Sol-gel processed ferroelectric and multiferroic thin films for integrated devices

Abstract

Ferroelectric barium titanate and multiferroelectric bismuth ferrite thin films have been fabricated by using sol-gel processing technique. The starting materials for fabrication of were barium 2-ethyl hexanoate and titanium (IV) isoproposxide. Bismuth nitrate and ferric nitrate were the precursors for the fabrication of thin films. The as-deposited films were annealed at higher temperature for crystallization. The X-ray diffraction study on the films showed that the as-grown films were found to be amorphous that crystalized to proper phases by annealing at 550?°C in air for one hour. All the samples showed high optical transparencies in the visible frequency range. The room temperature dielectric constant and loss tangent of barium titanate thin films at 1?kHz frequency were found to be 400 and 0.01 respectively. Both the dielectric constant and loss tangent showed small dispersion in the frequency range of 0.10–1000?kHz range. The ferroelectricity in barium titanate thin films was confirmed by the presence of bell shaped capacitance-voltage (C-V) butterfly loop and saturated polarization-field (P-E) hysteresis loop. The as-grown bismuth ferrite thin films were also found to be amorphous that crystallizes after annealing at 500?°C. These films also showed high optical transparencies in the visible region. The bismuth ferrite thin film samples showed saturated hysteresis loop and magnetic polarization-magnetic field hysteresis loop as well, confirming the multiferroic nature of the samples.     

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.     

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.     

Sputter deposition of ferroelectric thin films

Ferroelectric films are typically deposited by a variety of techniques, the two most common being chemical methods (sol-gel, metalorganic decomposition) and sputtering. In this paper we briefly review the sputtering techniques, and then discuss ion beam sputter deposition in greater detail. In particular, ion beam sputter deposition of epitaxial lead zirconate titanate (PZT) films is described. It is shown that the films with compositions close to the morphotropic boundary typically show well-developed ferroelectric hysteresis loops, Pmax around 45 μC/cm2, and Pr around 20 μC/cm2. In comparison with typical polycrystalline sol-gel PZT films, however, coercive fields of thin epitaxial films are large (120-200 kV/cm for 95 nm films). The pulsed fatigue behavior is remarkably similar to a polycrystalline non-oriented sol-gel PZT film investigated for comparison. The similarities suggest that the aging behavior may be dominated by the electrodes, which were Pt in both systems.     

Landau theory of thin ferroelectric films

Abstract

Landau-Devonshire theory¹ is a useful phenomenological model to describe the properties of ferroelectric phase transitions. Below the transition temperature, the Landau model can be generalized to describe the thermodynamic stability of a ferroelectric crystallite in a bistable polarized configuration, and to predict the response of the crystallite to external fields and charges. The three primary elements to be considered in modeling thin-film ferroelectric devices are the polar response of the ferroelectric itself, the contribution of electrode interfaces, and the interaction of mobile and immobile charged defects and carriers with the ferroelectric and the electrodes. First, the hysteresis properties of a single domain or crystallite are derived. This result is generalized to find the polar response in a polycrystalline film where there may be variations in the size and orientation of the crystallites and in the coercivity, remanence and offset of the domains. After postulating that metal electrodes form Schottky barriers with respect to the ferroelectric, we can then calculate the electric fields and potentials throughout the ferroelectric film. These calculations show that space charges form near the electrodes and the magnitude of the electric field in these regions is large. A further examination of the space charges results in a model for the C-V response of the ferroelectric capacitor, as the C-V response is dominated by space charge effects. The charge concentrations, contact potentials, high-field permittivity, and space charge widths can be extracted from the C-V data. Finally, the interactions between defects and domains leading to domain pinning and fatigue are investigated.     

Characterization of MOCVD Pt electrode for ferroelectric thin films

Abstract

Platinum thin films were deposited by low pressure chemical vapor deposition (LPMOCVD) on SiO₂/Si and (Ba, Sr)TiO₃/Pt/SiO₂/Si substrates using Pt-hexafluoroacetylacetonate at various deposition temperatures. The shiny mirror-like Pt thin films of a high electrical conductivity were obtained, when the deposition temperature is between 325°C and 350°C, whereas above 375°C Pt thin films showed rough surface as well as poor adhesion property to oxide substrate. Pt thin films had a good step coverage of 90%. The results indicate that LPMOCVD Pt thin films can be applied for the top electrode of high dielectric thin film, which is thought to be one of the best candidate materials for a capacitor of ULSI DRAM.     

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.     

Adaptive-learning neuron circuits using ferroelectric thin films

Abstract

Adaptive-learning neuron circuits are reviewed, in which a pulse frequency modulation (PFM) system is used and the interval of output pulses is changed through the learning process. Key devices of the circuits are MFSFETs (Metal Ferroelectric Semiconductor Field Effect Transistors). They are used for representing the synaptic weights of neurons and the polarity of the films is gradually changed by applying input pulses to the gates. In order to produce PFM signals, circuit using a UJT (unijunction transistor) is discussed. As a preliminary experiment for realization of MFSFETs, the electrical properties of metal ferroelectric metal (MFM) capacitor using sol-gel derived PZT films are discussed.     

Formation of ferroelectric thin films on ruthenium electrodes

Abstract

Sr_0.8Bi_2.4Ta₂O₉ (SBT) and Bi_3.25+xLa_0.75Ti₃O₁₂ (BLT) films were prepared on Ru electrodes by a sol-gel spin-coating method. It was found in the case of SBT/Ru that the oxidation of Ru was suppressed by annealing at temperatures lower than 650°C in O₂ atmosphere or by annealing lower than 700°C in N₂. However, the remanent polarization values of the films were as low as 2.3 μC/cm2 (2Pr) for the former case and 4.4 μC/cm2 for the latter case. On the other hand, the BLT/Ru samples crystallized at 650°C showed good crystallinity without oxidation of the Ru electrode. It was found that the ferroelectric properties depended on the amount of excess-Bi sensitively, and the film prepared under the optimum Bi composition showed an excellent P-V hysteresis loop with 2 Pr of 25 μC/cm2.     

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.     

Pulsed excimer laser deposition of ferroelectric thin films

Abstract

Pulsed UV excimer laser ablation was employed to deposit multi-axial, bi-axial and uni-axial ferroelectric compositions of PZT, bismuth titanate and lead germanate respectively. In general, a fluence lower than 2 J/cm² caused a preferential evaporation of volatile components, resulting in stoichiometric imbalance. However, the fluences beyond 2 J/cm² enabled the deposition of stoichiometric thin films of multi-component oxide systems. The intrinsic bombardment due to the energetic ablated species during the thin film deposition seemed to influence the composition, structure, orientation and the electrical properties. The electrical characterization of ferroelectric films indicated a dielectric constant of 800–1000, a P_r of 32μC/cm² and E_c of 130KV/cm for polycrystalline PZT films and the corresponding quantities were measured to be 150, 7 μC/cm² and 20 KV/cm for in-situ crystallized c-axis preferred oriented bismuth titanate films. Lead germanate thin films oriented along c-axis (003) showed a dielectric constant of 30, a P_r of 2.5 μC/cm² and E_c of 55 KV/cm.     

Dielectric and ferroelectric properties of BTFCO thin films

Journal of Electroceramics - Single phase Bi3.25La0.75Ti2.5Nb0.25Fe0.125Co0.125O12 (BTFCO) thin films were deposited on Pt/TiO2/SiO2/Si substrates by RF-magnetron sputtering. Ferroelectric domain...     

Sputtered ferroelectric thin films for dynamic random access memory applications

Abstract

A low thermal budget (with 550°C annealing) process with Ti-compensation for sputtered ferroelectric PZT thin films has been developed. PZT films with a composition near the morphotrophic phase boundary (Zr/Ti = 53/47) annealed at 550°C for 1 hr in a N₂ ambient exhibits high charge storage density and low leakage current density, which are the important requirements of dielectric materials for ULSI DRAM cells. It was also found that Ti compensated films show good fatigue endurance in comparison with non-Ti compensated films.     

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.     

Mocvd process model for deposition of complex oxide ferroelectric thin films

Abstract

Thin complex oxide films, such as ferroelectrics, pyroelectrics, waveguides, superconductors, MEMS/MOEMS and piezoelectrics are experiencing rapid growth in a wide variety of commercial markets. In particular, ferroelectrics as used in IC cards, embedded memories with micro-controllers, stand-alone memories, and other ASIC applications, require deposition by a technique that is compatible with deep sub-micron advanced geometry IC integration. Metal Organic Chemical Vapor Deposition (MOCVD) is the deposition method of choice for achieving conformal uniform (composition and thickness) contiguous pin hole free thin films over the challenging sub 0.2 micron geometry topology necessary for implementing advanced devices. MOCVD is free of the physical limitations that produce film defects associated with other liquid source and physical vapor deposition techniques. Of the different MOCVD approaches to complex oxide film deposition, we have found rotating disk reactor (RDR) MOCVD to be the most versatile and capable of producing uniform films efficiently. Using computational fluid dynamic methods, a process model for optimizing the multiple process parameters of RDR-MOCVD, single and multiple wafer production tools, has been developed. The models developed are compatible with plasma-assist, single or multiple precursor and graded composition deposition of films. The developed hardware and model have been combined to maximize thin oxide film properties. SMI modeled RDR MOCVD methodology and film results are presented.     

Enhanced ferroelectric properties of multilayer SBT-BTN thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉ – (Bi₄Ti₃)_1-xNb_xO₁₂ (SBT-BTN) multilayer thin films with various stacking periodicity have been synthesized on Ir/Ti/SiO₂/Si substrates by metal organic chemical vapor deposition technique (MOCVD). Tributylbismuth [Bi(C₄H₉)₃], strontium-bis[tantal(pentane-ethoxy)(2-methoxyethoxide)] [Sr[Ta(OEt)₅(OC₂H₄OMe)]₂], titanium bis(isopropoxy)bis(1-methoxy-2-methyl-2-propoxide) [Ti(OiPr)₂(mmp)₂] and niobium-ethoxide [Nb(OC₂H₅)₅] were selected as precursors. X-ray diffraction patterns show that the multilayer films annealed at 800°C consisted of a fully formed perovskite phase with polycrystalline structure. The remanent polarization (2·P_r) and coercive field strength (E_c) were 16.2 μC/cm² and 230 kV/cm, respectively, values which are much higher compared to pure SBT film (2·P_r = 6.4 μC/cm², E_c = 154 kV/cm).     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Dielectric response of ferroelectric thin films on non-metallic electrodes

The dielectric response of thin films of perovskite ferroelectrics fabricated on electrodes such as indium tin oxide is calculated as a function of frequency, film & barrier layer thickness, and dielectric constant using an equivalent circuit model based on properties of the bulk, the electrode and a series resistance. Using reasonable estimates of parameters it is shown that measurements of the dielectric constant and loss by conventional dielectric bridges can lead to results which vary in a complex fashion and which may bear little relation to the true dielectric properties of the film. In particular, observation of a Curie temperature in thin films can often be masked by circuit or electrode effects. Results are given in terms of direct frequency plots and as impedance spectra.     

Recent advances in the deposition of ferroelectric thin films

Abstract

Recent developments in ferroelectric thin film deposition involving plasma based approaches, are described, which include a) multi-magnetron sputter deposition, b) Multi-ion-beam reactive sputter (MIBERS) deposition, c) Pulsed excimer laser ablation and d) ECR (Electron cyclotron resonance) plasma assisted deposition. These methods commonly prevailed intrinsic low energy ion bombardment during the growth process, which may be used for the control over composition, crystallization temperature and microstructure. A low energy (60–75 eV) ion bombardment of the ferroelectric Pb(Zr, Ti)O₃ thin films indicated a reduction in the phase formation/crystallization temperature, improved the electrical properties, microstructure and the surface smoothness. Discussion is presented exphasizing the effects of low energy bombardment in different deposition processes. Recent findings using rapid thermal annealing process are also described.     

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.