GHZ polarization dynamics in ferroelectric thin films

Abstract

We present results from experiments which measure the local dielectric response of ferroelectric thin films driven by microwave-frequency electric fields. The repetition rate of a mode-locked Ti:Sapphire laser is used to generate a microwave drive signal that is phase-locked to an optical probe pulse and applied to the ferroelectric thin film. The induced polarization change in the ferroelectric film is measured stroboscopically via the electro-optic effect. Polarization images are acquired by scanning the laser beam across the sample in a confocal geometry. Time resolution is achieved by changing the delay between the electrical pump and the optical probe. Initial results show large local phase shifts in the ferroelectric response of closely separated regions of a Ba_0.5Sr_0.5TiO₃ thin film. This new experimental technique may help to understand the physical mechanisms of dielectric loss in these materials.     

Supression of size effects in ferroelectric films

Abstract

It is widely reported that the dielectric permittivity of ferroelectric films decreases with decreasing film thickness, and understanding and controlling these size effects are very important for charge storage application of these films. By combining phenomenological theory with careful experimental work, we have shown that the form of the boundary condition for the polarization plays a decisive role in the manifestation of size effects in ferroelectric films. We have taken two extreme boundary conditions to prove our point. For the case normal electrodes, it is assumed that the boundary condition for the component of polarization vector at the ferroelectric/electrode interface is P = 0. This case corresponds to the presence of a strong edge field, resulting in “freezing out” of the ferroelectric polarization at the interface and thus exhibiting severe size effects. However, if one utilizes conductive oxide electrodes that are ferroelectric in nature the polarization would not vanish at the ferroelectric/electrode interface and therefore the size effects are largely suppressed. To prove our point and to eliminate grain size, stress, and compositional effects, epitaxial SrTiO₃ thin films with stoichiometric composition on SrTiO₃ single crystal substrates were investigated. In fact, the experimental data also indicates that the use of ferroelectric electrodes indeed suppresses the size effects.     

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.     

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.     

Growth and microstructures of sputtered ferroelectric PbTiO3 thin films

Abstract

PbTiO₃ thin films, 5–200 nm in thickness, were epitaxially growth on miscut (001) SrTiO₃ substrates by planar magnetron sputtering for understanding of film growth mechanism and their ferroelectricity. The surface of the miscut substrates with miscut angle of 1.7 degree contains periodic step lines and terraces; the step height is 0.4 nm and terrace width is 14 nm. The surface structures of PbTiO₃ films comprised periodic striped patterns which was reflected in the initial surface of the substrate. It was found that under a stoichiometric film composition the film growth was governed by Frank-van der Merwe type and resultant epitaxial films showed extremely smooth surface. Deposition on a miscut substrate under a stoichiometric condition is essential to making the uniform ferroelectric thin films.     

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.     

Electrical characterizations of MgTiO3 thin films grown on Si

Abstract

We have analyzed MgTiO₃ thin films grown on the Si substrate with/without SiO₂ using pulsed laser deposition (PLD). We find that MgTiO₃ thin films start to crystallize at 600°C, causing electrical instabilities in the MIS capacitors above this temperature. Detailed analysis by XRD technique reveals that structural differences of MgTiO₃ thin films were not obvious below 600°C, whereas the electrical characteristics changes as a function of deposition temperature and the presence of thermally grown SiO₂. We observe that the decrease of deposition temperature results in the increase of leakage current and anomalous positive charge (APC) density. These drawbacks were effectively suppressed by growing 100A SiO₂ layer on the Si substrate prior to the deposition of MgTiO₃ thin films.     

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.     

Lead zirconate titanate thin films on ruthenium dioxide; in situ synthesis using organometallic chemical vapor deposition

Abstract

In this paper the organometallic chemical vapor deposition (OMCVD) of RuO₂ using the precursor ruthenocene, Ru(C₅H₅)₂, will be discussed. Stoichiometric RuO₂ thin films with a specific resistivity of about 50 μΩcm were obtained both on strontium titanate and platinized silicon wafers at temperatures between 300–700°C. PbZr_0.8Ti_0.2O₃ thin films were in situ deposited onto these RuO₂ electrodes. The ferroelectric behavior of the films obtained on the RuO₂ electrodes is compared with those obtained on platinum electrodes. Attempts to deposit in-situ a RuO₂ top electrode on the PbZr_0.8Ti_0.2O₃ were unsuccessful.     

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.     

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.     

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.     

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.     

Structure and properties of sol-gel processed (Pb,La)TiO3 ferroelectric thin films

Abstract

The influence of heat treatment and substrate materials on PLT thin films by sol-gel processing has been researched. Epitaxial growth PLT thin films with perovskite-type structure on sapphire, SrTiO₃ and MgO single crystal substrates have been prepared. The epitaxial relations are (100)PLT28/(100)SrTiO₃, (111)PLT28//(0001)sapphire and (100)PLT14//(100)MgO. The PLT polycrystal thin films with perovskite-type structure on Si single crystal and quartz glass substrates have been prepared. The remanent polarization Pr and the coercive field Ec of PLT15 ceramic thin films are 7.7 μc/cm² and 34 kv/cm at 4 KHz respectively. The optical transmittance of PLT28 ceramic thin films within the wavelength range of λ = 500–1000 nm is approximately 80%.     

BaMgF4 thin film development and processing for ferroelectric FETS

Abstract

A ferroelectric memory field-effect transistor (FEMFET) where a ferroelectric thin film is incorporated directly into the gate structure of the transistor is attractive, because it provides not only nonvolatility, but also nondestructive readout (NDRO). At Westinghouse, we are currently developing a FEMFET using thin film barium magnesium fluoride (BaMgF₄), a ferroelectric material that was discovered in 1969, but was not fabricated in thin film form until 1989. The BaMgF₄ films are grown by evaporation in an ultrahigh vacuum (UHV) chamber on clean Si(100). The natural tendency of these films to grow with the ferroelectric a-axis in the Si(100) plane has been overcome to obtain more random orientation with larger reversible polarization perpendicular to the film. A capping layer (SiO₂) has been found to be essential for process integrability of these BaMgF₄ films. Ti-W metallization produced only a slight reduction in the capacitance-voltage (C-V) memory window. Switching speed of these films has been measured to be 40 to 45 nanoseconds. The first FEMFET fabricated with BaMgF₄ has exhibited 18 Volt memory hysteresis window with better than 10⁵ on/off current ratio for 20 Volt programming.     

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.     

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.     

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.     

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.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.