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.     

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.     

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 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.     

Y_2O_3插层对Ni_(81)Fe_(19)薄膜各向异性磁电阻的影响

以Y_2O_3作为Ni_(81)Fe_(19)薄膜的氧化插层,利用磁控溅射法制备了一系列不同插层厚度的Ni_(81)Fe_(19)薄膜样品Ta(4nm)/Y_2O_3(t)/Ni_(81)Fe_(19)(20nm)/Y2O3(t)/Ta(3nm),利用非共线四探针法测量薄膜样品的各向异性磁电阻(AMR),用振动样品磁强计测量样品的磁滞回线,利用X射线衍射仪(XRD)分析样品薄膜结构,研究了Y_2O_3插层厚度对Ni_(81)Fe_(19)薄膜各向异性磁电阻的影响。结果表明,在基片温度为450℃时,Ni_(81)Fe_(19)薄膜AMR值随插层厚度增加先增后减,在插层厚度为2.5nm时样品具有最大AMR,其值为4.61%,比无插层样品的2.69%提高了71.3%。     

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.     

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.     

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.     

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.     

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.     

Fabrication and characterization of Au/SBT/LZO/Si MFIS structure

Ferroelectric SrBi₂Ta₂O₉ (SBT) films on a p-type Si (100) wafer with a LaZrO _x (LZO) buffer layer have been fabricated to form a metal-ferroelectric-insulator–semiconductor (MFIS) structure. The LZO thin film and SBT films were deposited by using a sol–gel method. The equivalent oxide thickness (EOT) value of the LZO thin film was about 8.83 nm. Also, the leakage current density of the LZO thin film is about 3.3?×?10^?5 A/cm² at bias sweeping voltage of ±5 V. SBT films were crystallized in polycrystalline phase with highly preferred (115) orientation. Also, the intensity of each pick slightly increased as thickness of SBT films increased. The C–V characteristics of Au/SBT/LZO/Si structure showed clockwise hysteresis loop. The memory window width increased as the thickness of SBT films increased. The leakage current density of Au/SBT/LZO/Si structure decreased as thickness of SBT films increased.     

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.     

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.     

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.     

Dielectric properties for Tantalum-doped strontium barium titanate thin films prepared by sol-gel method

In this work, Sr_0.5Ba_0.5Ti_1-zTa_zO₃ (SBT) thin films were prepared on a Pt/SiO₂/Si substrate by sol-gel process. The microstructures of SBT thin films were examined by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). The influences of Ta on the microstructure and dielectric properties of SBT thin films were studied. It is found that tetragonal perovskite crystal grains existed in SBT thin films. Ta⁵⁺ doping fines the grain of SBT thin films. It is found that Ta⁵⁺ doping decreases dielectric loss for SBT thin films.     

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.     

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.     

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.     

Strong thickness dependence of aurivillius phase formation in SrBi2Ta2O9 thin films

Sr_0.7Bi_2.4Ta₂O₉ (SBT) thin films were studied for the dependence of Aurivillius phase formation kinetics on their film thickness. SBT thin films were fabricated using a sol-gel process and spin coating, and their thickness was varied controlling the number of spin coating. The films were first heated at a low temperature for the complete crystallization of amorphous film to fluorite phase and then further heated at different elevated temperatures for the phase transformation to Aurivillius for 40 min. It was found that the phase transformation kinetics apparently increased with thickness up to ∼390 nm, and then it sharply decreased at higher values. The Aurivillius crystal size decreased and the density of crystals increased with the increase of film thickness up to ∼390 nm, implying increasing number of nuclei due to the reduced energy barrier for nucleation. Above the critical value both the size and density of crystals decreased. It is suggested that up to ∼390 nm the tensile strain energy in the films, which was stored by the shrinkage of thin films during the removal of remaining organic components from sol-gel chemistry, plays a major role for determining the phase transformation kinetics and above the critical value SBT films act as a free bulk material without substrate constraints.     

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).