Ce travail de thèse porte sur les propriétés structurales et électroniques des parois de domaines ferroïques ; il a pour objectif une meilleure compréhension des mécanismes de conduction dans les parois de domaines du niobate de lithium d’une part, et de la polarité des parois de domaine dans le titanate de calcium d’autre part. La première partie est consacrée aux interactions entre les défauts et les parois de domaine dans le niobate de lithium. L’observation d’une relaxation diélectrique de faible énergie d’activation et l’analyse de son comportement sous l’effet d’un recuit dans des échantillons avec et sans parois nous conduisent à proposer que les parois de domaines stabilisent des états polaroniques. Nous rapportons aussi l'évolution de modes Raman dans des échantillons congruents de niobate de lithium dopés de manière croissante en magnésium. Nous identifions des décalages en fréquence spécifiques aux parois de domaines. Les parois de domaines apparaissent alors comme des lieux de stabilisation des défauts polaires. Nous utilisons la microscopie électronique miroir (MEM) et la microscopie électronique de faible énergie (LEEM) pour caractériser les domaines et parois de domaines à la surface du niobate de lithium dopé magnésium. Nous démontrons que les réglages de la distance focale peuvent être utilisés pour déterminer la polarisation du domaine. Aux parois de domaines, un champ électrique latéral, provenant de différents états de charge de surface, est mis en évidence. Dans une seconde partie, nous étudions la polarité des parois de domaine dans le titanate de calcium. Nous utilisons la spectroscopie de résonance piézo-électrique pour mettre en évidence l’excitation de résonances élastiques par un signal électrique, ce qui est interprété comme une réponse piézoélectrique des parois de domaines. Une image directe des parois de domaine du titanate de calcium est obtenue par LEEM, et montre une différence de potentiel de surface entre domaines et parois. Ce contraste peut être modifié sous l’effet d’injection d’électrons, par un effet d’écrantage des charges de polarisation aux parois. / We investigate the structural and electronic properties of domain walls to achieve a better understanding of the conduction mechanisms in domain walls of lithium niobate and the polarity of domain walls in calcium titanate. In a first part, we discuss the interaction between defects and domain walls in lithium niobate. A dielectric resonance with a low activation energy is observed, which vanishes under thermal annealing in monodomain samples while it remains stable in periodically poled samples. Therefore we propose that domain walls stabilize polaronic states. We also report the evolution of Raman modes with increasing amount of magnesium in congruent lithium niobate. We identified specific frequency shifts of the modes at the domain walls. The domains walls appear then as spaces where polar defects are stabilized. In a second step, we use mirror electron microscopy (MEM) and low energy electron microscopy (LEEM) to characterize the domains and domain walls at the surface of magnesium-doped lithium niobate. We demonstrate that out of focus settings can be used to determine the domain polarization. At domain walls, a local stray, lateral electric field arising from different surface charge states is observed. In a second part, we investigate the polarity of domain walls in calcium titanate. We use resonant piezoelectric spectroscopy to detect elastic resonances induced by an electric field, which is interpreted as a piezoelectric response of the walls. A direct image of the domain walls in calcium titanate is also obtained by LEEM, showing a clear contrast in surface potential between domains and walls. This contrast is observed to change reversibly upon electron irradiation due to the screening of polarization charges at domain walls.

Lithium niobate (LiNbO3) and KTiOPO4 (KTP) are ferroelectric crystals of considerable interest in different fields of optics and optoelectronics. Due to its large values of the nonlinear optical, electro-optic (EO), piezoelectric and acousto-optical coefficients, LiNbO3 is widely used for laser frequency conversion using the quasiphase matching (QPM) approach where the sign of nonlinearity has been periodically modulated by electric field poling (EFP). In the microwave and telecommunication field LiNbO3 is used for surface acoustic devices and integrated optical modulators. KTP and its isomorphs, on the other hand, exhibit slightly lower nonlinear coefficients but have much higher photorefractive damage thresholds, so that it is mainly used in the fabrication of QPM devices for both UV, IR and visible light generation and in high power applications. This thesis focus on different key issues: (1) accurate characterization of specific optical properties of LiNbO3, which are of interest in nonlinear and EO applications; (2) in-situ visualization and characterization of domain reversal by EFP in LiNbO3 and KTP crystals for a through understanding of the ferroelectric domain switching; (3) fabrication of periodic surface structures at sub-micron scale in LiNbO for photonic applications. An interferometric method is used for accurate measurement of ordinary and extraordinary refractive indices in uniaxial crystals, which is of great interest in the proper design of QPM crystals. A digital holography (DH) based method is presented here for 2D characterization of the EO properties of LiNbO , which is considerably interesting in the applications where the proper design of the EO device requires a spatially resolved information about the EO behaviour and the existing pointwise techniques are not sufficient. A DH method for novel in-situ monitoring of domain reversal by EFP in both LiNbO3 and KTP, is also presented here. The technqiue could be used as a tool for high fidelity periodic domain engineering but also provides information about domain kinetics, internal field and crystals defects. 3 3 3 Finally this thesis presents novel results concerning nanoscale periodic surface structuring of congruent LiNbO3. Holographic lithography (HL) is used for sub-micron period resist patterning and electric overpoling for surface domain reversal. Surface structures are obtained by selective etching. Moiré effect is also used in the HL to fabricate complicated structures with multiple periods. The depth compatibility with waveguide implementation allows foreseeing possible applications of these structures for Bragg gratings or innovative photonic crystal devices, exploiting the additional nonlinear and EO properties typical of LiNbO3. / QC 20100824