Το φαινόμενο της μαγνητικής πόλωσης ανταλλαγής (exchange bias, EB) έχει προσελκύσει το επιστημονικό ενδιαφέρον εξαιτίας των σημαντικών εφαρμογών σε διατάξεις μαγνητικής αποθήκευσης πληροφορίας. Ιδιαίτερο ενδιαφέρον εμφανίζουν οι ΕΒ ιδιότητες των πολυστρωματικών φιλμ με σύσταση [La2/3Ca1/3MnO3(FM)/La1/3Ca2/3MnO3(AF)]15, που αποτελούνται από αντισιδηρομαγνητικά, La1/3Ca2/3MnO3 (AF), και σιδηρομαγνητικά, La2/3Ca1/3MnO3 (FM), στρώματα επειδή αυτή η κατηγορία ενώσεων ανήκει στα ισχυρώς συσχετιζόμενα ηλεκτρονικά συστήματα (strongly correlated electronic systems), όπου οι μαγνητικές-, ηλεκτρονικές-, και κρυσταλλικές-δομές αλληλεπιδρούν ισχυρά μεταξύ τους. Στην παρούσα διατριβή χρησιμοποιήθηκαν μετρήσεις περίθλασης και σκέδασης συντονισμού ακτίνων-Χ στην Κ-ακμή του Mn για την μελέτη της επίδρασης των ελαστικών τάσεων επιταξίας στο μηχανισμό της μαγνητικής πόλωσης ανταλλαγής της πολυστρωματικής δομής [La2/3Ca1/3MnO3/La1/3Ca2/3MnO3]15 που εμφανίζεται κάτω από την θερμοκρασία εμπλοκής ΤΒ≈80 Κ. Οι μετρήσεις περίθλασης ακτίνων-Χ έδειξαν ότι ο λόγος c/a, που αποτελεί το μέτρο της τετραγωνικής πλεγματικής παραμόρφωσης της ψευδοκυβικής δομής, φθάνει στην μέγιστη τιμή της, και ότι το μήκος συσχετίσεως εντός των (101) και (102) κρυσταλλογραφικών επιπέδων μεταβάλλεται σημαντικά κοντά στην ΤΒ. Αυτό το φαινόμενο οφείλεται στο γεγονός ότι στην ΤΒ η ψευδοκυβική πλεγματική σταθερά aML του φιλμ προσεγγίζει την τιμή της ψευδοκυβικής πλεγματικής σταθερά της ένωσης La1/3Ca2/3MnO3 από την οποία αποτελούνται τόσο το ενδιάμεσο στρώμα (buffer layer) όσο και τα AF στρώματα, αποδεικνύοντας έτσι ότι το EB φαινόμενο σχετίζεται με την εξισορρόπηση των επιταξιακών τάσεων εντός των AF και FM στρωμάτων. Οι μετρήσεις σκέδασης συντονισμού ακτίνων-Χ (RXS) αποκαλύπτουν ότι οι επιταξιακές τάσεις εξωθούν τα πολύεδρα MnO6 σε σιδηροπαραμορφωτική (ferrodistortive, FD) ευθυγράμμιση, όπου η FD υπερκυψελίδα συμπίπτει με την μοναδιαία κυψελίδα της κρυσταλλικής δομής. Εφαρμογή της τεχνικής συμβολής στα RXS φάσματα αποκαλύπτει μια κορυφή συντονισμού από την κύρια ακμή απορρόφησης των ιόντων Mn στα ~6.555 keV και μια, μικρότερης έντασης, δευτερεύουσα κορυφή συντονισμού στα ~6.55 keV, του οποίου η ενεργειακή μετατόπιση ελαττώνεται γραμμικά με την θερμοκρασία και το λόγο c/a μέχρι τους 80 Κ. Η εξαφάνιση της δευτερεύουσας κορυφής πάνω από τους 80 Κ(≈ΤΒ) μπορεί να σχετίζεται με κάποια αναδιάταξη των γωνιών που σχηματίζουν οι δεσμοί Mn-O-Mn εξαιτίας της εξισορρόπησης των επιταξιακών τάσεων στις FM/AF διεπιφάνειες κάτω από 80 Κ. / The exchange bias (EB) phenomenon has received considerable attention because of its important applications in magnetic storage devices. Of particular interest are the EB properties of colossal magnetoresistance (CMR) compositionally modulated structures consisting of antiferromagnetic (AF) and ferromagnetic (FM) (La,Ca)MnO3 layers because manganites are strongly correlated electron systems, in which the magnetic, electronic and crystal structures interact strongly with each other. Complementary x-ray synchrotron radiation diffraction (XRD) and resonant scattering (RXS) measurements were performed at the Mn K-edge between 10 and 300 K in order to analyze the effect of epitaxial strain and tetragonal lattice distortions on the exchange bias (EB) mechanism observed in [La2/3Ca1/3MnO3(FM)/La1/3Ca2/3MnO3(AF)]15 multilayers below a blocking temperature, TB, of 80 K. XRD measurements showed that the c/a axial ratio, an indication of the tetragonal lattice distortion in pseudocubic lattice settings, reaches its maximum at the onset of the EB effect and the corresponding structural correlation length varies substantially at the onset of TB. The in-plane lattice parameter a at TB is close to the bulk lattice parameters of the AF layers, thus indicating that the EB effect is related with the accommodation of strain inside the FM and AF layers. RXS measurements revealed that such anisotropic lattice strains force the MnO6 octahedral sites into a ferrodistortive (FD) alignment, where the FD supercell coincides with the unit cell of the crystalline lattice. The RXS intensity difference signal exhibits a main-edge feature and a post-edge feature at 6.57 keV that scales linearly with temperature and the c/a ratio up to 80 K. The disappearance of the post-edge feature above 80 K(=TB) may signify a rearrangement of Mn-O-Mn bonding angles due to strain-driven effects at the FM/AF interfaces, inducing disorder in FD octahedral tilt ordering which may pin the local distortions below the TB.

<p>Shape memory alloys (SMAs) belong to an important class of active materials. Beyond shape memory, these alloys exhibit super-elasticity and pseudo-plasticity, all originating from a reversible phase transformation from a high-temperature austenitic phase to a low temperature martensitic phase. Their unique thermo-mechanical properties make these SMAs desirable for a wide range of applications in automobiles, robotics, aerospace, construction, and medicine. Only a fraction of the known metallic alloys exhibits martensitic transformations, and a relatively small subset exhibits shape memory. Given this limited pool of SMAs, tunability of this martensitic transformation and, hence, thermo-mechanical properties is a way to move forward for effectively designing the next-generation SMAs for specific applications. The modification in composition has always been at the heart of designing new SMAs for future applications. However, a relatively recent discovery of incorporating a second non-transforming phase in base martensitic materials to tune martensitic transformation to achieve unprecedented thermo-mechanical properties has shown great promise.</p><p><br></p><p>The objective of this work is to utilize the second phase to provide design guidelines for next-generation SMAs and to understand the detailed physics behind the experimentally observed unprecedented thermo-mechanical properties in SMAs as a result of the incorporation of coherent second phases. We first investigate Mg-Sc shape memory alloys that are attractive for a wide range of applications due to their low density. Unfortunately, the use of these alloys is hindered by a low martensitic transformation temperature (173 K). We observe from first-principles calculations that epitaxial strains arising from appropriate substrate or coherent second phase selection increase the martensitic transformation and operational temperature to room temperature. Next, we develop a novel approach to induce martensitic transformation in composite systems of two non-transforming materials. While we demonstrate this approach for the technologically relevant ultra-lightweight Mg/MgLi superlattices, however, our approach is general and will open a wide material space for the discovery and design of next-generation SMAs.</p><p><br></p><p>Finally, to bridge the gap between computationally studied single-crystalline materials and experimentally studied polycrystalline systems, we characterize the role of nanoscale precipitates on temperature- and stress-induced martensitic phase transformation in nanocrystalline Ni63Al37 SMAs using multi-million-atoms molecular dynamics simulations. Simulations provide the understanding of underlying atomistic mechanisms of experimentally observed unprecedented thermo-mechanical properties and the guidelines to design low-fatigue ultra-fine grain shape memory alloys. As a result of the exploration of novel thermomechanical properties in SMAs via coherent second phases, we also published a software package</p><p>to discover coherent precipitates within a base multi-component system by coupling highthroughput equilibrium thermodynamics calculations with strain-based lattice matching.</p>

Two important mechanisms in preparation of ultrathin films of magnetic oxides were systematically investigated in this work. First, influence of epitaxial strain on resulting magneto-optical properties of La2/3Sr1/3MnO3 (LSMO) ultrathin films was studied. The investigated films were grown by pulsed laser deposition on four different substrates, providing a broad range of induced epitaxial strains. Magnetic properties were found to deteriorate with increasing value of the epitaxial strain, as expected due to the unit cell distortion increasingly deviating from the bulk and effect of the magnetically inert layer. A combination of spectroscopic ellipsometry and magneto-optical Kerr effect spectroscopy was used to determine spectra of the diagonal and off-diagonal elements of permittivity tensor. The off-diagonal elements confirmed presence of two previously reported electronic transitions in spectra of all films. Moreover, they revealed another electronic transition around 4.3 eV only in spectra of films grown under compressive strain. We proposed classification of this transition as crystal field paramagnetic Mn t2g → eg transition, which was further supported by ab initio calculations. A key role of strain in controlling electronic structure of ultrathin perovskite films was demonstrated. Dynamic application of...

Deux mécanismes importants reliant la préparation des couches ultraminces d’oxydes magnétiques à leurs propriétés physiques ont été étudiés dans ce travail. En premier lieu, l’influence de la contrainte épitaxiale sur les propriétés magnéto-optiques de la manganite La₂/₃Sr₁/₃MnO₃ (LSMO) a été étudiée. Les couches ultraminces ont été déposées par ablation laser pulsé sur quatre substrats différents, ce qui a fourni différentes valeurs statiques de la contrainte épitaxiale. Les propriétés magnétiques ont été révélées comme se détériorant avec l’augmentation de la contrainte, ce qui était prévisible à cause de la distorsion grandissante de la maille unitaire ainsi qu’à cause de l’effet de la couche magnétiquement inerte. La combinaison de l’ellipsométrie spectroscopique et de la spectroscopie Kerr magnéto-optique a été utilisée afin de déterminer les spectres des éléments diagonaux et non diagonaux du tenseur de permittivité. L’étude des éléments non-diagonaux a confirmé la présence déjà rapportée de deux transitions électroniques dans les spectres de toutes les couches. De plus, elle a révélé une autre transition électronique autour de l’énergie de 4.3 eV, mais seulement dans les spectres des couches déposées avec une contrainte compressive. Nous avons proposé la classification de cette transition comme une transition paramagnétique du champ cristallin Mn t2g → eg. Cette classification a été confortée par des calculs ab initio. Nous avons ainsi montré le rôle clé de la contrainte dans le contrôle des propriétés magnéto-optiques des couches pérovskites ultraminces. En revanche, l’application dynamique de la contrainte par l’utilisation d’une sous-couche piézoélectrique est restée peu concluante. Le transfert de la contrainte entre la sous-couche piézoélectrique et la couche LSMO nécessite des améliorations ultérieures. En second lieu, l’influence de la désorientation du substrat a été étudiée par rapport à la dynamique de l’aimantation dans l’oxyde SrRuO₃ (SRO). Comme attendu, nous avons trouvé qu’un grand angle de désorientation mène à la suppression de la croissance de plusieurs variants cristallographiques du SRO. Au moyen de la microscopie à force magnétique, nous avons montré que la présence de plusieurs variants de SRO mène à l’augmentation de la densité de défauts agissant comme points d’ancrage ou de nucléation pour les domaines magnétiques. Nous avons donc montré que l’emploi d’un substrat vicinal est important pour la fabrication des couches ultraminces de SRO de haute qualité, avec une faible densité de défauts cristallographiques et d’excellentes propriétés magnétiques. / Two important mechanisms in preparation of ultrathin films of magnetic oxides were systematically investigated in this work. First, influence of epitaxial strain on resulting magneto-optical properties of La₂/₃Sr₁/₃MnO₃ (LSMO) ultrathin films was studied. The investigated films were grown by pulsed laser deposition on four different substrates, providing a broad range of induced epitaxial strains. Magnetic properties were found to deteriorate with increasing value of the epitaxial strain, as expected due to the unit cell distortion increasingly deviating from the bulk and effect of the magnetically inert layer. A combination of spectroscopic ellipsometry and magneto-optical Kerr effect spectroscopy was used to determine spectra of the diagonal and off-diagonal elements of permittivity tensor. The off-diagonal elements confirmed presence of two previously reported electronic transitions in spectra of all films. Moreover, they revealed another electronic transition around 4.3 eV only in spectra of films grown under compressive strain. We proposed classification of this transition as crystal field paramagnetic Mn t2g → eg transition, which was further supported by ab initio calculations. A key role of strain in controlling electronic structure of ultrathin perovskite films was demonstrated. Dynamic application of strain via use of piezoelectric underlayer remained inconclusive, requiring further improvement of the strain transfer from the piezoelectric layer into the LSMO. Second, influence of substrate miscut on magnetization dynamics in SrRuO₃ (SRO) was studied. As expected we found that high miscut angle leads to suppression of multi-variant growth. By means of magnetic force microscopy we showed that presence of multiple SRO variants leads to higher density of defects acting as pinning or nucleation sites for the magnetic domains, which consequently results in deterioration of magnetic properties. We demonstrated that use of vicinal substrate with high miscut angle is important for fabrication of high quality SRO ultrathin films with low density of crystallographic defects and excellent magnetic properties.

Ce manuscrit est consacré à l’analyse théorique et expérimentale d’oxydes Ln2Ti2O7 (Ln = La, Nd, Sm, Gd) et BiFeO3.Les propriétés physiques de La2Ti2O7 et Nd2Ti2O7 ont été investiguées au moyen de calculs ab initio, confirmant ainsi leur ferroélectricité. D’autres oxydes de la famille Ln2Ti2O7, Sm2Ti2O7 et Gd2Ti2O7, ont ensuite été étudiés selon les mêmes méthodes théoriques. Nos calculs ont révélé une meilleure amplitude de polarisation pour ces composés par rapport au La2Ti2O7 et au Nd2Ti2O7. La deuxième partie de ce travail est consacrée aux propriétés structurales, électroniques et ferroélectriques du BiFeO3. L’évolution de ses propriétés lorsqu’il est soumis à une contrainte épitaxiale ont été investiguées au moyen de calculs ab-initio et de mesures en microscopie à champ proche réalisées sur des couches minces déposées sur un substrat de SrTiO3(001). Nos résultats mettent en évidence une modification de la structure interne du matériau sous effet de contrainte, qui se traduit par une réorientation progressive de la polarisation spontanée suivant la direction [001]. Notre étude s’est ensuite tournée vers l’élaboration et l’analyse des propriétés structurales et ferroélectriques de superréseaux (SrTiO3)n(BiFeO3)m. Nos calculs ont mis en évidence que la contrainte épitaxiale imposée au superréseau offrait un contrôle accru des propriétés du BiFeO3 par rapport à son comportement lorsqu’il est déposé seul en couches minces. Les analyses en microscopie à champ proche ont montré une réduction de la tension coercitive de tels films par rapport à celle mesurée sur des bicouches SrTiO3/BiFeO3 ou sur une couche mince de BiFeO3. / In this work, first-principles calculations and experimental measurements have been done in order to investiguate the structural, electroniq and ferroelectric properties of Ln2Ti2O7 (Ln = La, Nd, Sm, Gd) and BiFeO3 oxydes. Calculations on La2Ti2O7 and Nd2Ti2O7 confirmed their ferroelectricity. Other oxydes belonging to the Ln2Ti2O7 family have also been investigated. The results showed an enhancement of the spontaneous polarization within these compounds compared to that of La2Ti2O7 and Nd2Ti2O7. The second part of this work is related to the structural and ferroelectric properties of bismuth ferrite BiFeO3. The evolution of its properties when undergoing an epitaxial strain have been investigated by ab initio calculations and piezoresponse force microscopy measurements on thin films deposited on a (001)-SrTiO3 substrate. Our results showed a modification of the inner structure of BiFeO3 under stain, leading to a continuous reorientation of the spontaneous polarization vector towards [001]. The third part of our study consists in the computational design and synthesis of (SrTiO3)n(BiFeO3)m superlattices. Our calculations showed that epitaxial strain imposed to the superlattice brings a further control of physical properties of BiFeO3 as compared with its behaviour when deposited alone in a thin film. PFM analysis showed a decrease of the coercive field for STO/LNO/(STO)n(BFO)m superlattices as compared with those measured on STO/BFO bi-layers and on BiFeO3 thin films.

We have embarked on a systematic study of novel charge states at oxide interfaces. We have performed pulsed laser deposition (PLD) growth of epitaxial oxide thin films on single crystal oxide substrates. We studied the effects of epitaxial strain and rare-earth composition of the metal oxide thin films. We have successfully created TiO₂ terminated SrTiO₃ (STO) substrates and have grown epitaxial thin films of LaAlO₃ (LAO), LaGaO₃ (LGO), and RAlO₃ on STO using a KrF pulsed excimer laser. Current work emphasizes the importance of understanding the effect of both epitaxial strain and R³+ magnetism on the interface between RAlO₃ and STO. We have demonstrated that the interfaces between LAO/STO and LGO/STO are metallic with carrier concentrations of 1.1 x 10¹⁴ cm[superscript -2] and 4.5 x 10¹⁴ cm[superscript −2], respectively. Rare-earth aluminate films, RAlO₃, with R = Ce, Pr, Nd, Sm, Eu, Gd, and Tb, were also grown on STO. Conducting interfaces were found for R = Pr, Nd and Gd, and the results indicate that for R [does not equal] La the magnetic nature of the R³+ ion causes increased scattering with decreasing temperature that is modeled by the Kondo effect. Epitaxial strain between the polar RAlO₃ films and STO appears to play a crucial role in the transport properties of the metallic interface, where a decrease in the R³+ ion size causes an increase in sheet resistance and an increase in the onset temperatures for increased scattering. / text