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.     

Pyroelectric properties of sol-gel derived PZT thin films with various Zr/Ti ratios

Abstract

Integrated pyroelectric arrays are receiving serious attention for the next generation of room temperature uncooled IR cameras. Such pyroelectric arrays are based on monolithic ferroelectric(FE) thin films. FE films with large values of reported pyroelectric coefficients include PbTiO₃, Ca-doped PbTiO₃, La-doped PbTiO₃, PZT 53/47 and Pb(Sc_0.5Ta_0.5)O₃. The present paper reports a systematic study of the compositional dependence of PZT thin films on their pyroelectric properties. A series of sol-gel derived PZT (lead zirconate titanate) thin films with various Zr/Ti ratios, namely, PbTiO₃, PZT 20/80, PZT 35/65, PZT 53/47, PZT 65/35, PZT 92/8 and PbZrO₃, were prepared on platinized Si substrates. The films were fired to 650 – 700°C to crystallize them into single-phase perovskite. The degree of preferred orientation, grain size and firing temperature affect the pyroelectric responses. Pyroelectric coefficients as large as 2.5 × 10^?8 C/cm²-K were obtained, making such PZT thin films attractive in pyroelectric arrays.     

A 11×6 element pyroelectric detector array utilizing self-polarized pzt thin films grown by sputtering

Abstract

A planar multi target sputtering approach was used to deposit PbTiO₃ (PT) and Pb(Zr, Ti)O₃ (PZT) films on TiO₂/Pt bottom electrodes for the use in thin film pyroelectric IR detector arrays. PZT films with a Zr content of 28 at% (PZ28T) exhibited the best pyroelectric coefficient of typically 2×10^?4 Cm^?2K^?1. The PZ28T films have been used for fabricating a two dimensional 11×6 pixel pyroelectric detector array on Si wafers. The array pixels with a sensitive area of 280 ×280 μm² have a noise lequivalent power NEP of less than 0.7 nW at 1 Hz. It is planned to use the detector array in systems for motion detection.     

Pyroelectric properties and X-ray photoelectron spectroscopic study of R.F. magnetron-sputtering-derived PZT thin films deposited on various interlayers

PZT thin films and interlayers were fabricated by the radio frequency (r.f.) Magnetron-sputtering from the Pb_1.1Zr_0.53Ti_0.47O₃, PbO and TiO₂ target. As a result of the XPS depth profile analysis, we can confirm that the substrate temperature affects the oxidation condition of each element of interlayers and the PZT film. Compared to the PZT/Pt structure, the dielectric and pyroelectric properties of PZT thin films inserted by interlayers were measured to a relatively high value. In particular, the PZT/PbO structure had the highest pyroelectric properties (P = 189.4 μC/cm²K; F _D = 12.7×10⁻⁶ Pa^−1/2; F _V = 0.018 m²/C).     

Ferroelectric ceramics and thin films for pyroelectric applications

Abstract

The extensive work carried out at Caswell in recent years on ferroelectric ceramics for pyroelectric applications is reviewed briefly. With the ultimate aim of fully CMOS compatible integrated thermal detectors and imagers, pure and lanthanum doped lead titanate thin films have been deposited using the emerging PVD technique of dual ion beam sputtering (DIBS). The DIBS process produces high quality orientated perovskite films. Films have been formed at 500–600°C onto sapphire, MgO and silicon substrates by sputtering from an adjustable composite PLZT ceramic/Ti and Pb metallic target. Some substrates were coated with platinum/titanium prior to deposition to allow longitudinal electrical measurements to be made on the films. On silicon, the platinum/titanium electrodes were found to blister during the PLZT thin film deposition process. Pure and 7% lanthanum doped lead titanate films have shown pyroelectric effects with coefficients in the range 0.5–4.0 × 10^?4 Cm^?2 K^?1 and a figure of merit of 2.6 × 10^?5 Pa^?0.5 These results are encouraging with respect to the goal of integrated pyroelectric IR detector arrays on silicon. Further improvements should be possible since the process and substrate/electrode preparation have not yet been fully optimised.     

Piezo- and pyroelectric properties of lead scandium tantalate thin films

Abstract

This paper discusses the piezo- and pyroelectric properties of lead scandium tantalate thin films prepared by modified sol-gel technology. Films were deposited on Pt/Ti/SiO₂/Si-sub-strates at 530–630 °C. The quality of the thin films was optimized by design of both the deposition conditions and the solution chemistry. These approaches include spin coating speed, drying plus crystallization temperature and time, drying atmosphere, the use of rapid thermal annealing, PST sol composition, Pb-excess concentration and mixing method. The finished thin films were characterized by optical microscopy, X-ray diffraction, atomic force microscopy, and pyroelectric measurements at 30°C under a DC-bias. Piezo-response AFM was conducted on PST to monitor various piezoelectric responses, which depend on the micro-structure of the film. The maximum pyroelectric figure-of-merit F_D was 3.85×10^?5 Pa^?1/2 at 30°C and 1 kHz under a 35 V DC-bias.     

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.     

Preparation and characterization of PZT thin films deposited on PZT buffer layer with different lead content

Lead zirconate titanate (PZT) thin films deposited on Pt electrode and Pb_1+x(Zr_0.52,Ti_0.48)O₃ (x = 0.10, 0.15, 0.25, 0.30) buffer layer have been prepared by sol-gel methods to investigate the effects of lead content in the buffer layer on crystalline orientation, electric and fatigue properties of PZT films. XRD and SEM showed that all films exhibited dense perovskite structure with (100) preferential orientation. The maximum dielectric constant (1571 at 100 Hz) was obtained in the PZT film with buffer layer containing 25% excess lead, which increased by 42.5% compared with the film without buffer layer. Fatigue resistance was improved by introducing buffer layer.     

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.     

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.     

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.     

Pyroelectric, dielectric, and piezoelectric properties of MnO2-doped (Na0.82 K0.18)0.5Bi0.5TiO3 lead-free ceramics

MnO₂ doped (Na_0.82 K_0.18)_0.5Bi_0.5TiO₃ lead-free piezoelectric ceramics were prepared by conventional solid-state reaction process and the effect of MnO₂ addition on the pyroelectric, piezoelectric and dielectric properties were studied. The experiment results showed that the pyroelectric, piezoelectric, and dielectric properties strongly depended on MnO₂ addition in the (Na_0.82 K_0.18)_0.5Bi_0.5TiO₃ ceramics. Excellent electrical properties were obtained in (Na_0.82 K_0.18)_0.5Bi_0.5TiO₃ with 0.8?mol% MnO₂. The large dielectric loss of pure BNT ceramics was significantly reduced, the piezoelectric constant was improved, and it also showed excellent pyroelectric properties when compared with other lead free ceramics, with pyroelectric coefficient p?=?17?×?10^?4?C/m²K and figure of merit F _d ?=?6.56?×?10^?5?Pa^?0.5. With these outstanding pyroelectric properties, the 0.8?mol% MnO₂ doped (Na_0.82 K_0.18)_0.5Bi_0.5TiO₃ ceramic can be a promising material for pyroelectric sensor applications in future.     

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.     

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.     

Preparation of thick PZT films on stainless steel substrates

Abstract

Lead zirconate titanate (PZT, PbZr_0.52Ti_0.48O₃) films of thickness 22 μm have been deposited on stainless steel substrates by spin-coating a PZT solution containing PZT powder. The solution had a concentration of 1.2 M and was dispersed with PZT powder in a 1:1 powder/solution molar ratio. The films were rapidly heated to 400°C and annealed for 15 min, and then they were further annealed in an oven at 650°C for 30 min. The results of X-ray diffraction studies show that the films have a pure perovskite phase. The inter-diffusion of ions at the PZT/stainless steel interface was prevented by using a ZrO₂ barrier layer. The films were found to have good ferroelectric and piezoelectric properties.     

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.     

Fabrication of sub 50-nm direct-patterned Pb(Zr,Ti)O<Subscript>3</Subscript> films by electron beam-induced metal-organic deposition

Direct-patterned lead zirconate titanate (PZT) films prepared from an electron beam sensitive stock solution were investigated for advanced stage applications in sub 50-nm patterned systems. The required electron beam dose for the direct-patterning of PZT precursor films was 4.5 mC/cm². The PZT precursor films with pattern size of 500 × 500 μm² were exposed to an electron beam for 2 h and annealed at 400°C for 30 min under an O₂ ambient. After exposure and annealing, values of the remnant polarization and coercive field were 7.0 μC/cm² and 97 kV/cm at 10 V, respectively. These results suggest a possible application of PZT films in micro- or nano-electromechanical systems.     

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.     

Electrical and optical properties of PZT ferroelectric films fabricated by the PVP-assisted sol-gel method

Lead zirconate titanate (PZT) films were deposited on platinized silicon substrates by spin coating using organic macromolecule polyvinylpyrrolidone (PVP) as an additive, which has the hybrid effects, was dispersed uniformly into the sol-gel precursor solution of PZT. The films were coated by spin-coating and then annealed at a proper temperature by repaid thermal processing. PZT ferroelectric films were polycrystalline and perovskite phase structure. The Coercive Field and remnant polarization of the PZT films annealed at 600 °C were 91 kV/cm and 19 μC/cm² respectively. The fatigue resistance properties were improved and the polarization value decreased only 8% of the initial polarization at 10⁸ cycles. The optical properties were measured by spectrophotometer and the band energy was calculated about 3.59eV.     

Piezoelectric and Pyroelectric Properties of Pb(Zr,Ti)O3 Films for Micro-Sensors and Actuators

The piezoelectric and the pyroelectric properties of PZT films are systematically investigated for tetragonal (Zr/Ti = 30/70), morphotropic (52/48), and rhombohedral (70/30) compositions. The magnitude of the effective longitudinal piezoelectric coefficient (d₃₃) and pyroelectric coefficient (p) of these films is measured by atomic force microscopy and Byer-Roundy method, respectively. All films are consistently highly textured (111) orientation and have dense microstructures. Slightly less degree of texture in higher Zr-rich composition is observed due to the lattice mismatch between PZT and Pt bottom electrode and higher activation energy for nucleation. Squareness of polarization hysteresis loops is optimized in tetragonal composition, which indicates the tetragonal PZT is closer to the ideal hysteresis behavior than other compositions. It is shown that the piezoelectric coefficient and the pyroelectric figure of merit are dependent on the dielectric properties of the films. The morphotropic PZT films with high dielectric constant and low pyroelectric figure of merit show the largest piezoelectric coefficient values, while the tetragonal PZT films with low dielectric constant and high remanent polarization values show the largest pyroelectric figure of merit compared to other compositions, which indicate the suitability for PIR sensor devices.