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.     

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).     

Low-Temperature Process of Ferroelectric (Y0.95,Bi0.05)MnO3 Thin Films and Their Structural and Electrical Properties

[(Y_0.95,Bi_0.05)MnO₃] (YBM) films have been grown on Y₂O₃ buffered Si (001) by pulsed-laser deposition (PLD). We have compared the structural and dielectric properties of YBM films with those of typical YMnO₃ films from the viewpoint of lowering the process temperature. The highly c-axis oriented YBM film have been obtained on Y₂O₃/Si (001) at 700°C, which is a significantly reduced growth temperature from that of typical YMnO₃ films (850°C). The Bi modification was effective for the low temperature processing of YBM films. These highly c-axis oriented YBM films was obtained only at high ambient oxygen pressures, for example above 100 mTorr, contrary to YMnO₃ films which requires low ambient oxygen pressure for the growth of c-axis preferred orientation. The dielectric constant and dissipation factor was 29 and 0.017 at 1 MHz, respectively. The memory window due to ferroelectric polarization switching was found in a capacitance-voltage (C-V) characteristic. The YBM/Y₂O₃/Si structure with above characteristics of YBM films exhibited the C-V memory window of 1.2 V at a sweep voltage of 5 V. The flat-band voltage shifted symmetrically with increasing the sweep voltage up to 8 V due to little charge injection from Si. As a result, the memory window increased progressively with increasing the sweep voltage and amounted to 2 V at a sweep voltage of 8 V. The leakage current density was below 5 × 10^?7 A/cm² at a bias voltage of 8 V.     

Inverse Capacitance-Voltage Characteristics of Bi3.25La0.75Ti3O12 Thin Film Pulsed Laser Deposited on Thermally Oxidized n-Type Si Substrates

Comparative studies on the electrical properties of a metal-ferroelectric-insulator-semiconductor field effect transistor were conducted using pulsed laser ablated ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films deposited on SiO₂/Si substrates with different SiO₂ thicknesses. The SiO₂ layer was prepared on n-type Si substrates by dry oxidation at a temperature of 800°C. Small angle x-ray reflectivity studies were used to measure the SiO₂ thickness. The capacitance-voltage (C-V) measurements revealed that the films showed good interfacial properties. Shifts in flatband voltages were observable, but were effectively reduced by deposition of the ferroelectric films. Au/BLT/SiO₂/Si diodes with 8 nm SiO₂ layer showed to be stable with relatively large memory window values of about 0.3 V, 2.5 V, 5.0 V, and 7.0 V, at increasing bias voltages of ±5 V, ±7 V, ±10 V, and ±12 V, respectively.     

Electronic Conductivity and Dielectric Properties of Nanocrystalline CeO2 Films

The growth of dielectric layers on silicon substrates has attracted a great deal of recent interest given their potential applicability in the fabrication of high quality silicon-on-insulator (SOI) structures, high density capacitor devices, and stable buffer layers between silicon and other materials. In this study, nanocrystalline CeO₂ films were deposited on n-type (100) silicon substrates using pulsed laser deposition (PLD) to form a gate dielectric for a Pt/n-Si/CeO₂/Pt MOS device. XRD, AFM and FESEM measurements were used to characterize the crystal structure and grain size of the CeO₂ films. The electrical properties of the device structure were examined by capacitance-voltage (C-V) and impedance spectroscopy measurements. The CeO₂ films exhibited an activated conductivity, characterized by an activation energy E_a = 0.45 eV. An estimated room temperature electron mobility _e of 2.8 × 10^{– 7} cm²/Vs leads to a corresponding electron concentration n of 5.5 × 10¹⁷ cm^{– 3}. In contrast to conventional MOS capacitors, we find an additional capacitive contribution under strong accumulation conditions as a result of space charge effects inside the CeO₂ thin film.     

PZT capacitor with Ir/IrO2/Ir electrode fabricated by RTA

Abstract

PZT capacitor with direct contact between Si substrate and bottom electrode of the capacitor was obtained with Ir/IrO₂/Ir/Ti electrode, by crystallizing sol-gel PZT thin film using RTA (650°CC 30 sec.). Contact resistance for hole diameter of 0.72 μm was 19 Ω. It was observed by cross-sectional TEM that Ti silicide was formed at the interface, but there was not oxygen diffusion from PZT thin film. Fatigue property of the PZT thin film was improved by RTA compared with furnace annealed film (600°CC 60 min.). The absolute value of the remnant polarization was 13 μC/cm² for both films, but it did not degrade until 10⁸ cycles of switching for the film by RTA, while it degraded before 10⁵ cycles for furnace annealed film.     

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.     

Effects of Ar post-annealing on the electrical properties of Pt/YMnO3/p-Si and Pt/YMnO3/Y2O3/p-Si

Abstract

YMnO₃ thin films were prepared on p-Si(111) and Y₂O₃/p-Si(111) substrates by chemical solution deposition and annealed at 800°C for 1 hour under the oxygen pressure of 2 Torr. The YMnO₃ thin films showed good crystallinity and c-axis preferred orientation. Effects of Ar post-annealing on electrical properties were examined in Pt/YMnO₃/p-Si and Pt/YMnO₃/Y₂O₃/p-Si structures. Leakage current densities decreased considerably by Ar post-annealing. The Pt/YMnO₃/p-Si and Pt/YMnO₃/Y₂O₃/p-Si showed clockwise C-V hysteresis induced by ferroelectric polarization after Ar post-annealing and memory windows of MFS and MFIS structure were 1.1V and 0.6V, respectively.     

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.     

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.     

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.     

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.     

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.     

Effects of Substrate and Annealing Temperatures on the Characteristics of SrBi4Ti4O15 Thin Films

In this study, radio frequency (RF) sputtering was used as the method and the layer-structured bismuth compound of SrBi₄Ti₄O₁₅ + 4 wt% Bi₂O₃ ferroelectric ceramic was used as the target to deposit the SrBi₄Ti₄O₁₅ (SBT) thin films. The addition of excess Bi₂O₃ content in the target ceramic was used to compensate the vaporization of Bi₂O₃ during the sintering and deposition processes. SBT ferroelectric thin films were deposited on Pt/Ti/SiO₂/Si under optimal RF magnetron sputtering parameters with different substrate temperatures for 2 h. After that the SBT thin films were post-heated using rapid temperature annealing (RTA) method. The dielectric and electrical characteristics of the SBT thin films were measured using metal-ferroelectric-metal (MFM) structure. From the physical and electrical measurements of X-ray diffraction pattern, scanning electronic microscope (SEM), I-V curve, and C-V curve, we had found that the substrate temperature and RTA-treated temperature had large influences on the morphology, the crystalline structure, the leakage current density, and the dielectric constant of the SBT thin films.     

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.     

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.     

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.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Electrical characteristics of high dielectric constant BCTZ thin films

Abstract

High dielectric constant Ba_0.96Ca_0.04Ti_0.84Zr_0.16O₃ (BCTZ) thin films were deposited on Pt/Ti/SiO₂/Si substrates by spin on metal-organic decomposition (MOD) technique. Undoped and 0.4% Mg-doped BCTZ thin films were annealed in the temperature range from 600 to 900 °C for 1 hour in oxygen environment. The crystal structure of BCTZ thin films was analyzed by X-ray diffraction. The electrical properties of BCTZ thin films were investigated by capacitance—voltage (C—V) characteristics. Also, the electrical properties of these films were compared in conjunction with 0.4% Mg doping effect of BCTZ thin films for possible high dielectric constant material applications.     

Ferroelectric properties of SrBi2Ta2O9 thin films on Si (100) with a LaZrO x buffer layer

To obtain a metal–ferroelectric–insulator–semiconductor (MFIS) structure, we fabricated ferroelectric SrBi₂Ta₂O₉ (SBT) film on a p-type Si (100) wafer with a LaZrO _x (LZO) buffer layer by means of a sol–gel technique. The sol–gel deposited LZO film according to the different annealing temperatures had a good surface morphology even though the crystalline phase was not an amorphous phase. In particular, the root-mean-squared (RMS) surface roughness of the 750-°C-annealed LZO film was about 0.365 nm and its leakage current density was about 8.2?×?10^?7 A/cm² at 10 V. A Au/SBT/LZO/Si structure with different SBT film was fabricated. The C–V characteristics of the Au/SBT/LZO/Si structure showed a clockwise hysteresis loop. The memory window width increased as the SBT film thickness increased. The 600-nm-thick SBT film was crystallized in a polycrystalline phase with a highly preferred (115) orientation. The memory window width of the 600-nm-thick SBT film was about 1.94 V at the bias sweep voltage ±9 V and the leakage current density was about 6.48?×?10^?8 A/cm² at 10 V.