Miniature Microphone with Silicon-Based Ferroelectric Thin Films

A miniature microphone with silicon-based lead zirconate titanate (PZT) thin films has been fabricated and tested. The main structure of the device is composed of Al/Pt/PZT/Pt/Ti/SiO₂/Si₃N₄/SiO₂/Si multi-layer diaphragm. The PZT thin films have been prepared using an improved sol-gel method. Optimized fabrication process of the device has been developed, especially, RIE (reactive ion etching) and IBE (ion beam etching) processes have been used to etch the PZT thin film and electrode metal successfully. The sensitivity of microphone is 16 mV/Pa at 1 KHz and 158 mV/Pa at the resonant frequency of 17.3 KHz. The electrical and thermal reliability of the microphone is satisfactory. This miniature microphone can be widely used in hearing aids, mobile phones, and many other applications.     

PZT capacitors using IrO2 electrode by RF magnetron sputtering

Abstract

RF magnetron sputtered Pb(Zr_x, Ti_1-x)O₃ [PZT] films were prepared on IrO₂/SiO₂/Si and Pt/IrO₂/SiO₂/Si substrates using the ceramic PZT target with Pb_1.1(Zr_0.52Ti_0.48)O₃ composition. In order to obtain single perovskite phase, PZT film was sputtered at room temperature under Ar plasma and followed by high temperature annealing under oxygen atmosphere. In case of Pt/PZT/IrO₂ capacitor, Δ P (=P*-P∧) was decreased with oxygen annealing temperature. However, it was increased in Pt/PZT/Pt/IrO₂ capacitor. Leakage current density of Pt/PZT/Pt/IrO₂ capacitor, which was used for improving leakage characteristics, was about 10^-2A/cm^?2 order lower than that of Pt/PZT/IrO₂ capacitor. Leakage current density of Pt/PZT/Pt/IrO₂ capacitor annealed at 700°C was 6.6x10^-6A/cm². From the fatigue test, Pt/PZT/IrO₂ capacitor annealed at 650°C and Pt/PZT/Pt/IrO₂ capacitor annealed at 700°C showed 3% and 12% degradation of Δ P after 5×10¹⁰ fatigue cycles, respectively.     

Study on property variation due to the interface between PZT and electrode

Abstract

The ferroelectric capacitors are fabricated using RuO₂/Pt electrode to examine the electrode effect on ferroelectric properties. PZT films are prepared by metalorganic decomposition (MOD) on sputter deposited electrodes. In particular, inductively coupled plasma(ICP) etcher is used to minimize the etching damage. In addition, TiO₂ reaction barrier layer is also employed to retard the degradation of ferroelectric properties due to the reaction between a passivation layer and PZT film. The better hysteretic properties were obtained from Pt/RuO₂/PZT/RuO₂/Pt ferroelectric capacitors. The enhancement of ferroelectric properties is likely attributed to the modification in the microstructure of PZT film. The interfacial modification would be affected by the factors such as surface roughness, stress, and porosity of RuO₂ film. The result implies RuO₂/Pt would be a good electrode for a nonvolatile memory application.     

Improvement on ferroelectric properties of metal-organic decomposited PZT thin film prepared by using prenucleation layer

Abstract

Perovskite SrRuO₃ (SRO) layer was, for the first time, been successfully synthesized by using metal-organic decomposition (MOD) process. The presence of SRO buffer layer on Pt(Si) substrates has significantly enhanced the crystallization and densification behavior of the subsequently deposited Pb(Zr_0.52Ti_0.48)O₃ films. The pyrochlore free perovskite phase can be obtained by post-annealing the PZT/SRO/Pt(Si) films at 500°C, which is 50°C lower than that needed in PZT/Pt(Si) films. The fine grain (～0.3 μm) microstructure can be attained by post-annealing at 650°C for PZT/SRO/Pt(Si) films and 700°C for PZT/Pt(Si) films. The ferroelectric hysteresis properties of the two PZT films are comparable to each other. The leakage current properties of PZT/SRO/Pt(Si) films increased pronouncedly with post-annealing temperature, resulting in inferriar leakage behavior to PZT/Pt(Si) films.     

Energy harvesting MEMS device based on thin film piezoelectric cantilevers

A thin film lead zirconate titanate Pb(Zr,Ti)O₃ (PZT), energy harvesting MEMS device is developed to enable self-supportive sensors for in-service integrity monitoring of large social and environmental infrastructures at remote locations. It is designed to resonate at specific frequencies of an external vibrational energy source, thereby creating electrical energy via the piezoelectric effect. Our cantilever device has a PZT/SiN_x bimorph structure with a proof mass added to the end. The Pt/Ti top electrode is patterned into an interdigitated shape on top of the sol-gel-spin coated PZT thin film in order to employ the d ₃₃ mode. The base-shaking experiment at the first resonant frequency of the cantilever (170 × 260 μm) generates 1 μW of continuous electrical power to a 5.2 MΩ resistive load at 2.4 V DC. The effect of proof mass, beam shape and damping on the power generating performance are modeled to provide a design guideline for maximum power harvesting from environmentally available low frequency vibrations. A spiral cantilever is designed to achieve compactness, low resonant frequency and minimum damping coefficient, simultaneously.     

Modification of PZT nucleation and growth using oxide layer in multi-layered electrodes

Abstract

The ferroelectric properties of PZT on RuO₂ electrodes were compared to those on RuO₂/Pt electrodes. The better hysteretic properties were obtained from Pt/RuO₂/PZT/RuO₂/Pt ferroelectric capacitors. The enhancement of ferroelectric properties is likely attributed to the modification in the microstructure of PZT film. The interfacial modification would be affected by the factors such as surface roughness, stress, and porosity of RuO₂ film. As the result of the interfacial modification, better quality PZT films are produced, thereby resulting in better ferroelectric properties. We made an effort to understand the relationship between the grain size and the coercive voltage in terms of the domain formation and the domain pinning in connection with defects like grain boundaries.     

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.     

Enhancement of Ferroelectric Properties of Pb(Zr,Ti)O3 Films Grown by Metal-Organic Chemical Vapor Deposition on Noble-Alloy Bottom Electrodes

Pb(Zr,Ti)O₃ (PZT) films grown on Ir electrodes by a metal-organic chemical vapor deposition (MOCVD) have suffered from high leakage and rough surface. We sputtered Pt and Ir simultaneously onto Ti/SiO₂/Si substrates and formed Ir-Pt alloy bottom electrodes with various compositions. With an optimal composition of Ir and Pt, PZT films grown by MOCVD on this substrate showed smoother surface and suppressed leakage via the bottom interface. At the specific composition of Ir and Pt, two different phases seemed to be acquired. They constituted the electrodes and affected the PZT grain nucleation independently so that the grains with different origins grew and restrained the vicinal grains, and finally soothed the faceted-grain-formation. No fatigue was observed even in PZT on Ir-Pt alloy with much Pt content.     

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.     

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.     

PZT Capacitors on Top of CrTiN/TiN Double Barrier Layers

In this paper we investigated the thermal stability of a novel CrTiN/TiN double barrier, compared to those of TiN and CrTiN single layer barriers. The CrTiN/TiN double layer was stable against heat treatments at higher than 700°C in oxygen ambient for 30 min. However, the double layer showed a severe Pt and Cr interdiffusion issue after crystallization annealing for PZT. We found that pre-annealing treatments prior to deposition of Pt significantly reduced the interdiffusion. In addition, we also demonstrated ferroelectric characteristics of PZT capacitors on top of Pt/CrTiN/TiO₂/Si bottom electrode system for ultra-high density memory applications.     

EFFECT OF SILICON CARBIDE PASSIVATION FILM ON THE RESONANCE CHARACTERISTICS OF CANTILEVER

ABSTRACT

We have used silicon carbide (SiC) thin films as an insulating material of the PZT micro cantilevers for electrical and biological passivation. The use of SiC thin films as a passivation layer of the PZT microcantilevers is also seemingly viable to insure the high mass sensitivity as well as the stable passivation. In this study, we report the effect of SiC passivation layer on the performance of the PZT microcantilevers. The micromachined PZT microcantilevers having a structure of SiN_x/Ta/Pt/PZT/Pt were fabricated through MEMS processes. In order to improve the mass sensitivity and the passivation, SiC thin films of the high elasticity material were deposited on the cantilever using plasma enhanced chemical vapor deposition (PECVD) at the temperature of 400°C. Plane-strain modulus of SiC thin film was measured by nanoindentation. We observed that SiC thin films showed higher Young's modulus than Si and SiO₂. Before and after the deposition of SiC thin films, the end-tip deflection and the resonant frequency change of microcantilevers were measured by a confocal microscope and an impedance analyzer. It was confirmed that end-tip deflection of microcantilever was reduced by 13～18% through the deposition of SiC thin films, indicating the stress relaxation of the microcantilevers.     

EFFECTS OF PZT BUFFER LAYERS ON PZFNT FERROELECTRIC THIN FILMS

ABSTRACT

PZFNT thin films were fabricated on 5-inch Pt/Ti/SiO₂/Si and PZT/Pt/Ti/SiO₂/Si substrates by RF magnetron sputtering method and rapid thermal annealing process. By investigating the two thin films at various annealing temperatures, the results show that the annealing temperature of PZFNT thin films without PZT buffer layers is about 730°C, which is higher than that of PZFNT films with PZT buffer layers. By use of PZT buffer layers, the annealing temperature of PZFNT films is decreased greatly, and the dielectric and ferroelectric properties are improved. In the optimum process, the thin films with PZT buffer layers have a dielectric constant of 1199 and dielectric loss of 3.0% at 1 KHz. The remanent polarization and coercive field of the thin films are 21.1 μC/cm² and 53.5 KV/cm respectively. The films have the significant potential for FRAM and pyroelectric infrared detectors.     

Preparation of Zr-rich PZT and La-doped PbTiO3 thin films by RF magnetron sputtering and their properties for pyroelectric applications

Abstract

Zr-rich PZT and La-doped PT films were fabricated on a PLT/Pt/Ti/SiO₂/Si or Pt/Ti/SiO₂/Si substrate by an RF planar magnetron sputtering equipment using powder targets with compositions of PbZr_{0 94}Ti_0.06O₃, PbZr_0.92Ti_0.08O₃ and Pb_0.85La_0.15 Ti_0.96O₃ with excess PbO of 20 mol%. The dielectric constants of PZT and PLT films showed anomalies at the transition temperatures of around 246 and 300°C, and their dielectric constants at room temperature were 350 and 1070, respectively. Significant pytroelectric currents were observed in both as-grown PZT and PLT films even without a poling treatment. The pyroelectric coefficients of those films were 10 and 30 nC/cm²K, respectively. Therefore, Zr-rich PZT and [111]-oriented PLT films sputtered on Pt/Ti/SiO₂/Si substrates possess desirable properties for potential applications to pyroelectric devices.     

Low temperature sintering of screen-printed Pb(ZrTi)O3 thick films

Abstract

There has been increasing interest in ferroelectric lead zirconate titanate (PZT) films for the applications in piezoelectric and pyroelectric devices. Many potential applications require a film thickness of above 10 μm for higher force, better sensitivity and stability. But it is very difficult to fabricate the PZT thick film on the silicon substrate because of the volatility of PbO and the interdiffusion of the Pb and Si through the bottom electrode during the sintering at normal temperatures (such as above 1200°C). We speculated densification and reaction mechanism of the PZT thick films fabricated at relatively low temperature (under 1000°C) without sintering aids. The PZT thick films were screen-printed on Pt / Al₂O₃ substrate using a paste of PbO, ZrO₂ and TiO₂ powder mixture. Highly densified PZT thick films could be fabricated on Pt / Al₂O₃ substrate at 1000°C, and we achieved the density, remanent polarization, coercive field, dielectric permittivity, dissipation factor and breakdown field of 98%, 10 μC/cm² and 20 kV/cm, 540, 0.009 and 15 MV/m, respectively. The results show the possibility of densification of the PZT thick film at relatively low temperature without sintering aids, and the results are promising for the use of PZT thick films in various applications.     

Laser ablation-deposited PZT thin films for piezoelectric microsensors and microactuators

Abstract

We report on growth and deposition process optimization of laser ablation-deposited Pb(Zr_0.53Ti_0.47)O₃ thin films for application in piezoelectric microdevices. Films were grown on three different substrates: (100) cut LaAlO₃ single crystals, Pt/Ti/SiO₂/Si, and Pt/Ti/Si_3+xN₄/Si. On all three substrates, a deposition temperature of 620°C yielded perovskite films with good ferroelectric hysteresis properties. La_0.5Sr_0.5CoO₃ bottom and top electrodes were used for all films. PZT films on Pt/Ti/SiO₂/Si showed a variation of texture with film thickness. Thin membranes of PZT on Si_3+xN₄ were also fabricated.     

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.     

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).     

Influence of the Lead Source Materials on the Microstructure and Ferroelectric Properties of PZT Films Sputter-Deposited Using Lead and Lead Oxide

In this investigation, PZT films were sputter-deposited on Si/SiO₂/Ti/Pt substrates using a dual-target system. The dual targets Pb/PZT(PbZr_0.54Ti_0.46O₃) and PbO/PZT(PbZr_0.54Ti_0.46O₃) were used to reveal the effects of various lead compensation source materials on the microstructure and ferroelectric properties of the films. The structures of the films were characterized by X-ray diffractometry (XRD) and field emission scanning electron microscopy (FESEM). The chemical binding state was determined using X-ray photoelectron spectrometry (XPS). Ferroelectric polarizability was measured using a Radiant Technology RT66A tester. The influence of deposition temperatures on the microstructure and ferroelectric properties of the films was studied. Perovskite PZT films were successfully deposited using the Pb/PZT and the PbO/PZT dual target sputtering systems at a substrate temperature of between 500 and 580C. Structural change was elucidated as a function of deposition temperatures and the lead sources were correlated with the ferroelectric properties of the film. The ferroelectric characteristics of the PZT films deposited using the PbO/PZT dual target were better than those of films deposited using the Pb/PZT dual target, because the former films had a higher bonding energy.     

Studies of a PT/PZT/PT sandwich structure for feram applications using sol-gel processing

Abstract

A silicon-based PbTiO₃/Pb(Zr,Ti)O₃/PbTiO₃ (PT/PZT/PT) sandwich structure with Pt electrodes are prepared by a sol-gel method. Effects of the PT buffer layers to the phase formation of the PZT films are studies. Dielectric and ferroelectric properties of the sandwich structure are measured. Maximum dielectric constant of about 900 is obtained at the coercive field 20 kV/cm. The leakage current density is less than 5 × 10^?9 A/cm2 below 200 kV/cm, which is much lower than that of PZT/PT structure. And there is almost no fatigue even after 5 × 109 read/write cycles for the PT/PZT/PT sandwich structure.