Growth and characterization of non-c-axis-oriented SrBi2Ta2O9 epitaxial thin films on Si(100) substrates with SrRuO3 bottom electrodes

Abstract

We have successfully grown non-c-axis-oriented epitaxial ferroelectric SrBi₂Ta₂O₉ (SBT) films with (116) and (103) orientations on Si(100) substrates using epitaxial (110)- and (111)-oriented SrRuO₃ (SRO) bottom electrodes, respectively. The SRO orientations have been induced by coating the Si(100) substrates with epitaxial YSZ(100) and MgO(111)/ YSZ(100) buffer layers, respectively. All films were sequentially grown by pulsed laser deposition. Specific in-plane orientations of the epitaxial SBT films were found, which are in turn determined by specific in-plane orientations of the epitaxial SRO bottom electrodes. These include a diagonal rectangle-on-cube epitaxy of SRO(110) on YSZ(100) and a triangle-on-triangle epitaxy of SRO(111) on MgO(111).     

STRESS CONTROLLED FERROELECTRIC (BA0.5Sr0.5)TiO3 THIN FILMS PREPARED ON GD2O3/SRTiO3(001) BY A PULSED LASER DEPOSITION

ABSTRACT

Stress controlled epitaxial ferroelectric Ba_0.5Sr_0.5TiO₃ (BST) films have been deposited on Gd₂O₃/SrTiO₃ by pulsed laser deposition with oxygen background pressure of 200 mTorr at the deposition temperature of 750°C. In order to control the stress in BST films, oxygen pressures for Gd₂O₃ buffer layers have been varied from 0.1 to 100 mTorr, while that of BST films have been fixed at 200 mTorr. It has been found that the lattice parameters of the BST films deposited on Gd₂O₃ were changed. Furthermore, microwave properties of co-planar waveguide (CPW) fabricated on BST films were investigated by a HP 8510C vector network analyzer from 1–20 GHz. Large dielectric tunabilities were observed from the CPW's fabricated on BST films deposited on Gd₂O₃ layers deposited at low and high oxygen pressures, 0.1 and 100 mTorr, respectively.     

Properties of PbZrxTi1−xO3/CeO2/SiO2/Si structure

Abstract

We report the crystalline quality and electrical properties of PbZr_xTi_1?xO₃ (PZT) films on n-type Si(100) substrates with CeO₂/SiO₂ dual buffer layers. PZT films and CeO₂ buffer layers were prepared by pulsed laser deposition technique, and SiO₂ buffer layers were formed by thermal dry oxidation. It was found that CeO₂/SiO₂ dual buffer layers effectively prevented Si and Pb interdiffusion between PZT and Si substrates. Furthermore, the capacitance-voltage (C-V) characteristics of the PZT/CeO₂/SiO₂/Si heterostructures demonstrated ferroelectric switching properties, showing a memory window as large as 2.7 V at 1 MHz.     

Pulsed laser deposition (PLD) of oriented bismuth titanate films for integrated electronic applications

Abstract

In this paper we describe recent successes of growth of epitaxial bismuth titanate (BTO) films by pulsed laser deposition (PLD) suitable for electro-optic and electrical switching device structures, and fabrication of an improved gate structure for a ferroelectric memory FET (FEMFET). TEM and x-ray results indicate that excellent crystalline quality BTO films were achieved on LaAlO₃. Polarization switching was demonstrated for BTO capacitors with epitaxial superconducting YBa₂Cu₃O₇ as the lower electrode. Using an SiO₂ buffer layer, a BTO/Si structure was fabricated and direct charge modulation in the Si by polarization reversal in the BTO was demonstrated.     

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.     

Microstructural Properties of Ba0.6Sr0.4TiO3/RuO2 Multi-Layers Grown on MgO and YSZ by Pulsed-Laser Deposition

The microstructure of Ba_0.6Sr_0.4TiO₃ (BST)/RuO₂ multi-layers grown on (100) MgO and (100) YSZ substrates, respectively, by pulsed-laser deposition (PLD) has been studied by transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). The RuO₂ films deposited at 700°C adopt epitaxial relationships with both substrates. The epitaxial films on (100) MgO consist of two variants with an orientation relationship given by (110) RuO₂//(100) MgO and [001] RuO₂//[011] MgO. The epitaxial films on (100) YSZ contain four variants with an orientation relationship given by (200) RuO₂//(100) YSZ and [011] RuO₂//[001] YSZ. The BST films deposited on the RuO₂ electrode are epitaxial on the (200) RuO₂ films deposited on YSZ, and non-epitaxial on the (110) RuO₂ films deposited on MgO. The epitaxial relationship between the BST and (200) RuO₂ films can be described as (111) BST//(200) RuO₂ and [1&1macr;0] BST//[011] RuO₂. The BST films contain at least four variants. The growth and microstructural properties of the multi-layer structures can be understood based on geometrical consideration of the crystal structures.     

Recent progress in sputtering PZT thin films for ferroelectric memories

Abstract

This paper describes amorphous Pb(Zr, Ti)O₃ (PZT) thin films deposited by cosputtering Pb(Zr_0.5 Ti_0.5)O₃ and PbO targets. By optimizing the amount of the excess Pb and the deposition temperature, PZT thin films with a single perovskite phase were obtained successfully on Ir substrates and Pt substrates at 520°C. 250-nm-thick PZT films crystallized by rapid thermal annealing (RTA) at 600°C for 20 s exhibited excellent ferroelectric properties: a coercive voltage of 1.0 V, a remanent polarization density of about 40 μC/cm², and a polarization switching endurance over 1x109 cycles. Although a heat treatment in a reductive ambient causes degradation of ferroelectric properties of PZT thin films, their degraded ferroelectric properties can be easily recovered from by a 1-min RTA in an oxygen at 400°C.     

Ferroelectric La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O heterostructures on silicon

Abstract

Ferroelectric Pb_0.9La_0.1Zr_0.2Ti_0.8O₃ (PLZT) thin film capacitors with symmetrical La-Sr-Co-O top and bottom electrodes have been grown on [001] Si with a Yttria stabilized zirconia (YSZ) buffer layer and on SiO₂Si substrates. A layered perovskite “template” layer (300–500 Å thick), grown between the YSZ buffer layer or the SiO₂ layer and the bottom La-Sr-Co-O electrode, is critical for obtaining the required orientation of the subsequent layers. The fatigue, retention and aging characteristics of these new structures are quite desirable for nonvolatile memory operation. Preliminary studies show that this ferroelectric performance obtained in large (50–100 μm diameter) capacitors can be replicated in smaller capacitors (down to 4 μm diameter) processed by ion milling.     

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.     

Growth of MgTiO3 thin films by pulsed laser deposition and their electrical properties

Abstract

MgTiO₃ thin films have been grown on various substrates by pulsed laser deposition (PLD) to investigate the application for microwave dielectrics and optical devices. Highly oriented MgTiO₃ thin films were obtained on sapphire (c-plane Al₂O₃). MgTiO₃ thin films deposited on SiO₂/Si and platinized silicon (Pt/Ti/SiO₂/Si) substrates were polycrystalline nature. MgTiO₃thin films grown on sapphire were transparent in the visible and had a sharp absorption edge at 280 nm. These MgTiO₃ thin films had extremely fine feature of surface morphology, i.e., rms roughness of 0.87 nm. Dielectric constant and loss of MgTiO₃ thin films deposited by PLD were about 24 and 1.5% at 1MHz, respectively. These MgTiO₃ thin films also exhibited little dielectric dispersion.     

The Effect of Stress on the Microwave Dielectric Properties of Ba0.5Sr0.5TiO3 Thin Films

Single phase, (1 0 0) epitaxial Ba_0.5Sr_0.5TiO₃ (BST) films have been deposited onto (1 0 0) LaAlO₃ and MgO substrates by pulsed laser deposition (PLD). The capacitance and dielectric losses of as-deposited and annealed films have been measured from 1–20 GHz as a function of electric field (0–80 kV/cm) at room temperature. The dielectric properties are strongly affected by the substrate type, post-deposition annealing time (6 h) and temperature (1200°C). For epitaxial BST films deposited onto MgO, it is observed that, after a post-deposition anneal the dielectric constant and the dielectric loss decreases. For epitaxial BST films deposited onto LAO, a post-deposition anneal (1000°C) results in an increase in the dielectric constant and an increase in the dielectric loss. The dc electric field induced change in the dielectric constant tends to increase with the dielectric constant and is largest for as-deposited films on MgO and post-deposited annealed films on LAO. In general, for epitaxial BST films, a large electric field effect is observed in films that have a large dielectric loss and a small electric field effect in films that have a low dielectric loss. High resolution X-ray diffraction measurements indicate that deposited film exhibit a significant tetragonal distortion which is strongly affected by a by a post deposition anneal. The observed differences in dielectric properties of the epitaxial BST films on MgO and LAO are attributed to the differences in film stress which arise as a consequence of the lattice mismatch between the film and the substrate and the differences in the thermal coefficient of expansion between the film and the substrate. A thin amorphous buffer layer of BST has been used to relieve stress induced by the lattice mismatch between the film and the substrate. Unlike epitaxial films, stress relieved films do not show an inverse relationship between dielectric tuning and Q (1/tan) and may be superior materials for tunable microwave devices.     

Epitaxial structure SrBi2Ta2O9<116> /SrTiO3<011> /Ce0.12Zr0.88O2<001> /Si<001> for ferroelectric-gate FET memory

Abstract

Epitaxial thin film growth of SrBi₂Ta₂O₉/SrTiO₃/Ce_0.12Zr_0.88O₂ on Si was studied, and this epitaxial layer structure was applied to fabrication of ferroelectric-gate field effect transistors (FETs). The films were prepared by a pulsed laser deposition technique and epitaxial growth was identified by x-ray diffraction. The devices exhibited excellent electrical performances: Capacitance-voltage characteristic of a metal-ferroelectric-insulator-semiconductor (MFIS) diode showed a retention longer than 10 days and I_d-V_g characteristic of an MFIS-FET showed 1 day retention. It is proved that the crystalline quality of ferroelectric thin films is of great importance to develop integrated devices with high performance.     

Effects of oxidants on the deposition and dielectric properties of the SrTiO3 thin films prepared by liquid source metal-organic chemical vapor deposition (MOCVD)

Abstract

SrTiO₃ thin films are deposited by a liquid source metal-organic chemical vapor deposition (MOCVD). The effects of oxidants on the deposition characteristics and dielectric properties of the films are mainly tested. O₂, N₂O and O₂ + N₂O gases are used as the oxidants and the films with Ti-rich and Sr-rich compositions are obtained when O₂ and N₂O is used, respectively. Deposition of thin initial layer under O₂ atmosphere is very effective to obtain large dielectric constant of the SrTiO₃ thin film when the main layer is deposited under O₂ + N₂O atmosphere. The dielectric constants of 40 nm thick SrTiO₃ films with thin O₂, N₂O initial layers and without the initial layers are 235, 145 and 210, respectively.     

Fabrication and structural characterization of interdigitated thin film La1 − x Sr x CoO 3 (LSCO) electrodes

For the prospective use as micro-Solid Oxide Fuel Cell (μ-SOFC) cathodes and for the investigation of reaction kinetics, La_{1 − x}Sr_xCoO₃ (LSCO) mixed ionic electronic conducting thin films were deposited by DC and RF sputtering onto a number of different substrate materials and characterized. Standard photolithographic and wet chemical etching methods were utilized to microstructure the LSCO films and XRD, SEM, AFM, WDS, and RBS were used to characterize their structure, topography, and chemistry. Sputtering resulted in very homogeneous and smooth thin crystalline films with Sr deficiency and submicron sized grains. Hydrochloric acid was found to readily etch LSCO with the etching quality strongly dependent on substrate material. LSCO films were most easily etched when deposited directly on silicon substrates, etched at intermediate rates when deposited on Gd:CeO₂ films, and most resistant to etching after deposition onto single crystal yttria stabilized zirconia (YSZ) substrates. Imperfect etching was attributed to interface formation and the presence of impurities.     

Rapid Thermal Annealing of Oxide Electrodes for Nonvolatile Ferroelectric Memory Structures

We report on the properties of a ferroelectric stack comprising (La_0.5Sr_0.5)CoO₃ (LSCO)/Pb(Nb,Zr,Ti)O₃ (PNZT)/LSCO deposited on 4 inch diameter platinized Si wafers (Pt/Ti/SiO₂/Si). The LSCO electrodes were deposited at room temperature by pulsed laser ablation and the ferroelectric layer was deposited by the sol-gel technique. Rutherford backscattering was performed to confirm the uniformity in composition, thickness and stoichiometry of LSCO across the wafers. Conventional furnace or rapid thermal annealing was performed to crystallize the electrodes. The oxidation resistance of the conducting barrier layers, Pt/Ti, was found to be dependent on the annealing procedure adopted for the bottom electrode. In the case where the bottom LSCO was crystallized by rapid thermal annealing, Rutherford backscattering analysis and transmission electron microscopy studies revealed that there was no oxidation of the Pt/Ti conducting barrier composite. This is in contrast to the observations for in-situ deposition or conventional furnace annealing of the bottom electrode. The resistivity, coercive field and polarization of the ferroelectric stack were uniform across the 4-inch wafers. The ferroelectric capacitors showed no fatigue up to 10¹¹ cycles and no imprint at 100°C. The ferroelectric properties were independent of the annealing procedure used for crystallizing the electrodes.     

Reactive Ion Etching and Ion Beam Etching for Ferroelectric Memories

The fabrication of the FeRAM requires the development of etching processes for ferroelectric thin films and electrodes as well as deposition processes. But different etching methods have different impacts such as resolution and process-induced damages. In this paper, reactive ion etching (RIE) and ion beam etching (IBE) for ferroelectric thin films and Pt electrodes have been studied in details. Different silicon-based ferroelectric thin films and their corresponding electrodes have been etched successfully. To compensate the possible oxygen loss caused by the etching process, the samples should be annealed in O₂ at 550°C for 30 min after RIE and IBE etching.     

Preparation and characterization of copper based cermet anodes for use in solid oxide fuel cells at intermediate temperatures

Two Cu-based anode cermets suitable for direct hydrocarbon oxidation in Solid Oxide Fuel Cells (SOFC) based on yttria stabilized zirconia (YSZ) electrolyte were tested in the temperature range (500–800°C). The ceramic components were CeO₂ and the perovskite La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−d (LSCM). The cermets were made in both the form of pellets and films applied onto the YSZ electrolytes. Pellets exhibited good mechanical strength and resistance to fracture in both oxidized and reduced state. Cu–LSCM cermets exhibited good redox cycling behavior between 700–800°C. Reduction temperature plays a significant role on final morphology with Cu segregation occurring at 800°C. Cu–LSCM films were found to exhibit lower polarization resistances than Cu–CeO₂ under 5% H₂. Examination of the data revealed a poorer contact of the Cu–CeO₂ electrode with the YSZ surface than the Cu–LSCM electrode. Reduction temperature should be less than 750°C to ensure suitable microstructure and adhesion of both film electrodes with the electrolyte.     

Studies on piezo coefficients of PLD and sol-gel grown PZT thin film for devices

Abstract

The effect of electrical (DC) contact poling processes on the ferroelectric and piezoelectric properties of sol–gel and pulsed laser-deposited PZT thin films has been investigated as a function of the poling field, temperature and time. The remnant polarization and piezoelectric coefficient are found to increase with and saturate at dc-poling field of 100- 300?kV/cm, temperature of 100–120?°C and poling time of 10–20?min. as compared with un-poled PZT thin films. The P-E hysteresis loops of poled PLD grown PZT films shows sharper switching behaviour as compared to imbalanced loop in sol-gel grown films. An improvement of piezoelectric and ferroelectric properties of sol–gel PZT thin films is found, as compared to those deposited using pulsed laser deposition (PLD), indicating that a poling process is required for sol–gel PZT thin films.     

Effect of excess-PB and prenucleation layer on properties of Pb(ZryTi1-y)O3 thin films prepared by mod process

Abstract

A modified metal-organic decomposition process, MOD has been successfully utilized to improve the ferroelectric properties of Pb(Zr_0.52Ti_0.48)O₃, PZT, thin films. Multilayer PZT/Pt(Si) films, which contain 0.12 μm layer of spin coated PbO-excess (10 mol%) precursors on top of 0.12 μm layer of stoichiometric PZT precursors, exhibit superior ferroelectric properties (P_r=14.2 μC/cm²; E_c=62 kV/cm) to the single layer PZT/Pt(Si) films of the same thickness (0.24 μm), which are either stoichiometric or 10 mol% Pb-enriched. The ferroelectric properties are further improved when the PZT films were synthesized using a thin pulsed laser deposited (PLD) prenucleation layer (0.06 μm). The subsequently MOD-prepared PZT films posses high remanent polarization (P_r=23.2–26.6 μC/cm²) and low coercive field (E_c=62.9–69.0 kV/cm).     

Effect of seed layer on electrical properties of Pb(Zr,Ti)O3 films grown by metalorganic chemical vapor deposition

Abstract

Pb(Zr_xTi_1?x)O₃ (PZT) ferroelectric thin films were prepared by metalorganic chemical vapor deposition (MOCVD) on Pt/Ti/SiO₂/Si substrate. Very thin PZT films, which were deposited at a lower temperature and post-annealed at higher temperature for crystallization, were used as a seed layer. PZT films grown on the seed layer exhibited superior characteristics in the crystalline structure and electrical properties, compared to those deposited without seed layer. Depending on the deposition conditions of PZT seed layer, a wide variation of surface morphology and stoichiometry was found between samples, whereas chemical composition was found to be very similar.