Conducting oxide electrodes for ferroelectric films

Abstract

Suitability of oxide electronic conductors [e.g. ruthenium oxide (RuO_x) and indium-tin-oxide (ITO)] as contact metallization for ferroelectric films (e.g. PbZr_xTi_1?xO₃) was investigated using techniques such as Rutherford backscattering spectrometry, x-ray diffraction and electron spectroscopy for chemical analysis. Thin films of RuO_x and ITO were deposited on Si substrates by reactive sputtering. Either PbO or PZT (x = 0.53) films were deposited onto the conducting oxides and the specimens were annealed at various temperatures between 400°C and 700°C. Less intermixing was found in Si/RuO_x/ PZT films when compared to Si/ITO/PZT under similar processing conditions. The ferroelectric properties of PZT films on RuO_x electrodes are compared to those on Pt electrodes. The PZT films show improved fatigue properties on RuO_x electrodes.     

Electrodes for ferroelectric thin films

Abstract

Platinum and ruthenium oxide (RuO₂) deposited by ion beam sputter-deposition are evaluated for use as electrodes for PZT thin film capacitors. The effect of deposition temperature, film thickness, and the presence of oxygen on hillock formation in platinum is discussed. It is shown that the hillock density in Pt/Ti/SiO₂/Si films can be significantly reduced by properly controlling the processing conditions and film thickness. Stress measurements correlate with the experimental observation that depositing thinner platinum films (<800 Å) is an effective means of reducing hillock formation. The use of an intermediate deposition temperature 200–250°C also helps minimize hillock formation. Diffusion of the Ti adhesion layer into and/or through the platinum was significantly reduced by replacing the Ti with a TiO_x adhesion layer. RuO₂ electrodes are compared to Pt in terms of resistivity, surface morphology, microstructure and film orientation.     

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.     

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.     

Growth and electrical properties of (211) BaTiO3 thin films on Pt-coated Si(100) substrates

Abstract

Barium titanate (BaTiO₃) thin films with high (211) orientation have been prepared on Pt(111)/Si(100) substrates by R. F. magnetron sputtering at a substrate temperature between 550°C and 580°C in an Ar/O₂ atmosphere. The I-V curve of a thin film capacitor (Ag-BaTiO_3-Pt) has been measured and the C-V curves are obtained for frequencies between 100Hz and 1MHz. Neither the I-V curve nor the C-V curves are symmetrical and a very large change in the slope of all curves is found to occur at ～+0.5v.     

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.     

Strain tensor effects on SrTiO3 incipient ferroelectric phase transition

Structural distortion of ferroelectric thin films caused by film strain has a strong impact on the microwave dielectric properties. SrTiO₃ thin films epitaxially grown on (110) DyScO₃ substrates using molecular beam epitaxy (MBE) are extremely strained (i.e., ～1% in-plane tensional strain) from 3.905 Å of bulk SrTiO₃. The room temperature dielectric constant and its tuning of the films are observed to be 6000 and 75% with an electric field of 1 V/μm, respectively. The control of strain in SrTiO₃ provides a basis for room temperature tunable microwave applications by elevating its phase transition peak to room temperature. Also, a significant in-plane anisotropy in dielectric constant and tuning was observed in these SrTiO₃ films. The observed in-plane anisotropic dielectric properties have been interpreted based on the phenomenological thermodynamics of film strain.     

Theory of size effects in ferroelectric ceramic thin films on metal substrates

The aim of this paper is to show how a Landau thermodynamic theory might be utilized to study size effects in ferroelectric thin films on metal substrates via reflectivity measurements that could be carried out with terahertz radiation, particularly in the far-infrared region. The approach taken is to minimize a Landau free energy functional that includes a gradient term to describe the size effects. Landau-Khalatnikov equations together with Maxwell’s equations for the electromagnetic field are then solved simultaneously to describe how the radiation interacts with the film. From this reflectivity curves can be calculated and related to experimental studies. Attention is paid to how the metal substrate can influence the reflectivity curves compared to free standing films without substrates. The significance of the work lies in the fact that ferroelectric ceramic thin films are becoming of increasing technological importance, and films on metal substrates such as electrodes are of obvious relevance to applications such as memory devices which rely on applied electric fields to change the polarization direction. The main conclusion is that terahertz wave measurements in the far-infrared provide an informative and sensitive probe of the size effects and substrate influence.     

Improved ferroelectricity of strained SrTiO3 thin films on sapphire

Magnetron sputtered and laser deposited SrTiO₃ thin films are deposited on CeO₂ buffered sapphire substrates. Their structural properties are investigated and correlated to the dielectric properties of the SrTiO₃ films. It is shown, that the biaxial compressive strain imposed by the substrate on the ferroelectric films leads to a considerable increase of the permittivity and tunability of SrTiO₃ thin films in technically relevant temperature regimes. Generally, the permittivity and tunability decreases with increasing strain. However, the ferroelectric phase transition of the SrTiO₃ films is shifted to higher temperatures compared to that of single crystalline SrTiO₃. As a consequence, the permittivity of the films is larger than that of undistorted SrTiO₃ single crystals for small strain (Δa/a < 0.005) and temperatures above the Curie temperature. Furthermore, a linear dependence of the loss tangent and the tunability on the permittivity is observed, which indicates, that all three properties are affected by the same mechanism that itself is affected by the lattice strain.     

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.     

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.     

Short-time switching of polarization in thin ferroelectric films

Abstract

The peculiarities of repolarization in thin-film metal-PZT-metal structures with varioùs areas of electrodes have been investigated. The nonclassical mechanism of polarization switching was determined to take place at short durations of voltage pulses. The repolarization was shown to carry out according to the mechanism of formation and lateral widening of domains at long times.     

Dielectric properties of ferroelectric (Ba0.6Sr0.4)TiO3 thick films prepared by tape-casting

Thick BST films have been fabricated by a tape casting and firing method. Dielectric constants of BST films are changed from 5700 to 7000 at 1 MHz after focused beam annealing. Furthermore, surface morphologies and depth profile of chemistry have been altered after annealing. Especially, Sr atoms diffuse out to the surface, while Ba atoms diffuse into the center. The possibility of the surface alteration of the thick films have been clearly demonstrated in this study, which may applied for the integration of ferroelectrics and other dielectrics and/or conductors for low cost microwave tunable devices.     

Preparation of (PbxBa1-x)TiO3 thin films by MOCVD using an aerosol-assisted liquid delivery system

Abstract

Thin films of PbTiO₃, BaTiO₃ and (Pb_xBa_1-x)TiO₃ (PBT) have been prepared by metal-organic chemical vapor deposition using a horizontal reactor with an aerosol-assisted liquid delivery system. Structural and electrical properties have been investigated as a function of the lead content x. First results on PBT thin films grown on platinized silicon substrates show, for x < 0.8, an increasing tetragonal distortion of the lattice cell (c/a >1), and accompanying ferroelectric behavior which is similar to the bulk material. For smaller lead content (x < 0.8) no ferroelectric behavior is established and a small tetragonal distortion of opposite type (c/a <1) is observed. This distortion is attributed to a thermally induced tensile film stress and may be responsible for the suppression of the ferroelectric phase transition.     

Decay of remanent polarization in ferroelectric films using polarization-dependent photovoltages

Abstract

Following polarization reversal, the strength of photovoltaic currents from lead-based perovskite film capacitors shows a dependence on time. An initial photovoltaic current decays rapidly to an almost steady-state current, which then decays slowly. We use a nonswitching surface layer model to explain remanent-polarization-dependent photovoltaic outputs in terms of photocarrier-generated screening of an incompletely compensated depolarization field within the film bulk. The rapid decrease in the initial photovoltaic current (photovoltaic transient) is explained as resulting from a change in the potential distribution within the film. The initial distribution results when charges compensating polarization are confined to the electrodes; the final distribution results when compensating charges occupy defect states within the volume of the surface layers. The slow decay in the steady photovoltaic current is explained as the result of changes in the potential distribution resulting from a slow decay in the remanent polarization. The log time rate of decay of the photovoltaic current is then equal to that of the remanent polarization, its determination serves as a measure of the log time decay rate of remanent polarization.     

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.     

UHV processing of ferroelectric barium magnesium fluoride films and devices

Barium magnesium fluoride (BaMgF4) has recently emerged as a strong candidate for application as the gate dielectric in ferroelectric random access memory (FERRAM) devices with nondestructive readout (NDRO). In earlier papers we reported the successful growth of oriented BaMgF4 films on Si(100) and other substrates in a ultrahigh vacuum (UHV) system, as well as the results of the structural and electrical characterization of these ferroelectric films. In the present paper, we review some of the earlier results, and also examine the effect of variations in the growth temperature and various post-growth anneals on the stoichiometry, crystallinity, orientation, and electrical characteristics of the BaMgF4 films. Initial attempts at integrating the ferroelectric field-effect transistor (FEMFET) with the standard CMOS VLSIC processing, as well as the effect of adding a thin capping layer of SiO2 on the BaMgF4 will also be described.     

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).     

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.