Fabrication of PZT Thick Films on Silicon Substrates for Piezoelectric Actuator

In recent years, there has been an increased interest in ferroelectric lead zirconate titanate (PZT) films for applications in piezoelectric devices. Many potential applications require a film thickness of about 10 m for higher force, better sensitivity and stability. In this study we fabricate lead zirconate titanate (PZT) thick films by screen printing on silicon substrates with a platinum bottom electrode. Various substrates were studied. The longitudinal piezoelectric coefficient, d₃₃, was measured by the normal load testing method. Breakdown voltage, tan , P-E hysteresis loop and permittivity were measured on the PZT thick films. The results are promising for the use of PZT thick films in various applications, for example, in silicon micromachined micro-pump.     

Ultrasonic Micromotors Based on PZT Thin Films

The integration of piezoelectric Pb(Zr,Ti)O₃ thin films on silicon substrates for ultrasonic motor applications is reviewed. With suitable buffer and bottom electrode layers the problems due to high processing temperatures in oxygen ambient can be handled. Reproducibility can be increased by stabilized electrode systems and seeding layers for PZT nucleation. Elastic fin micromotors of millimeter size have been fabricated. They achieve the necessary torques, low speeds, and battery voltage operation for applications in wristwatches. However, their efficiency needs to be improved. Better figure of merits of the material still can be achieved. Better designs with larger coupling factors are desirable.     

Non-Linear Imprint Behavior of PZT Thin Films

Ferroelectric thin film capacitors are promising candidates for non-volatile ferroelectric Random Access Memories (FeRAM's) as they exhibit a switchable polarization. There are three important failure-mechanisms influencing the performance of these capacitors and disturbing the long-term stability and reliability under operation conditions fatigue, retention, and imprint. The imprint effect of lead zirconate titanate (PZT) thin films was investigated in this paper. Establishing and maintaining a polarization state leads to a shift of the hysteresis loop on the voltage axis and also to a loss of polarization. The voltage shift as well as the loss of polarization can cause a failure of the ferroelectric memory cell (read and write failure). The experimental results obtained on PZT films are discussed in view of the predictions of imprint models proposed in the literature.     

Effect of Pyrolytic Film Thickness on the Texture Evolution of PZT Thin Films

This paper describes the effects of pyrolysis temperature and film thickness before annealing on the orientation and microstructure of the lead zirconate titanate (PZT) thin films prepared by chemical solution deposition method (CSD). Different thickness of the pyrolytic films were obtained by repeating deposition and pyrolysis with different times. The orientation and microstructures of the PZT thin films were characterized by X-ray diffractometry (XRD) and field-emission scanning electron microscope (SEM). The results show that the thickness of the pyrolytic films was the principal factor that affects the crystalline structures in PZT thin films.     

Improvement of Capacitive Behavior on Gradient-Free PZT Thin Films

PbZr_0,52Ti_0,48O₃ thin films were synthetized by sol-gel techniques on large scale Pt(111)/TiO_x/SiO₂/Si substrates (200 mm in diameter). The Zr/Ti ratio gradient – that appears through the thickness of the layer with standard processing – can be reduced using an optimized “gradient-compensated” approach. Capacitance measurements revealed an augmentation of the effective permittivity from 5 to 15% using “gradient-free” PZT (reaching 1700 for 2μm). Large scale breakdown voltage analysis revealed an increase of 20% for the breakdown field for low thicknesses (1.25MV/cm for 240 nm-thick layer) suitable for capacitor integration.     

Optimized PZT Thin Films for Pyroelectric IR Detector Arrays

A planar multi target sputtering technology was used to deposit highly (111) oriented Pb(Zr _x Ti_1–x )O₃ (PZT) thin films with x ranging from 0–0.6. The preparation of a stable Pt/ZrO₂ electrode is described and analyzed in terms of stress and stress-temperature behavior. The PZT films with low Zr content are under compressive stress after deposition. The dielectric constant and loss peaks occur at a composition close to the morphotropic phase boundary. Films on the tetragonal side of the phase diagram with a Zr content up to about 25% exhibited a strong self polarization and strong voltage shifts in the C(V) curves. High pyroelectric coefficients of >2×10^–4 C/(m²K) have been measured on these films without additional poling. The self polarization fades out with increasing Zr content. The low values of the pyroelectric coefficient for the PZT film with 60% Zr is discussed in terms of the possible crystallographic variants after distortion and the tensile stress state during the phase transition. Based on the systematic study of stress and electrical properties of PZT films with a wide range of composition presented in this paper, films with a Zr content up to about 25% turned out to give the best properties for the use in pyroelectric detector arrays.     

Influence of Stress on the Performance of PZT Thin Films for Microphone Application

ABSTRACT

A series of microphone cells based on integrated PZT thin films were fabricated by typical MEMS process. The thickness of back silicon as a load of the vibrating diaphragm was controlled by changing ICP (Inductive Coupling Plasma) etching time and power. Concaved diaphragms with different radius were formed due to the balanced tensile stress among the multi-layer films structure. The remnent and saturated polarization strength of microphone cells decreased with the increased deformation of diaphragm. The phenomenon was explained as the weakening of mechanical-electrical coupling in piezoelectric thin films in stressed state.     

Effect of Solution Processing on PZT Thin Films Prepared by a Hybrid MOD Solution Deposition Route

Lead zirconate titanate, Pb(Zr_0.53Ti_0.47)O₃ (PZT), thin films were prepared by a hybrid metalorganic decomposition (MOD) solution deposition route; the effects of processing conditions on the film structure and properties were investigated. Solutions were synthesized by mixing and reacting Zr acetylacetonate and Pb acetate trihydrate with a solution prepared from Ti isopropoxide, acetic acid and water. Chemical changes in the solution during preparation and solution storage (i.e., aging) were investigated by visual observation and FTIR, and were evidenced by changes in phase content and properties of the final PZT films. Results suggest that Zr acetylacetonate and Pb acetate trihydrate react with a Ti oxoacetate-based precursor, and that this reaction continues during aging at room temperature. The PZT film quality and properties improved with aging time of the solution before deposition. To achieve good properties and design a convenient processing route, an accelerated aging scheme, including a brief aging at 60°C and freezing to prevent further reaction, was developed. PZT films prepared from these solutions had average dielectric constants of 1040, loss tangents of 0.05, remnant polarizations of 26 C/cm², and coercive fields of 39 kV/cm.     

Mobile defect contribution to the dielectric non-linearity of PZT ferroelectric thin films

Abstract

Effect of the speed of bias voltage variation v on the dielectric non-linearity of metal-PZT-metal thin film capacitors has been studied. A distance ΔV between two maxima of C-V dependence on the voltage scale, characteristic for ferroelectric phase, as a function of the v value was investigated. It was established that decreasing vvalue led to ΔV decrease: ΔV = 1.8–2.0 V when v = 1.6x10⁴ V/s, and ΔV ? 1.0 V when v = 6.5x10^?2 V/s. The ΔV(v) dependence can be explained by the decreasing of the coercive field of the film due to the migration of charged mobile defects such as the doubly ionized oxygen vacancies, and the formation of space charge regions near the electrodes. Using the experimental data some parameters of the migration process were evaluated: the concentration of oxygen vacancies and their mobility were found to be about 10²⁴ m^?3 and 10^?11 m²/Vs, respectively. These values are close to the data published in the literature obtained using the alternative methods of investigation.     

Ferroelectric SrBi 2 Nb 2 O 9 Thin Films by Aqueous Chemical Solution Deposition

SrBi 2 Nb 2 O 9 (SBN) thin films on a Pt/Ti/SiO 2 /Si substrate were prepared by aqueous chemical solution deposition. The precursor solution was synthesized by means of an 'aqueous solution-gel method', starting with stable, inexpensive and easily available inorganic salts which are dissolved in an aqueous solution of chelating or coordinating ligands (acetates and citrates). Afterwards the synthesized precursor was spin-coated. However, problems arose as a consequence of insufficient 'wetting' of the substrate surface by the aqueous solution (poor film-substrate adhesion). Instead of improving surface adhesion by the addition of a surface-wetting reagent, a new strategy was developed: prior to spin-coating the platinum surface characteristics were modified using a UV/ozone technique. In this way the precursor solution was not chemically changed. Wetting/wettability was verified by means of contact angle measurements. A uniform, three-layer thin film with a total thickness of about 200 nm was obtained after thermal treatment, as could be verified using SEM and XRD.     

Preparation of PZT Thin Films by Liquid-Source MOCVD Using of Cyclohexane Solvent

Pb(Zr, Ti)O₃ thin films were grown on 8-inch Ir(111)/SiO₂/Si substrate by a MOCVD system aiming at application utilizing high-density ferroelectric memory (FRAM). Two types of solvents, THF and cyclohexane were used for liquid source delivery. It was found that the ferroelectric properties of the MOCVD-PZT films using cyclohexane solvent were better than them using THF solvent. By choosing cyclohexane as solvent, the MOCVD-PZT thin films showed strong ?111? preferred orientation and the Pt/PZT/Ir capacitors exhibited promising ferroelectric performances, for instance, large switching charge (Qsw) of 56.4 uC/cm².     

Chemical solution technique to prepare perovskite PZT and PLZT thin films and powders

Abstract

PbZr_0.65Ti_0.35O₃ and Pb_0.91La_0.09Zr_0.65Ti_0.35O₃ thin films with thickness of around 100 nm were prepared by the chemical solution deposition technique on Si (100) substrate. Complex metal alkoxide precursors were synthesized by alcoholisis and alcohol exchange reactions starting from metallorganics compounds. NMR spectroscopic techniques, ¹H and ¹³C, and FTIR analysis were used to study the arrangement of the metals and oxygen in the precursor molecules. The films were deposited on Si (100) by spin coating technique and thermal treated by Rapid Thermal Processing for film crystallization. The thermal evolution and structural characterization were performed by DTA-TG/FTIR and by glazing incidence XRD and XRD powder. A PLZT powder with a well-crystallized perovskite structure was obtained at 700°C free of pyrochlore phase whereas the PLZT film exhibits a distorted perovskite structure and residual pyrochlore. The PZT films were less crystallized. The silicon substrate affects the crystal structure of the film. The residual acetylacetonate groups in the precursor of PLZT, would reduce the clustering of Zirconium species.     

Fabrication of PZT Composite Thick Films for High Frequency Membrane Resonators

High frequency, thickness mode resonators were fabricated using a 7 m PZT thick film which was produced using a modified composite ceramic sol-gel process. Initial studies dealt with the integration of the PZT thick film onto the substrate. Two different diffusion barrier layers were tested, titanium oxide and zirconium oxide, in conjunction with the use of 2 types of silicon substrate (differing in the etch stop layer employed, either silicon nitride or silicon oxide). Zirconium oxide gave good results in conjunction with silicon oxide. Using these conditions, devices were produced and the acoustic properties measured for different electrode sizes ranging from 45*45 to 250*250 m². The best electrode size, which maximised the acoustic response and minimised the insertion loss, was found to have an area of 110*110 m². This device showed a resonant frequency of about 200 MHz, an effective electro-mechanical coupling coefficient of 0.29 and a Q factor of 22.     

Effect of Buffer Layer on the Properties of Laser Ablated PZT Thin Films

Lead zirconate titanate (PbZr _x Ti_1?x O₃) or PZT ceramics are a class of piezoelectric materials that are currently experiencing widespread use in industry as electromechanical devices. PtSi/ZnO/PZT thin films were deposited by pulsed laser deposition at relatively low substrate temperature. The PZT thin films on PtSi substrates and on ZnO buffer layer were deposited at substrate temperature 300°C. The composition analysis shows that the film deposited at low temperature is stoichiometric. The films exhibit ferroelectric nature with coercive field of 19.6 kV/cm for 800 nm thick film. The leakage current density of the films shows a good insulating behavior.     

Pyroelectric Properties of PZT/PMNZTU Composite Thick Films

Lead zirconate titanate/uranium doped lead magnesium niobate—lead zirconate titanate (PZT/PMNZTU) composite thick films have been fabricated on silicon substrates at 710°C using a composite sol gel technique. A slurry, made up of PMNZTU powder and PZT sol, was spun onto a silicon substrate and fired to yield a porous skeletal ceramic structure. Subsequent sol infiltration and pyrolysis was used to modify the density of the films prior to final sintering at 710°C.Pyroelectric and dielectric properties have been measured as a function of sol infiltration. The pyroelectric coefficients (p _max = 2.41 × 10^–4 Cm^–2 K^–1) of the composite thick films were found to be comparable to the tape cast and monolithic ceramics of similar composition (2.8 and 3.0 × 10^–4 Cm^–2 K^–1 respectively).Maximum figures of merit (F _V = 2.23 × 10^–2 m² C^–1, F _D = 0.89 × 10^–5 Pa^–1/2), calculated using the electrical properties of the thick films, can be compared with those of screen printed thick films (F _V = 2.7–3.9 × 10^–2 m² C^–1, F _D = 0.8–1.1 × 10^–5 Pa^–1/2) processed at temperatures of ca 1100°C. The ability to directly integrate thick pyroelectric films onto substrates at temperatures as low as 710°C, while maintaining competitive figures-of-merit is of considerable interest for future device applications.     

XPS Studies of PZT Films Deposited by Metallic Lead and Ceramic PZT Dual Target Co-Sputtering

The dependence of the chemical states of the constituent elements of a PZT thin film prepared by RF magnetron co-sputtering using ceramic PZT and metallic Pb dual target materials on the Ar⁺ etching time was studied using XPS. The metallic Pb, lead oxide and Pb in PZT led to the different binding energies of the Pb lines. The intensity of binding energy of metallic Pb relative to that of bulk Pb increased with the depth of the film. The peak position and the line shape of the O_1s electron was associated with the different binding energies of oxygen, which interacts with Pb and Ti and Zr atoms to form the metal oxides, and the softening of the O_1s bonds by the bonding interaction in Ti–O, Zr–O and Pb–O. The broad Ti_2p3/2 line in the PZT film could has been associated with the various charge state of Ti and no spectral changes of Ti_2p and Zr_3d were observed as the Ar⁺ ion sputtering time was increased.     

Thickness Dependence of Piezoelectric Properties for PZT Thin Films with Regard to MEMS Applications

In this work we report on the investigation of the piezoelectric and ferroelectric properties of Pb(Zr,Ti)O₃ (PZT) thin films with a composition of 45% zirconium and 55% titanium prepared by chemical solution deposition (CSD) regarding the major properties required in MEMS applications. Therefore we have measured the polarization and the piezoelectric coefficient d ₃₃ and strain using a high-resolution double beam laser interferometer. We found that d ₃₃ alike the strain is nearly independent of the sample thickness. To estimate the lifetime of MEMS we stressed the samples by applying switching and non-switching voltage pulses. In the non-switching case, no change of the material properties was observed whereas the use of switching voltage pulses resulted in a strong decrease of the piezoelectric properties and the polarization. Here we found a linear behavior between the material properties in the fatigued state and the sample thickness.     

The dependence of ferroelectric and fatigue behaviors of PZT films on annealing conditions

Films of PZT about 0.2 μm thick with the composition PbZr_0.53Ti_0.47O₃ were prepared using the metalloorganic decomposition (MOD) process. The amorphous films produced by pyrolysis at 350°C were annealed at 550, 575, 600 and 650°C for 10 minutes, 1 hour or 4 hours. Films annealed at temperatures below 550°C showed no ferroelectric behavior while others annealed above 650°C showed signs of loss of ferroelectric behavior. Most films demonstrated satisfactory ferroelectric properties such as low switching voltage and high polarization values. Some PZT films also demonstrated fatigue life-time of more than 10⁹ switching reversals. The performance of the films was dependent on the annealing time and temperature. It was found that films with better initial polarization values did not necessarily demonstrate better fatigue behavior. The causes of film degradation as a result of switching based on the pinning of domains at grain boundaries triggered by the migration of pores is discussed.     

Mechanical and electric fatigue of PZT(53/47) films on metallic substrates

Abstract

We have investigated the fatigue of electromechanical and dielectric properties of sol-gel derived PZT(53/47) thin films deposited on metallic substrates by means of electric and mechanical cycling. For the mechanical cycling a two point bending method was used to apply transversal stress to the samples. During mechanical cycling the piezoelectric coefficient d₃₁ remained constant up to about 10⁵ cycles, for a higher number of cycles a strong decrease was observed. During electric cycling no significant changes in the ferroelectric and electromechanical hysteresis loops could be found up to about 3×10⁵ cycles. Above this number the coercive field increases, the maximum strain and the remanent polarization decrease.

Obviously each electric cycling of the investigated films is accompanied by a mechanical cycling. It is assumed, that microcracks induced by mechanical stress are the main reason for the deterioration of the physical properties films during electric and mechanical cycling both.     

Microstructure and Properties of Solution Deposited, Nb-Doped PZT Thin Films

Nb doped PZT films with Nb concentrations of 0, 5, 8 and 12 mol% are being processed via chemical solution deposition on platinized Silicon substrates. An original processing route including seed layer and additional PbO coating is presented whereby homogeneous, pyrochlore free microstructures with 111/100 texture are obtained. The temperature dependence of the dielectric constant shows diffuse peaks corresponding to the paraelectric to ferroelectric transition. The transition temperature is found to decrease from 325°C to 220°C with increasing Nb content. Nb is however found to lead to a substantial increase in the dielectric constant in comparison to non-doped PZT. The dependence of the dielectric constant on DC bias field is also reported. Strong asymmetries towards positive values both in the values of the dielectric constant and coercive fields are obtained at room temperature, and become replenished at 100°C. This is interpreted in terms of space charge effects on the pinning of domain walls. Furthermore, the loss tangent shows a relaxation peak which shifts to higher frequencies with increasing Nb content, and suggests that Nb-doping affects the dielectric properties of the interfacial layer. Finally, Nb addition is found to lead to slant hysteresis loops with lower remnant polarization and coercive field.