A Mathematical Model for the Fatigue Behavior of Ferroelectric Thin Films for Memory Applications

The process improvement of PLZT thin film capacitors for FRAM applications enabled a fatigue free endurance performance up to 3 × 10¹¹ cycles. Evaluating the fatigue behavior of the improved PZT capacitor stack in short time becomes difficult. In order to be able to predict the fatigue behavior beyond the practical testing limit, a precise analytical expression of fatigue behavior is needed. This paper presents a mathematical expression that can precisely describe the fatigue behavior of PLZT thin films. The model consists of a distribution of the critical fatigue cycles due to various fatigue mechanisms and a linear term as a function of log (fatigue cycle) to describe the switch charge wake-up or linear switch charge degradation. Using this model together with high field acceleration test, fatigue performance of ferroelectric thin film capacitors under low field can be predicted.     

Process dependent electrical characteristics and equivalent circuit model of sol-gel based PZT capacitors

Abstract

Studies of electrical properties and an equivalent circuit model is developed for ferroelectric PZT(Ti = 60%) thin film capacitors made by sol-gel spin coating with Pt electrodes. The equivalent circuit consists of two major parts: serial space charge capacitors demonstrating surface effects and parallel elements modeling the inner polycrystalline ferroelectric regions. This model is based on device physics which can demonstrate both the measured capacitance voltage characteristics and hysteresis curves. From the model fit to the data, an estimate of the space charge concentration at the surface and inner grain boundary region of 57times;10²⁰ cm^?3 and 1×10¹⁸ cm^?3 respectively is made. Further electrical characterizations such as pulse switching and polarization degradation (fatigue) have also been studied. Using the equivalent circuit, other characteristics such as the switching time can be studied showing its dependence on applied voltage and capacitor area. The applied voltage dependence of fatigue is shown via an empirical equation where the degradation rate is electric field activated.     

Fatigue properties of Sb doped PZT thin films deposited by dc reactive sputtering

Abstract

Sb doped reactive sputtering-derived Pb(Zr, Ti)O₃ (Zr/Ti=48/52) thin films were investigated with the intention of improving ferroelectric properties. Also, the atomic valence of Sb in PZT thin film was confirmed as trivalent cation (Sb³⁺) by x-ray photoelectron spectroscopy (XPS). According to the tolerance factor t, Sb³⁺ tends to occupy the B-site of ABO₃ perovskite structure and acts as an acceptor that generates oxygen vacancies and holes. Transmission Electron Microscope(TEM) was used to observe the structural changes of PZT thin films by Sb addition. The leakage current densities and P_r of PZT thin films increased as the Sb contents increased. 0.7at% Sb doped PZT(PZST07) thin films exhibited improved fatigue properties (about 10% degradation of the remanent polarization after 10¹⁰ switching cycles).     

Characteristics of PZT films with SRO/Pt stack electrodes for high density mbit feram devices

Abstract

Reliable PZT capacitors have been developed by using stable PZT sputtering technique and Pt/thinSRO(SrRuO₃) stack electrodes. Introduction of SRO electrodes with no leakage current degradation is a key to realize reliable and scalable PZT capacitors. Roles of top electrode (TE) SRO and bottom electrode (BE) SRO were investigated respectively from reliability and process damage points of view. The SRO works as hydrogen resistant electrodes, fatigue free interfaces and nucleation sites for perovskite formation. Relationship between SRO crystallinity and PZT electrical properties was elucidated. Templates made of thin SRO were found to function as barrier layers against diffusion of Pb and Ru from BE resulting in new possible cell structures.     

Etching effects on ferroelectric capacitors with multilayered electrodes

Abstract

Dry etching of PZT thin film capacitors with RuOx/Pt multilayered electrodes was studied to examine the etching effects. PZT films were deposited on RuOx/Pt/Ti/SiO₂/ Si substrates by sol-gel process and Pt films were prepared by DC magnetron sputtering. PZT and Pt thin films were etched with Cl₂/C₂F₆/Ar gas combination in an Inductively Coupled Plasma (ICP) by varying the etching parameters such as coil RF power, DC bias to wafer susceptor, and gas pressure.

Etching effects were investigated in terms of etch rate, etch selectivity, etch profiles, and electrical properties of etched capacitors. Quantitative analysis of the etching damage was obtained by calculating the shift of the coercive field and the switchable polarization in hysteresis loops. Finally, the etching damage mechanism was discussed and the optimization of etching processes for the fabrication of PZT capacitors was attempted to minimize the etching damage to ferroelectric capacitors.     

Fatigue and dielectric properties of undoped and Ce doped PZT thin films

Abstract

Ce doping improves the ferroelectric properties of sol-gel derived PZT thin films by facilitating easier domain wall movement. It also decreases the leakage current densities by reducing the concentration of free carriers through a decrease in concentration of Pb and O vacancies. Ce-PZT films retain good dielectric dispersion characteristics since the concentration of defects and defect dipoles are reduced. Ce doping dramatically improves the fatigue resistance of PZT thin films. We have studied the frequency dependence of fatigue behavior and shown that the loss of polarization due to fatigue follows a universal scaling behavior with N/f², where N is the number of the switching cycles and f is the frequency. The origin of the scaling is attributed to the drift of oxygen vacancies, which is the rate limiting process in the growth of the interface layer responsible for fatigue. Empirical fits for both undoped and cerium doped samples show that switchable polarization follows a stretched exponential decay with time or N/f. Cerium doping is believed to improve fatigue resistance by impeding the motion of oxygen vacancies.     

Electrical properties of Pb(Zr0.53Ti0.47)O3 thin film capacitors with modified RuO2 bottom electrodes

Abstract

Growth of Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films on RuO₂ electrodes by the sol-gel process is usually accompanied by the formation of second phases. The resulting RuO₂/PZT/RuO₂ capacitors are fatigue-free up to nearly 10¹¹ switching cycles, but they have high leakage currents (J～10^?3 A/cm² at 1 volt) and large property variation. We have developed several modifications of the RuO₂ bottom electrode which enhance nucleation of the perovskite phase, eliminate or reduce the second phases, and control film orientation and properties. The PZT films deposited on the modified RuO₂ electrodes have leakage current densities which are two to four orders of magnitude lower than those of PZT films deposited on the unmodified RuO₂ electrodes. In most cases, the excellent resistance to polarization fatigue which is characteristic of the RuO₂/PZT/RuO₂ capacitors, is maintained.     

Fatigue and retention of Pb(Zr0.53Ti0.47)O3 thin film capacitors with Pt and RuO2 electrodes

Abstract

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were deposited on Pt and RuO₂ coated Si and MgO substrates using the sol-gel process. Fatigue and retention tests were performed on these samples. The films grown on RuO₂ electrodes are fatigue-free up to nearly 10¹¹ cycles. Their retention life-time extrapolates to more than 10¹⁰ seconds. The fatigue behavior of films grown on Pt electrodes depends on the PZT film orientation. Highly oriented (001) PZT films maintain 50% of their initial P?r-P?r value after 10¹¹ cycles. The randomly oriented films maintain less than 3% of the initial P?r-P?r value after 10¹¹ cycles. However, the retention life-time of both highly oriented and randomly oriented PZT films grown on Pt electrodes extrapolates to higher than 10¹¹ seconds. It appears that fatigue of films grown on RuO₂ is mainly controlled by the film/electrode interface. On the other hand, fatigue of films grown on Pt appears to depend on both the film/electrode interface as well as on bulk effects.     

Flat-band voltage and breakdown in single-grained ferroelectric thin film capacitors

Abstract

Single-grained ferroelectric Pb(Zr, Ti)O₃(PZT) thin films, with thickness varying from 0.1 to 0.7μm, were prepared on Pt-coated silicon substrates by pulsed laser deposition combined with rapid thermal annealing method. The current-voltage characteristics of the Pt/PZT/Pt capacitors, with various thickness of PZT, were measured. Two important turning points in J-V curves, namely flat-band voltage and breakdoiwn voltage according to the totaly minority-carrier injection model, were discussed. The electrical strength of the film was also studied by applying the square test pulses with different pulser duration.     

Preparation and properties of sol-gel derived PZT thin films for decoupling capacitor applications

Abstract

The use of ceramic thin films as decoupling capacitors offers the possibility of capacitor integration within the integrated circuit (IC) package, and potentially, directly onto the IC itself. Since these configurations minimize series inductance, higher operational speeds are possible. In the present study we have investigated the dielectric and leakage characteristics of sol-gel PZT films. For compositions near the morphotropic phase boundary, dielectric constants of 1000, and loss tangents of about 0.02, were observed. The current-voltage behavior of the capacitors was characterized by a non-linear response, and significant asymmetry in both the leakage and breakdown characteristics as a function of bias sign was observed. Breakdown fields for PZT 53/47 thin films were typically ～800 kV/cm at 25°C. We have also studied the effects of La and Nb dopant additions and alternate firing strategies on film leakage characteristics. Donor doping at 2–5 mol% lowered leakage currents by a factor of 10³ For films prepared by a multilayering approach, firing each layer to crystallization resulted in leakage currents that were a factor of 10² lower than films prepared by the standard process.     

Fabrication and characteristics of piezoelectric PZT cantilever for high speed atomic force microscopy

Abstract

A PZT actuator integrated onto cantilever structure was fabricated for high speed atomic force microscopy (AFM). Five different electrodes were used to investigate the effect of top electrodes on the adhesion and the electrical properties in the PZT capacitors. The PZT capacitors with RuO₂ top electrodes exhibited the best characteristics of five electrodes. The tip deflection and the resonant frequency of the PZT actuator were 11 μim at 10 V and 79 kHz, respectively. The PZT actuator provided much better AFM image quality and imaging speed than those done by using the conventional bulk PZT tube scanner. The creep distortion in the AFM image was greatly improved by using the high speed PZT film actuator.     

The effects of PECVD silicon dioxide passivation on the electrical characteristics of Sol-Gel deposited PZT film capacitors

Abstract

Plasma-enhanced chemical vapor deposition (PECVD) of doped and undoped silicon dioxide layers is widely used throughout the semiconductor industry for the passivation of processed devices before the final metallization processing steps. However, a reduction in the remanent polarization of PZT platinum-electrode capacitors has been observed when the capacitors were passivated with PECVD silicon dioxide films. This paper presents the results of a study to determine the effects of a standard PECVD silicon dioxide process on the retained polarization of Sol-Gel derived PZT capacitors with platinum electrodes. The retained polarization of the capacitors was measured before and after the silicon dioxide depositions. Measurements indicate that for PZT capacitors with temperature-stabilized top electrodes, there is relatively little change in the retained polarization after the depositions. However, for the PZT capacitors without the temperature-stabilized top electrodes, reductions in excess of 70% in the retained polarization can occur.     

Improvement of the electrical properties of PZT thin films using TiO2 buffer layer

Abstract

Thin TiO₂ layers were sputter-deposited on Pt/Ti/SiO₂/Si wafers, as buffer layers for PZT thin film capacitors. It was found that TiO2 buffers of less than 4-nm-thickness could assist in obtaining highly uniform PZT thin films with no second phase. The leakage current behaviors of the PZT based capacitor are improved, while retaining the ferroelectric properties of PZT thin films such as remanent polarization and coercive field. In addition, the uniform distribution of oxygen in PZT on TiO₂/Pt indicates that the TiO₂ buffer layer act as a barrier for lead-platinum reaction, as well as for oxygen diffusion.     

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.     

Process integration of pzt thin films with oxide electrodes for high density nonvolatile memories

Abstract

Over the past five years extensive research and development efforts have conclusively proven that perovskite metallic oxide (e.g., La-Sr-Co-O) contacts to PZT thin films yields excellent ferroelectric properties and reliability including fatigue and imprint free capacitors. Currently, our effort is focused on process integration approaches to grow the LSCO/PNZT/LSCO capacitors on top of a poly-Si plug with conducting barrier layers, lowering the operating voltage from 5V to 2.5V and understanding the microscopic details of imprint and fatigue phenomena in ferroelectric capacitors. In collaboration with researchers at Sandia National Laboratories, Radiant Technologies, Virginia Tech. and Raytheon, a robust high density Ferroelectric RAM process is being developed. These research efforts have provided us with a comprehensive understanding of the origins of imprint and fatigue within the framework of a novel process that yields robust capacitors with switched polarization values in the range of 15–25 μC/cm² (for an operating voltage of 3–5V). In this presentation we will present an overview of our progress in these areas.     

Ferroelectric switching and fatigue behavior for PZT/YBCO thin film heterostructures

Abstract

The dielectric and ferroelectric properties for Au/Pb(Zr,Ti)O₃/YBa₂Cu₃O_7?x heterostructures at low temperatures are reported. The fatigue behavior and the ferroelectric switching effect for the structures are also investigated. The PZT/YBCO thin film heterostructures were deposited on MgO(100) substrates by laser ablation. The ferroelectric and dielectric properties and optical response of the oriented PZT films with different thicknesses have been studied over the temperature range from 20 K to 300 K. The dielectric loss of the structure was found to decrease by an order of magnitude when the YBCO bottom electrode became superconducting. A very low fatigue rate of the structure has also been obtained below T _c of YBCO layer.     

Effects of Ti/Ir top electrodes of PZT capacitors on the hydrogen related degradation

Abstract

Hydrogen annealing damages on properties of PZT capacitors and a role of Ti/Ir hybrid structure top electrodes on capacitors are investigated in this study. It is demonstrated that the capacitors with Ti/Ir structure top electrodes improve a resistance against hydrogen related degradation. As the thickness ratio of Ti/Ir increases, the capacitors show enhanced endurance against hydrogen damages. Especially, PZT (350nm) capacitors with Ti(80nm)/Ir(20nm) hybrid top electrodes show only 26% decrease in nonvolatile polarizations (P?_r) under ± 7V, while 67% of P?_r of ferroelectric capacitors with Ir top electrodes is reduced after forming gas annealing at 250°C for 10min. Based on the XPS analysis, ferroelectric characteristics of PZT thin film capacitors are degraded by destruction of Pb-O bond into metallic Pb due to hydrogen anneal on the catalytic top electrodes (Ir, Pt).     

PIEZOELECTRICALLY DRIVEN MICROTRANSDUCER MASS SENSORS

ABSTRACT

Various types of piezoelectrically driven microtransducers which have a similar physical dimension, i.e., microcantilever, microdiaphragm and microbridge, were fabricated by micro electromechanical system (MEMS) technique and are compared on the mass sensing behavior. The diol based sol-gel derived Pb(Zr_0.52,Ti_0.48)O₃ (PZT) thin film capacitors were integrated for the piezoelectric actuation. We have used the resonant frequency change of microtransducer upon mass increase as a sensing mechanism. The resonant frequency of the microtransducer was measured by analysis of electrical signals from microtransducer such as impedance, capacitance, phase and dielectric loss. The fundamental resonant frequencies of the microcantilever, microbridge and microdiaphragm with similar dimension (～300 μm) were about 26 kHz, 260 kHz and 290 kHz, respectively. The mass sensitivities of bare microtransducers were measured by metallic thin film deposition and analysis of spectral responses from microtransducers. When various microtransducers are compared, the microcantilever exhibited the highest gravimetric sensitivity factor (Δf/Δm×f₀ = 694.4 cm²/g), followed by the microbridge and microdiaphragm. However, the microbridge showed the highest mass sensitivity (Δf/Δm = 137.5 Hz/ng) among those transducers.     

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.     

Characteristics of ferroelectric gate mos and mosfets

Abstract

Electrical characteristics of metal-insulator-semiconductor (MIS) capacitors of a variety of ferroelectric materials like lead zirconate titanate (PZT), lead titanate (PT) and barium magnesium fluoride (BMF) on p-silicon have been studied. PZT was deposited by r.f. magnetron sputtering from a composite target and PT from co-evaporation. The films were annealed in oxygen atmosphere in the temperature range 550–700°C for various times. PZT and PT films which are directly deposited on silicon showed low effective dielectric constant.¹⁰ For normal applied bias voltages (±5 V), the C-V curves did not show significant hysteresis. The effective dielectric constant was improved significantly by the incorporation of a buffer layer. BMF film was deposited in ultra high vacuum on a heated substrate and the film was encapsulated by a zirconium oxide layer. The C-V curves for these MIS capacitors shows hysteresis and the direction of hysteresis corresponds to ferroelectric polarization.