PZT thick films by diol chemical solution deposition

Process optimization and properties of lead zirconate titanate (PZT) films for piezoelectric micromachined ultrasonic transducers (pMUTs) for scanning probe devices will be presented. The goal of the work was a replacement of the tetragenic and mutagenic solvent and a decrease of time-consuming PZT 2-methoxy ethanol (2MOE) route. An alternative diol-based solution synthesis process was developed and "Design Of Experiment" (DOE) was used to achieve processing optimization for thick and crack free films. Tight parameter control allowed to develop a highly reproducible PZT diol process. The crystallization behaviour of crack-free PbZr0.53Ti0.47O3 films (1-5 mu m) with oriented perovskite structure was examined by X-ray diffraction and surface analysis using scanning electron microscopy. Piezoelectric and dielectric properties were examined. The effective transverse piezoelectric coefficient e(31,f) of sol-gel processed films was investigated for 4 mu m thick layers. Best properties were achieved with {1 0 0}-textured films, where a remanent e(31,f) value of -7.3 C/m(2) was measured for 4.1 mu m thick films.

Properties and phase transitions in lead free piezoelectrics

Naama Klein

Piezoelectric materials are used in a wide range of applications, with lead zirconate titanate (PZT) ceramics being the dominant family of materials, due to high piezoelectric coefficients, dielectric permittivity and coupling factors. The high properties have been found in compositions in the proximity of a morphotropic phase boundary (MPB). The MPB exhibits a weak temperature dependence so that the stability of the properties is attained over a large temperature range. However, environmental problems rising from the toxicity of lead have driven scientists around the world to search for lead free piezoelectric materials. These new materials should exhibit properties comparable to those of PZT and the efforts are at the present concentrated on solid solutions with an MPB. In this thesis an emphasis was made on constructing the phase diagrams and detecting an MPB in two of the most promising families of lead-free solid solutions: bismuth sodium titanate based and potassium sodium niobate based ceramics and single crystals. By investigating the structure of the phases, using X-ray and neutron diffractions and Raman spectroscopy, and measuring the dielectric and piezoelectric properties at temperatures from -266 °C to 550 °C, the phase transitions were assigned and phase diagrams constructed. Both systems (1-x)(Bi0.5Na0.5)TiO3-xBaTiO3 (0 ≤ x ≤ 0.09) (BNBT) and (1-x)(K0.5Na0.5)NbO3-xLiNbO3 (0.02 ≤ x ≤ 0.1) (KNLN), reveal similar MPBs to the one found for PZT. However, in PZT the MPB is pseudovertical up to about 350 °C whereas the MPB in BNBT is vertical only till 75 °C and in KNLN is till -50 °C. This difference in the temperature stability range is crucial in most applications. Other interesting findings in the BNBT phase diagram correspond to the phase sequence at the temperature range from 200 to 300 °C, where ferroelectric phase transforms into a mixed phase (antiferroelectric or paraelectric) with polar regions. As temperature rises, the polar regions gradually disappear. Whereas dielectric and piezoelectric properties of BNBT could compete with those of PZT in some compositions, and fairly simple processing of the ceramics is used, the fabrication of KNLN ceramics has shown to be complex and reproducible properties difficult to obtain. Even after the critical processing conditions were identified in this thesis, and reproducibility was achieved, properties were significantly lower than for PZT. Exceptional values of the thickness coupling coefficients were measured on potassium niobate (KN) and KNLN single crystals rotated away from the Z axis by θ = 45° about the orthorhombic Y axis, [001]C-cut. Monodomain and domain-engineered single crystals cut at this angle showed very high coefficients (kt ≤ 70%), which are extremely stable over a large temperature range and after thinning to thickness below 60 µm. Together with low permittivity, these properties make KN single crystals a good candidate for high-frequency applications. The higher permittivity of KNLN makes it an attractive crystal for applications at lower frequencies. Another possible application of lead free piezoelectrics could be in biological systems. For this reason, preliminary in-vitro biocompatibility study of KNLN and PZT ceramics was conducted, showing similar microscopic attachment of cells to the two ceramics and slightly lower viability values when compared to non coated tissue culture plates. Laboratory attempts to introduce KNLN ceramics as an implant in the mineral of the bone, hydroxyapatite (HA), ended with a strong chemical reaction between the two. However, some piezoelectric response could be measured from the composite of HA and KNLN.

EPFL2009

Extrinsic contributions to the piezoelectric response of lead-based ferroelectrics

The present study aims at a better understanding of the high piezoelectric properties encountered in lead-based ferroelectrics by focusing on the extrinsic contributions to the response. The main characteristics of these materials are the highly nonlinear character of the electro-mechanical response and the presence of a morphotropic phase boundary (MPB) where properties are reaching a maximum. Thus, our approach was first to develop a new description for the piezoelectric hysteresis and nonlinearities and second to investigate MPB effects on the extrinsic contributions to the piezoelectric response. For these purposes, lead titanate (PT), lead zirconate titanate (PZT), and lead nickel niobate-lead zirconate titanate solid solution (PNN-PZT) were chosen as prototype compositions. The sample preparation was classical for the first two compounds whereas two new synthesis routes of PNN-PZT were developed. The first consists in the preparation of a B-site precursor combining all the perovskite B-site cations before calcination with lead oxide, enhancing chemical homogeneity and insuring good reproducibility in the final properties. The second processing method aimed at more time efficiency: the use of a nickel hydroxy-carbonate instead of nickel oxide permitted to obtain in one single calcination step a pure perovskite phase exhibiting properties as high as those obtained for two firing steps procedures. The piezoelectric hysteresis and nonlinearity description was undertaken using the Preisach formalism, first developed in ferromagnetism. This approach considers that each hysteretic system satisfying the wiping-out and the congruency properties can be seen as composed of bistable units characterized by distributed coercive and bias fields. In our case, the use of a general expression for the unit parameters distribution function permitted to describe the most significant piezoelectric coefficient nonlinearities such as applied field dependence, saturation or threshold fields. Moreover, a minimal expression describing the piezoelectric nonlinearity in lead-based compounds was derived from experimental determination of the distribution function topography. Advanced piezoelectric hysteresis modelling was attained by coupling the classical viscous descriptions with Preisach-inspired loops expressions. This allowed to separate piezoelectric losses into viscous and field dependent parts. Moreover, the possibility of extracting distribution function parameters from the loops was established. The versatility of the Preisach hysteresis description was also demonstrated by deriving pinched ferroelectric loops from the supposed microscopical mechanisms in hard-doped ferroelectrics. Morphotropic phase boundary study started with the derivation of a composition-temperature phase diagram for PNN-PZT using dielectric and pyroelectric measurements along with X-ray diffraction. The MPB of this solid solution was shown to be strongly curved toward the rhombohedral side. Therefore, certain compositions undergo a tetragonal to rhombohedral transition upon cooling. The influence of electric field and thermal history on this morphotropic transition was first investigated in view of optimizing the poling conditions of such materials. Then, the piezoelectric extrinsic contributions at MPB for both PZT and PNN-PZT were studied as a function of composition and temperature. The peak of properties occurring in this region was assigned to intrinsic effects coupled with an extension of the irreversible contributions. Using the developed hysteresis and nonlinearity formalism, this extrinsic contributions increase could be related to an extended response of each defect rather than to an increase in the defects density.

EPFL2001

Pulsed laser deposition of (SrBa)Nb2O6 thin films and their properties

Anna Infortuna

Strontium barium niobate (SrxBa1-xNb2O6, shortly SBN) is a solid solution system with tetragonal tungsten bronze crystal structure. It exhibits a ferroelectric phase with only one polar axis and a transition temperature depending on the Sr/Ba ratio. This thesis studies the growth of SBN thin films, in order to obtain a ferroelectric thin film model system for the study of 180° domain switching close to the ferroelectric phase transition. SBN has been chosen not only because uniaxial, but because it is possible to tune the temperature of phase transition varying the Sr/Ba ratio. It is thus possible to study electric properties of the phase transition close to room temperature, where conduction phenomena related to defects are normally lower. Thin films of SBN were grown by Pulsed Laser Deposition in a vacuum system constructed during this thesis work. For the formulation of a model it is desirable to have a system as close as possible to a single crystal. Therefore deposition parameters have been optimized to grow SBN thin films with the polar axis oriented perpendicular to the film plane. The films are integrated in parallel plate capacitor structures, in order to measure dielectric properties. The stability of the ferroelectric phase is found to be sensitive to impurities; contaminants with concentration below 1% induce a lowering of the transition temperature of about 100°C. Strain as well has influence on the phase transition; in the case of substrate with thermal expansion coefficients different from the SBN ones, the SBN film is under stress. A 0.6% tensile strain induces a lowering of the transition temperature of about 100°C, this is the case of silicon single crystal substrate. Grown on strontium titanate single crystals (STO), whose thermo-mechanical properties are close to the one of SBN, the films exhibit a phase transition temperature compatible with the one measured on single crystals. The obtained films suffer from leakage that is reduced by thermal treatment in oxygen rich atmosphere. The oxygen vacancies, created during the deposition process, are considered to be responsible of leakage. Vacancies recovery upon annealing does not eliminate the problem, and measurement of polarization at room temperature is difficult. However, piezoelectric measurements performed on individual grains, with atomic force microscope, prove that these have ferroelectric properties; by these experiment has been proved that it is possible to switch the polarization. Films with a disordered structure of grains are much less leaky than the ones with columnar grains spanning the whole cross section. These observations lead to the conclusion that conduction goes trough the grain boundaries. On STO single crystals, SBN grows epitaxial in Volmer-Weber mode. With a suitable preparation of the substrate surface, it is possible to induce the growth of films with different orientations of the polar axis: in the film plane, perpendicular to it or inclined of 45°. A model is proposed, explaining the epitaxial relation with the substrate on the basis of the perovskite kernel contained in the unit cell of the tetragonal tungsten bronze structure. The film grows from the nucleation of the perovskite structure that rules the orientation of the film; the high temperature at which the substrate is kept during the deposition, assure the necessary mobility for the arriving atoms to organize in the SBN structure around these nuclei. The study of literature data allows to state that such a model is valid not only for substrates with perovskite structure, but can be extended to substrates with a cubic crystal structure, like magnesium oxide.

EPFL2005