Advanced sol-gel processing of PZT thin films for piezoelectric MEMS structures

Micro-electro-mechanical systems (MEMS) technology is revolutionizing industrial and consumer products by replacing bulky devices by miniaturized versions that are suitable for portable applications as for instance in mobile phones. Besides small size, the keys for the success are reproducibility, batch processing, and significantly cheaper prices due to mass production. Whereas standardMEMS processing relied fromits beginning on standard CMOS materials, increasing need in extreme requirements or exploitation of specific phenomena demands for the integration of new materials. The interest is particularly strong in piezoelectric MEMS devices due to their higher efficiency in converting electrical to mechanical energy and vice versa, and thus their ability to provide electro-mechanical transducers. Since most of the actively used piezoelectric materials are ceramic in nature, they must be synthesized at rather high temperatures, which pose challenges to integration routes. The recent years can be considered as the starting phase of product development of piezo-MEMS. As a result, a very high interest is put on further improving the quality of piezoelectric thin films, meaning higher sensitivity in MEMS sensors and larger stroke inmicro-actuators is remaining a key priority. Themost widely used piezoelectric thin filmmaterials forMEMS devices are zinc oxide (ZnO), aluminumnitride (AlN) and lead zirconate titanate (PZT). AlN is used extensively forMEMS resonator structures due to its high quality factor and low losses. It is also investigated for sensors where linearity and stability of the piezoelectric response is mandatory. PZT films are used in actuators and acoustic transducer applications because of their high piezoelectric coefficients and electromechanical coupling coefficients. In this work, energy harvesting is specifically considered as motivation for property evaluation and optimization. In this case, the piezoelectric thin filmis used like a sensor for vibrations andmotions, though with the optimization requirement that the product of current and voltage must be maximal. [...]

Internal electric fields and electrode effects in ferroelectric thin films for piezoelectric energy harvesting

Robin Nigon

The continuing decrease of power requirements of electronic circuits offers the potential to deploy wireless systems as embedded sensors for cars or industrial tools, and implanted medical devices. Harvesting ambient vibrations by an appropriate energy harvesting (EH) device allows to avoid an undesirable battery replacement. At the scale of micro-electromechanical systems, where severe size constraints must be met, microfabricated EH devices with piezoelectric thin films offer the best energy density. Ferroelectric lead zirconate titanate (PZT) thin films with interdigitated electrodes (IDE) appear as the most promising device design for this purpose. Accurate characterization of the thin film response is necessary to determine the PZT composition and doping, the electrode geometry, and the stack design for maximum EH efficiency. Unfortunately, there is no rigorous description of the physical behavior of the IDE system to date. One goal of this thesis was thus to provide a better understanding of the experimental observations made by previous researchers. In addition, only a limited PZT composition and doping range has been investigated in this configuration. It was the second goal of this thesis to widen this range in order to determine the combination that yields the best EH efficiency. Finally, the risk of partial or total depoling over the device lifetime is always present in ferroelectric materials. The phenomena of aging and self-poling are of great interest to ensure proper retention of the poled state and, thus, the reliability of the harvesting device. Neither of the two are well understood. It was the third goal of this thesis to investigate the aging behavior and methods to promote self-poling. In this thesis work, we have have proposed a description of the physical behavior of the IDE system, and we have developed an analytical model for extracting the effective material properties from standard characterization measurements, which is well supported by both finite element (FE) simulations and experimental data. We found that if the substrate is conductive enough, a parasitic capacitance is present in parallel to the material response. We have provided a method to subtract the contribution of the parasitic capacitance, which has an accuracy of better than 4% in a wide range of IDE geometries as determined by FE simulations. We have investigated the performances of doped PZT thin films with IDE for several combinations of dopant and composition. We have improved an existing fabrication route to obtain textured PZT films on an insulating MgO layer. We found that dopants systematically reduced the piezoelectric response and retention capability, and increased the dielectric constant. All three are detrimental for EH. Undoped compositions should be chosen. We have studied methods to improve the stability of the poled state through aging and self-poling. Introducing the latter into the IDE configuration did not provide sufficiently strong effects to be of practical interest. On the contrary, the aging process may allow to tune the extrinsic contributions to the dielectric and piezoelectric response. It is likely caused by polarization discontinuities at grain boundaries. Further work is needed for fully optimizing this phenomenon. Finally, from the previous investigations, we could deduce and propose golden rules for the design of IDE structures, and discuss typical applications where they are advantageous.

EPFL2017

Pb(Mg1/3Nb2/3)O-3 and (1-x)Pb(Mg1/3Nb2/3)O-3-xPbTiO(3) relaxor ferroelectric thick films: Processing and electrical characterization

Dragan Damjanovic, Nava Setter

The lead magnesium niobate [Pb(Mg1/3Nb2/3)O-3 or PMN], and its solid solutions with lead titanate (PbTiO3 or PT), are of great interest because of their high electromechanical properties. At large PMN content, these materials exhibit relaxor characteristics with large electrostrictive strains and a large permittivity, while compositions near the morphotropic phase boundary present very interesting piezoelectric properties. So far, properties of these materials in ceramic, thin film and single-crystal form have been investigated. In this paper, we report on preparation and properties of pyrochlore free PMN and 0.65PMN-0.35PT thick films ( thickness = 10 to 20 mum). The films were prepared from ethyl cellulose ink by screen printing on alumina substrate. The influence of various parameters, such as powder characteristics, inks formulation and films sintering conditions, on films densification are discussed. The dielectric and electromechanical properties of the films were examined. Relaxor-like behaviour was clearly demonstrated in PMN films. The maximum relative permittivity for PMN film was 10000 (at 0.1 kHz), which is lower than in bulk ceramics ( 17800 at 0.1 kHz) prepared under the same conditions. For 0.65PMN-0.35PT, the maximum relative permittivity was around 15500 against 24000 in the bulk. Several parameters, which might be responsible for the lower permittivity, are discussed. Poled 0.65PMN-0.35PT thick films exhibit relatively large piezoelectric response (d(33) up to 200 pm/V) and unipolar strains approaching 0.1%, making these films of interest for various actuator and transducer applications.

2004

Polarisation reversal in ferroelectric PVDF and PZT films

Roman Gysel

Ferroelectrics are characterised by a spontaneous polarisation that can be reversed by an external electric field. The stability of the polarisation states and the possibility for controlled switching between the states render ferroelectric materials very attractive for memory applications, in which polarisation states are associated to a binary information "0" or "1". Fast, dense, and reliable data storage has gained enormous importance in our information technology based society. In this context, the fundamental physics of ferroelectric materials attracted great interest with the ultimate goal of reaching memory elements with shortest access times and highest densities. Two model systems of ferroelectric materials were studied in this thesis on the polarisation reversal: an inorganic, classical perovskite and an organic polymer. Despite the fundamental structural differences between lead zirconate titanate [Pb(Zr,Ti)O3] and the investigated polyvinylidene fluoride-trifluoroethylene [P(VDF-TrFE)] copolymer, the switching kinetics in these materials can be described by a similar formalism. Our approach of a combination of macroscopic and microscopic techniques enables an insight into the mechanisms of the polarisation reversal and allows for a better understanding of macroscopic effects governed by mechanisms occurring on the nanoscale. The experimental techniques developed for the ferroelectric capacitor structures have been successfully applied for studying a first hybrid PVDF/silicon ferroelectric transistor for non-volatile information storage. The major accomplishments of this thesis are the following: We demonstrated for the first time a piezoelectric scanning probe study on the cross section of ferroelectric thin films. In combination with switching pulses, this allowed us to directly image the polarisation reversal in ferroelectric films quasi-dynamically. The utility of cross-sectional domain imaging as a powerful tool for the study of the polarisation reversal in ferroelectrics has been corroborated. The apparent contradiction between observations interpreted as a fast sideways growth and the classical scenario of a fast forward growth could be explained by an oblique polarisation direction with respect to the film plane. A surface-stimulated nucleation of reverse domains, with preference on the electrode with a negative potential was observed. It was interpreted in terms of a built-in field due to a depletion layer at the ferroelectric-electrode interface. A combination of microscopic and macroscopic methods used for the first time in organic ferroelectric thin films enabled a better insight into polarisation reversal of the copolymer of vinylidene fluoride and trifluoroethylene P(VDF-TrFE). The polarisation reversal was found to be impeded by a restricted domain growth. This limits the applicability of the conventional Kolmogorov-Avrami model as well as the nucleation-limited switching model with a broad distribution of nucleation times. We demonstrated that an interface-adjacent passive layer may impact on the switching properties and gives rise to a retardation of the polarisation reversal. Furthermore, an extraordinary dielectric constant increase was observed in the films with a passive layer due to an additional domain wall contribution. We fabricated for the first time a hybrid silicon/ferroelectric polymer ferroelectric single transistor memory element with non-volatile operation. The observed difference of the polarisation reversal kinetics of the ferroelectric in the simple capacitor and in the transistor structure was explained by the gate oxide buffer layer in the transistor. Our previously developed tools and approaches enabled a better understanding of retention loss mechanism. A semi-quantitative retention model was suggested that explains the observed exponential retention loss. The investigation of relevant fundamental aspects of ferroelectric materials and the development of novel characterisation techniques in this work can be of interest for further development of non-volatile memory devices.