Bismuth layer-structured ferroelectrics have been recognised as promising film materials for ferroelectric random access memory application due to their excellent fatigue resistance and other electrical properties. This work deals with the deposition and characterisation of epitaxial and polycrystalline W-doped SrBi2Ta2O9 (SBT) and lanthanide-doped bismuth titanate (BiT) films. SBT and W-doped SBT films were fabricated by pulsed laser deposition (PLD) on platinised silicon substrates. The effects of fabrication temperature and W-doping level on film properties were studied. The crystallinity of SBTW films improved with increasing fabrication temperatures, resulting in enhanced ferroelectric properties and dielectric properties above the fabrication temperature of 750 °C. Dense ceramic samples of Nd- and Sm-doped BiT (BNdT and BSmT) were successfully fabricated for PLD targets by solid state processing. Highly epitaxially (001)-, (118)-, and(104)-oriented Nd-doped bismuth titanate (BNdT) films were grown by PLD on (001)-, (011)-,and (111)-oriented SrTiO3 (STO) single crystal substrates, respectively. A three-dimensional orientation relationship between films and substrates was derived as: BNdT(001)//STO(001),BNdT[ 110 ]//STO[100]. Films showed strong dependence of structural and ferroelectric properties on the crystal orientation. PLD-grown BSmT films on platinised silicon substrates were studied as a function of fabrication temperature, effects of Pt bottom layer orientation, Sm doping level, and LaNiO3 buffer layer. An alkoxide-salt chemical solution deposition (CSD) method was adopted to prepare the precursors for BSmT (BNdT) film fabrication. Precursors of Bi-Sm(Nd)-Ti which were stable for at least eight months in air ambient were successfully developed. In-situ FT-IR studies suggest that acetic acid serves as chelating agent to improve the homogeneity of the precursor solution by generating a dense and homogeneous Ti-O-Ti polymeric network. The electrical properties of the films fabricated in this study (dielectric and ferroelectric properties, leakage current characteristics and electrical fatigue properties), are comparable or superior to these previously reported for similar films developed by other techniques or with other doping elements. Low temperature electrical properties of BSmT films suggest that the films are very promising for extremely low temperature nonvolatile memory applications. The results of BNdT films annealed at different oxygen partial pressure (O2, air, N2) showed that oxygen ambience affected structural properties of the films by enhancing the growth of perovskite phase (phase formation), increasing grain size (grain growth), and assisting the growth of (117)-oriented grains (crystallographic orientations). Piezoresponse force microscopy (PFM) was adopted to characterise BSmT films. Domain structures were clearly observed in a PLD-grown BSmT film, which were closely related to the grain structures. Domain manipulation was carried out in a CSD-derived BSmT film, showing that the film can be nearly uniformly polarised, which can be used in nanoscale device fabrication. Clear hysteresis loops were measured by PFM, which was an important proof of ferroelectricity. Large spatial variations of piezoelectric hysteresis loops of a CSD-derived BSmT film were observed across the film surface. Effective electrostriction coefficient (Qeff) of a PLD-grown BSmT film was measured, showing that BSmT films had better piezoelectric properties (higher Qeff, higher dzz) than SBT films, un-doped BiT ceramics and films. It suggests that BSmT films are promising piezoelectric materials for MEMS use.

Piezoelectric materials are widely used for sensors, actuators and trasducers. Traditionally, piezoelectric applications are dominated by multicomponent oxide ferroelectrics such as lead zirconate titanate (PZT), which have the advantage of high piezoelectric coefficients. Recently, one-dimensional piezoelectric nanostructures such as nanowires of zinc oxide (ZnO) and gallium nitride (GaN) has gained a lot of attention due to their combined piezoelectric and semiconducting properties. The focus of this thesis is to study the processing and electric properties of such piezoelectric thin films and nanostructures for various applications. There is an increasing interest to form thin films of multicomponent ferroelectric oxides such as PZT on three-dimensional structures for charge storage and MEMS applications. Traditional vapor phase deposition techniques of PZT offer poor conformality over threedimensional surfaces due to their reactant transport mechanisms. As an alternative, solgel synthesis may provide new process possibilities to overcome this hurdle but the film quality is usually inferior, and the yield data was usually reported for small device areas. The first part of this study is dedicated to the characterization of the electric properties and yield of PZT thin film derived from the sol-gel process. PZT thin films with good electric property and high yield over a large area have been fabricated. La doping was found to double the breakdown field due to donor doping effect. LaNiO3 thin films that can be coated on a three-dimensional surface have been synthesized by an all-nitrate based sol-gel route, and the feasibility to form a conformal coating over a three-dimensional surface by solution coating techniques has been demonstrated. ZnO and GaN micro/nanowires are promising piezoelectric materials for energy harvesting and piezotronic device applications. The second part of this study is focused on the growth of ZnO and GaN micro/nanowires by physical vapor deposition techniques. The morphology and chemical compositions are revealed by electron microscopy. Utilizing the as-grown ZnO nanowires, single nanowire based photocell has been fabricated, and its performance was studied in terms of its response time, repeatability, excitation position and polarization dependence upon He-Cd UV-laser illumination. The excitation position dependence was attributed to the competition of two opposite photo- and thermoelectric currents originated from the two junctions. The excitation polarization dependence was attributed to the difference in optical properties due to crystallographic anisotropy. Employing the as-grown GaN nanowires, single nanowire based strain sensor is demonstrated, and its behavior is discussed in terms of the effect of strain-induced piezopotential on the Schottky barrier height.

Une des méthodes utilisées pour étudier la ferroélectricité à l'échelle nanométrique dans les couches minces est la technique appelée « Piezoresponse Force Microscopy » (PFM). La PFM est un mode dérivé de l’AFM (Atomic Force Microscopy) en mode contact. Cette technique est basée sur l’effet piézoélectrique inverse : lorsqu’on applique un champ électrique sur un matériau piézoélectrique celui-ci se déforme. La pointe est posée sur la surface et mesure donc une déformation locale due à la tension appliquée. Les résultats obtenus par PFM sur des couches minces deviennent difficiles à interpréter dès lors que des charges d’origine non ferroélectriques (différentes de la charge de polarisation) entrent en jeu : charges électroniques piégées dans l’oxyde après l’injection de courant dues aux courants de fuite, charges déjà présentes dans la couche, les charges de surface, ainsi que les différents phénomènes électrochimiques due à la présence de la couche d’eau sous la pointe lors des mesures sous atmosphère ambiante. Le but de ce travail de thèse est de montrer que dans le cas de couches très minces les courants de fuite et les phénomènes électrochimiques peuvent conduire à l’interprétation de résultat PFM erroné. Des mesures PFM ont été réalisées sur des couches minces de PbZrTiO3, BaTiO3 et des nanostructures de BiFeO3 ferroélectriques. Les paramètres de mesure utilisés en PFM sont discutés avec une attention particulière sur la première résonance de contact qui permet d’amplifier le signal PFM. L’impact des phénomènes électrochimiques sur le contraste en PFM est discuté et mis en évidence d’un point de vue expérimentale. Des images PFM sur des couches minces non-ferroélectriques sont obtenues semblable à celle obtenues lors de l’utilisation d’une procédure standard sur des échantillons ferroélectriques. Ces images sont réalisées sur des couches minces d’aluminate de lanthane (LaAlO3), d'oxyde de Gadolinium (Gd2O3) et d’oxyde de Silicium (SiO2). Les motifs obtenus sur le LaAlO3 et le Gd2O3, similaires à des domaines de polarisation opposés, tiennent dans le temps sous atmosphère ambiante. Ces mesures sont comparées avec des résultats obtenus sur des couches minces de BaTiO3 préparées par MBE (Molecular Beam Epitaxy). Différentes méthodes de caractérisation électriques à l’échelle macroscopique sont présentées afin de confirmer la ferroélectricité des couches minces étudiées dans cette thèse. L'objectif est de disposer d'une procédure permettant d'affirmer qu'un échantillon dont on ne sait rien est ou n'est pas ferroélectrique. / Piezoresponse Force Microscopy (PFM) is a powerful tool for the characterization of ferroelectric materials thanks to its ability to map and control in a non destructive way domain structures in ferroelectric films. Most of the time, the ferroelectric behaviour of a film is tested by writing domains of opposite polarization with the Atomic Force Microscope (AFM) tip and/or by performing hysteresis loops with the AFM tip as a top electrode. A given sample is declared ferroelectric when domains of opposite direction have been detected; corresponding to zones of distinct contrast on the PFM image, or when an open hysteresis loop is obtained. More prudently in certain cases, the ferroelectricity is at last attested only when the contrast is stable within several hours. But as the thickness of the films studied by PFM decrease, data become difficult to interpret. In particular, charges trapped after current injection due to leakage currents and electrochemical phenomena due to the water layer under the tip may contribute in a non-negligible way to the final contrast of PFM images. In this thesis, some PFM measurements are performed on ferroelectric PbZrTiO3, BaTiO3 thin films and BiFeO3 nanostructures. Different parameters used in PFM measurements are discussed with special attention on the buckling first harmonic PFM measurements which allow the amplification of the PFM signal. The impact of electrochemical effects on the PFM contrast are discussed and are shown experimentally. Then, the standard procedure which is used in order to show the ferroelectricity of a film is applied to a non-ferroelectric sample with apparently the same results. To do so, we use a LaAlO3, Gd2O3 and SiO2 amorphous dielectric films and apply similar voltages as for artificially written ferroelectric domains. The resulting pattern is imaged by PFM and exhibit zones of distinct PFM contrasts, stable with time, similar to the one obtained with ferroelectric samples. These results are explained and is compared with results obtained on BaTiO3 thin films prepared by Molecular Beam Epitaxy which are supposed to be ferroelectric. In order to confirm the ferroelectricity of our thin films, several macroscopic electrical techniques are introduced. The aim of this study is to establish a reliable procedure which would remove any ambiguity in the characterization of the ferroelectric nature of such samples.