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.     

Investigation on the electrical characteristics of sol-gel derived Pb1.05(Zr0.53Ti0.47)O3 thin films

Abstract

Lead zirconate titanate (PZT) thin films with composition Zr/Ti ～ 0.53/0.47 were deposited by the sol-gel technique. The films were characterized in terms of its polarization relaxation, fatigue and imprint characteristics. We have found that the polarization relaxation is due to the presence of a depolarization field which increases dramatically with the rise in temperature. Improved fatigue performance was observed when the film was fatigued with higher frequency. The direction of imprint depends on the state of polarization. With the increase in net polarization, the trapped charge density at the film-electrode interface increases which leads to imprint characteristics. Also the imprint increases considerably with the rise in temperature. Finally, we have made an attempt to correlate simultaneously fatigue, polarization relaxation, and imprint characteristics with the presence of mobile charge defects (viz. V_o) and defect dipoles (viz. V_Pb – V_o) in the film.     

Electrical characteristics of high dielectric constant BCTZ thin films

Abstract

High dielectric constant Ba_0.96Ca_0.04Ti_0.84Zr_0.16O₃ (BCTZ) thin films were deposited on Pt/Ti/SiO₂/Si substrates by spin on metal-organic decomposition (MOD) technique. Undoped and 0.4% Mg-doped BCTZ thin films were annealed in the temperature range from 600 to 900 °C for 1 hour in oxygen environment. The crystal structure of BCTZ thin films was analyzed by X-ray diffraction. The electrical properties of BCTZ thin films were investigated by capacitance—voltage (C—V) characteristics. Also, the electrical properties of these films were compared in conjunction with 0.4% Mg doping effect of BCTZ thin films for possible high dielectric constant material applications.     

Modulation on the electrical and optical properties of Na and Rh co-doped Ruddlesden-Popper layered Ca3Ti2O7

Layered perovskite Ca_2.91Na_0.09Ti_2-xRh_xO₇ (x?=?0.00, 0.02, 0.04, 0.06) were synthesized by a conventional solid-state reaction. Room temperature ferroelectricity has been confirmed. The remanent polarization increases with an increase of Rh content, which is due to a larger oxygen octahedral distortion by Rh doping. The coercive field increases with Rh doping as the pinning effect of oxygen vacancies reduce the mobility of domain wall. Remanent polarization and coercive field are caused by different mechanisms, so it is possible to modulate them independently to meet the requirement of application in ferroelectric field. The concentration of oxygen vacancy increased with Rh doping, leading to the significant increase of leakage current density. The bandgap of samples doped with Rh drastically decrease and the visible light response of the sample was improved by Rh doping due to the formation of impurity energy levels within the band gap.

     

Temperature dependence of the dielectric dispersion and ferroelectric properties of neodymium doped bismuth titanate ceramics

Nd-doped bismuth titanate Bi_{4 − x} Nd _x Ti₃O₁₂ ceramics (x = 0–1.0) were prepared by the solid state reaction method. The temperature dependence of the dielectric dispersion and ferroelectric properties were investigated. With the increase of the Nd substitution for Bi ion, the Curie temperature decreased and the corresponding dielectric constant peak broadened. In addition, the strong low-frequency dielectric dispersions were exhibited. The Nd doping decreases the temperature dependence of the ac conductivity and increases the temperature dependence of the remanent polarization, which is caused by the induced polarization by defects, such as bismuth and oxygen vacancies.     

A novel diffusion barrier using oxygen stopping layer for high density FRAM

Abstract

A novel diffusion barrier was successfully developed by using an oxygen stopping layer between Ir barrier films. The oxygen stopping layer was generated by inserting a Ti layer between Ir films, which results in the sandwiched form of Ir/Ti/Ir multi-layer. The diffusion barrier properties were enhanced by refraining oxygen from penetrating into polysilicon plug, which might be attributed to the reaction of oxygen with the Ir-Ti layer. It was confirmed in Auger depth profile that the oxygen was well localized in the stopping layer after annealing at 700°C for 10 min in O₂ ambient. The multi-stack barrier exhibited low contact resistance of 320 and 650 ohm for contact size of 0.6×0.6 and 0.4×0.4 μm², respectively. The PZT films prepared on Pt/IrO²/Ir-Ti-Ir/poly substrate shows remnant polarization of 20 μC/cm² and coercive voltage of 1.2V at 5V. It was demonstrated that this novel barrier can solve barrier contact problem occurred in high density 16Mb FRAM.     

Processing and characterization of LiNbO3 thin film for metal Ferroelectric Semiconductor field effect transistor (MFSFET) application

Abstract

LiNbO₃ thin films were deposited on P-Si(111) substrates. C-axis (006) oriented films were fabricated with RF magnetron sputtering and (012) oriented films were achieved by metal organic decomposition (MOD). High frequency C-V measurement showed a clockwise rotation hysteresis curve, which corresponded to the ferroelectric switching. A polarization vs. voltage hysteresis curve of a Metal-Ferroelectric-Semiconductor (MFS) capacitor was measured with a modified Sawyer-Tower circuit. Remnant polarization as high as 65μC/cm² was found from sputtering deposited sample.     

Deposition of large-area graded (Pb1−xLax)TiO3 thin films by pulsed laser depesition

Abstract

Thin films of the composition (Pb_1?xLa_x)TiO₃, PLT, with x=0.05, 0.10 and 0.15 were sequentially pulsed laser deposited on Pt(Si) substrates at 200°C, followed by post-annealing at 550–600°C in furnace to result in a film with graded composition. The ferroelectric properties of the graded materials are markedly different from those of the uniform thin PLT films. For down graded materials, which contain PLT5 composition (x=0.05) at the top and PLT 15 composition (x=0.15) at the bottom of the films, the hysteresis loops are slim and the width of the P-E curves increases with voltage cycling, attaining an equilibrium polarization states similar to the P-E properties of PLT 15 thin films. By contrast, the ferroelectric hysteresis properties reaches the same value as those of PLT5 thin films when the composition is up-graded.     

La doped PZT 60/40 films by MOD technology

Abstract

Ferroelectric La doped PZT 60/40 thin films with uniform composition have been synthesized using metallo-organic precursor solutions. These metallo-organic precursors have been stored for more than four years and are very stable in ambient conditions, compared to the sol-gel solutions. The structural properties of these films have been studied using X-ray diffraction and atomic force microscopy. The excellent ferroelectric properties of the films, such as less than 10% polarization loss after 10¹¹ cycles, low leakage current of 3·06×10^?12 A at 2 V, and small separation of polarization peaks in a voltage loop by the small-signal measurement, are attributed to the high quality of the metalloorganic solutions used in this study, which have been carefully home-synthesized. The oxygen vacancy in the films was reduced by optimizing the annealing conditions, and to minimize the blocking oxygen vacancy at the interface by Pt electrodes a suitable amount of La ions was doped. We suggest that greater attention should be paid to the elimination/minimization of the oxygen vacancy in the ferroelectric PZT films instead of using oxide electrodes, which allow a relatively larger leakage current flowing through the films and the electrodes.     

LARGE AREA PIEZOELECTRIC ACTUATORS USING METAL FOIL SUBSTRATES WITH Pb(Zrx,Ti1 - x)O3 THIN FILMS

ABSTRACT

We report on the deposition of Pb(Zr_x,Ti_{1 - x})O₃ (PZT) thin films by chemical solution deposition (CSD) on stainless steel foils. The electrical characterization proves good ferroelectric properties with a remnant polarization of 38 μ C/cm². Since PZT is also piezoelectric the 35 μ m and 50 μ m thick metal foils are used to make piezoelectric actuated cantilever beams of several millimeter lengths. Actuated with 10–30 V a displacement up to 32 μ m was measured in quasi-static mode. In resonance mode the displacement increases several times at the same driving voltage.     

Self-polarization effect in Pb(Zr,Ti)O3 thin films

Abstract

The self-polarization effect is investigated in Pb(Zr,Ti)O₃ (PZT) thin films deposited by sol-gel and magnetron sputtering techniques. The effective piezoelectric coefficient of as-grown films, which is proportional to their initial polarization (self-polarization), is measured by a sensitive interferometric technique as a function of the annealing temperature, PZT composition, film thickness and bottom electrode material. The results indicate that the films are self-polarized by an internal bias field upon cooling through the phase transition temperature. It is suggested that a built-in field of a Schottky barrier between the PZT film and the bottom electrode is responsible for the observed effect. Self-polarization of the films is found to be very stable and in some cases to be as high as 90% of that produced by the subsequent room temperature poling. This property is very useful for piezoelectric and pyroelectric applications of PZT films since the poling procedure can be avoided. The properties of self-polarization are found to be similar for the films produced by sol-gel and sputtering techniques, suggesting that the same mechanism is operative in both cases.     

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.     

Effect of ion damage on the crystallization of PZT thin films

Abstract

Effects of Ar ion damage prior to the phase transformation from pyrochlore to perovskite structure of PZT thin films have been investigated. As the degree of damage increased by increasing the acceleration voltage in the ion mass doping system, the phase transformation temperature decreased such that the temperature could be lowered down to 550°C when the film was damaged at 15kV for 5 minutes. When the films were damaged prior to the heat treatment, the final grain size of the perovskite thin films became less than 300Å. The microstructure showed the granular type rather than columnar structure after ion damage treatment and annealing. It turned out that relatively high value of the remanent polarization (about 30 μC/cm²) as well as improvement of the fatigue characteristics to a large extent are closely related to the fine grain size of thus obtained PZT films.     

BIPOLAR RESISTIVE SWITCHING IN Au/TiO2/Pt THIN FILM STRUCTURES

ABSTRACT

The conditions and physical mechanisms of electroforming and subsequent resistive switching in Au/TiO₂/Pt thin film structures were investigated. It was concluded that the electroforming, being a current-limited electric breakdown of the TiO₂ films, resulted in a considerable increase of the oxygen vacancy concentration in the bulk and on the surface of the films. The resistive switching implemented by short voltage pulses of different polarities is proposed to be due to the change of the Schottky barrier height at the Pt/TiO₂ interface as a result of the current-induced variation of the occupancy by electrons of the surface states in the band gap of TiO₂.     

High-permittivity lead-based perovskite dielectrics for DRAM applications

Abstract

Suppression of the nonvolatile polarization in lead zirconate titanate films by La doping or by use of films 100 nm or less in thickness provides the highest charge storage densities yet observed. These films also satisfy leakage current density and TDDB requirements for very high density DRAMs, and show good resistance to fatigue.     

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.     

Defects of BaTiO3 thin films on Ti-deposited Si substrate by hydrothermal method

Abstract

Defects of barium titanate thin films synthesized on Ti-deposited substrate by the hydrothermal method were defined by the heterogeneities of the surface morphology and phase-composition. In present work, the defects observed on the films have been classified, and the feature of these defects on the morphology and phase-composition summarized, and the formation process discussed. It has been proven experimentally that the homogeneity of the films was strongly affected by the surface state of the deposited Ti layer on the Si substrate and the reaction conditions. It is important to use a defectless and well-pretreated substrate and to process at high temperature above 180°C in the Ba(OH)₂ solution of high concentration for long enough reaction time and is an effective way to eliminate the defects.     

Ferroelectric and dielectric properties of sol-gel and excimer-laser-deposited lead zirconate titanate and barium titanate films

Abstract

Switched remanent polarization was measured as a function of accumulated switching cycles for a variety of ferroelectric films using sinusoidally driven hysteresis loops. Switched remanent polarization and dielectric constant and loss were also obtained as a function of the cycling frequency. PZT films with niobium additives appeared to lose switched remanent polarization with accumulated cycles at a lesser rate than films without niobium. The switched remanent polarization was found to decrease with increasing frequency, which we attribute to the effect of grain size. Also, a decrease of dielectric constant with increasing frequency and an increase of dielectric constant with increased applied voltage are attributed to the effects of domain wall motion contributions to dielectric constant.     

Ferroelectric Na0.5K0.5NbO3 thin films by pulsed laser deposition

Abstract

Highly c-axis oriented single phase Na_0.5K_0.5NbO₃ (NKN) thin films have been deposited onto polycrystalline Pt₈₀lr₂₀ substrates and SiO₂/Si(001) wafers using pulsed laser ablation of stoichiometric ceramic target. Strong self-assembling of NKN films along the [001] direction has been observed. Properties of NKN/Pt thin film structures have been successfully tailored by oxygen pressure control from the ferroelectric state, characterized by the remnant polarization of 12 uC/cm², dielectric constant ? ～ 520 and tan δ ～ 0.024 @ 100 kHz, to superparaelectric state with tan δ as low as 0.003 and ? = 210 with very small 1.7% dispersion in the frequency domain 0.4–100 kHz and less than 10% variation in the temperature range 77–415 K. NKN films grown onto SiO₂/Si(001) substrates show quadrupled super-lattice structure along c-axis, loss tan δ less than 0.01, and ? ～ 110 @ 1 MHz. C-V measurements for Au/NKN (270nm)/SiO₂/Si MFIS-diode structure yield memory window of 3.26 V at the programmable voltage of 8 V.     

Dielectric and lattice dynamical properties of SrTiO3 thin films

Abstract

Pulsed-laser-deposited SrTiO₃ thin films are used as all example to illustrate the effects of strain. oxygen vacancies, and interfacial dead layer on the dielectric and lattice dynamical properties in ferroelectric thin films. We found that strain, both lattice mismatch-induced and due to local defects such as oxygen vacancies, dramatically influences the properties of the thin films. The cubic-to-tetragonal structural phase transition is greatly modified by the strain in the films. Raman scattering shows the symmetry-forbidden optical phonons, indicating the reduction of symmetry. The line shape of the polar phonon shows a Fano asymmetry, which we suggest to be due to the micro polar regions or other local polar structures around the oxygen vacancies. The temperature dependence of the low-frequency complex dielectric constant shows markedly distinct quantum fluctuation behaviors from those of the single crystals. The soft mode is considerably hardened in the thin films compared to the single crystals.