constant under zero bias was 490 at room temperature. A typical upside-down butterfly DC bias-capacitance curve was obtained in the KLNN film capacitors at room temperature, indicating that polarization reversal occurred in the obtained KLNN films.     

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.