The spin-splitting energies in strained bulk wurtzite aluminum nitride (AlN) are studied using the linear combination of atomic orbital method. It is found that strain and crystal field induce not only a linear-k (£\wz ) but also two cubic-k terms (£^¡¦and £f¡¦ ) in the two-band k¡Dp Hamiltonian Hso=(£\wz-£^¡¦k2//+£f¡¦k2z)(£mxky-£mykx)+H0so, where H0so=(-£^0k2//+£f0k2z)(£mxky-£mykx) is for ideal wurtzite and generates a cone-shaped minimum-spin-splitting (MSS) surface. As biaxial strain increases, the shape of the MSS surface changes from a hexagonal hyperboloid of two sheets in unstrained AlN to a hexagonal cone, and eventually becomes a hyperboloid of one sheet. The spin-splitting energies of first conduction band for A-plane and M-plane wurtzite are calculated by the sp3 linear combination of atomic orbital (LCAO). The results show the spin-splitting energies are dominated by linear-k term but contribution of cubic-k terms can not be neglected for larger k//. The parameter of linear-k and cubic-k terms are evaluated from the LCAO calculated spin-splitting energies fitting to two band k¡Ep model as increasing well width. The coefficients of linear-k and cubic-k terms decrease.

In modern technology exciting developments are related to the ability to understand and control interfaces. Particularly, magnetic interfaces revealing spindependent electron transport are of great interest for modern spintronic devices, such as random access memories and logic devices. From the technological point of view, spintronic devices based on magnetic interfaces enable manipulation of the magnetism via an electric field. Such ability is a result of the different quantum effects arising from the magnetic interfaces (for example, spin transfer torque or spin-orbit torque) and it can reduce the energy consumption as compared to the traditional semiconductor electronic devices. Despite many appealing characteristics of these materials, fundamental understanding of their microscopic properties and related phenomena needs to be established by thorough investigation. In this work we implement first principles calculations in order to study the structural, electric, and magnetic properties as well as related phenomena of two types of interfaces with large potential in spintronic applications: 1) interfaces between antiferromagnetic 3d-metal-oxides and ferromagnetic 3d-metals and 2) interfaces between non-magnetic 5d(4d)- and ferromagnetic 3d-metals. A major difficulty in studying such interfaces theoretically is the typically large lattice mismatch. By employing supercells with Moir e patterns, we eliminate the artificial strain that leads to doubtful results and are able to describe the dependence of the atomic density at the interfaces on the component materials and their thicknesses. After establishing understanding about the interface structures, we investigate the electronic and magnetic properties. A Moir e supercell with transition layer is found to reproduce the main experimental findings and thus turns out to be the appropriate model for simulating magnetic misfit interfaces. In addition, we systematically study the magnetic anisotropy and Rashba band splitting at non-magnetic 5d(4d) and ferromagnetic 3d-metal interfaces and their dependences on aspects such as interdiffusion, surface oxidation, thin film thickness and lattice mismatch. We find that changes of structural details strongly alter the electronic states, which in turn influences the magnetic properties and phenomena related to spin-orbit coupling. Since the interfaces studied in this work have complex electronic structures, a computational approach has been developed in order to estimate the strength of the Rashba band splitting below and at the Fermi level. We apply this approach to the interfaces between a Co monolayer and 4d (Tc, Ru, Rh, Pd, and Ag) or 5d (Re, Os, Ir, Pt, and Au) transition metals and find a clear correlation between the overall size of the band splitting and the charge transfer between the d-orbitals at the interface. Furthermore, we show that the spin splitting at the Fermi surface scales with the induced orbital moment weighted by the strength of the spin-orbit coupling.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22238号 / 理博第4552号 / 新制||理||1654(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 松田 祐司, 教授 石田 憲二, 教授 寺嶋 孝仁 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Neste trabalho de mestrado apresentamos um estudo sobre a manifestação do efeito Rashba em isolantes topológicos na ausência de simetria de inversão estrutural. Os cálculos das propriedades atomísticas, energéticas e as estruturas eletrônicas são abordados através de métodos de primeiros princípios baseados na teoria do funcional da densidade. E seus resultados foram utilizados para o desenvolvimento de hamiltoniana efetiva baseado no modelo de Zhang. Realizamos o estudo de dois sistemas: 1) Bi$_2$Se$_3$ com átomos de Sn depositados na superfície: Este sistema pode ser entendido através da manifestação do efeito Rashba sobre um isolante topológico dada a quebra de simetria de inversão estrutural. Para um sítio de deposição específico, os átomos de Sn causam uma reconstrução da superfície e um terceiro cone de Dirac é observado na estrutura eletrônica. Este terceiro cone é não localizado na superfície e pode ser entendido como a manifestação do efeito Rashba. 2) PbBiI: Reportado aqui como um novo isolante topológico 2D com efeito Rashba. Descobrimos este sistema por um estudo sistemático sobre uma família de materiais formados por átomos tipo IV, V, e VII, cuja estrutura cristalina é hexagonal e não centrossimétrica. Mostramos que o PbBiI possui: i) Estabilidade mecânica, ii) Spin-splitting Rashba de 60 meV, iii) um gap de energia não trivial de 0.14 eV, iv) retroespalhamento proibido entre os estados de borda e v) retroespalhamento proibido entre os estados do bulk no entorno do nível de Fermi. Estas propriedades fazem do PbBiI um candidato para construção de dispositivos de spintrônica que atenua a perda de energia. / In this work, were studied the Rashba effect in topological insulators without structural inversion symmetry. We performed a first principles study based on density functional theory to calculate the atomistic properties, formation energy and electronic structure. These results were used to development a effective Hamiltonian based on Zhang model. They were studied two systems: 1) Bi$_2$Se$_3$ with Sn atoms deposited on the surface: This system can be seen as the Rashba effect manifestation on a topological insulator due to the structural inversion symmetry breaking. For a specific deposition site, the Sn atoms cause a reconstruction of the surface and display a third Dirac cone in the electronic structure. This third cone is not located on the surface and can be understood as the giant Rashba effect manifestation. 2) We propose a new non-centrosymmetric honeycomb-lattice QSH insulator family formed by the IV, V, and VII elements. The system formed by Bi, Pb and I atoms is reported here as a new 2D topological insulator with Rashba effect. We show that this system has: i) Mechanical stability, ii) spin-splitting Rashba of 60 meV, iii) nontrivial energy gap of 0.14 eV, iv) backscattering forbidden for both edge and bulk conductivity channels in the nanoribbon band structure. These properties make PbBiI a good candidate to construct spintronic devices with less energy loss.

This thesis is focused on the electronic, spin-dependent and dynamical properties of thin magnetic systems. Photoemission-related techniques are combined with synchrotron radiation to study the spin-dependent properties of these systems in the energy and time domains. In the first part of this thesis, the strength of electron correlation effects in the spin-dependent electronic structure of ferromagnetic bcc Fe(110) and hcp Co(0001) is investigated by means of spin- and angle-resolved photoemission spectroscopy. The experimental results are compared to theoretical calculations within the three-body scattering approximation and within the dynamical mean-field theory, together with one-step model calculations of the photoemission process. From this comparison it is demonstrated that the present state of the art many-body calculations, although improving the description of correlation effects in Fe and Co, give too small mass renormalizations and scattering rates thus demanding more refined many-body theories including nonlocal fluctuations. In the second part, it is shown in detail monitoring by photoelectron spectroscopy how graphene can be grown by chemical vapour deposition on the transition-metal surfaces Ni(111) and Co(0001) and intercalated by a monoatomic layer of Au. For both systems, a linear E(k) dispersion of massless Dirac fermions is observed in the graphene pi-band in the vicinity of the Fermi energy. Spin-resolved photoemission from the graphene pi-band shows that the ferromagnetic polarization of graphene/Ni(111) and graphene/Co(0001) is negligible and that graphene on Ni(111) is after intercalation of Au spin-orbit split by the Rashba effect. In the last part, a time-resolved x-ray magnetic circular dichroic-photoelectron emission microscopy study of a permalloy platelet comprising three cross-tie domain walls is presented. It is shown how a fast picosecond magnetic response in the precessional motion of the magnetization can be induced by means of a laser-excited photoswitch. From a comparision to micromagnetic calculations it is demonstrated that the relatively high precessional frequency observed in the experiments is directly linked to the nature of the vortex/antivortex dynamics and its response to the magnetic perturbation. This includes the time-dependent reversal of the vortex core polarization, a process which is beyond the limit of detection in the present experiments. / Diese Dissertation beschäftigt sich mit den elektronischen, spinabhängigen und dynamischen Eigenschaften dünner magnetischer Systeme. Auf dem Photoeffekt basierende Untersuchungsmethoden werden zusammen mit Synchrotronstrahlung eingesetzt, um die spinabhängigen Eigenschaften dieser Systeme im Energie- und Zeitbereich zu untersuchen. Im ersten Teil dieser Arbeit wird mit spin- und winkelaufgelöster Photoemission die Stärke von Elektronenkorrelationseffekten in der spinabhängigen elektonischen Struktur von ferromagnetischerm bcc Fe(110) und hcp Co(0001) untersucht. Die experimentellen Ergebnisse werden verglichen mit theoreteischen Berechnungen im Rahmen der Näherung der Drei-Körper-Streuung und der dynamischen Molekularfeldtheorie, zusammen mit Berechnungen des Photoemissionsprozesses im Rahmen des Ein-Stufen-Modells. Ausgehend von diesem Vergleich wird gezeigt, dass die gegenwärtig fortgeschrittensten Rechnung, obgleich sie die Beschreibung von Korrelationseffekten in Fe und Co verbessern, zu kleine Massenrenormalisierungen und Streuraten ergeben, was zu der Forderung nach verfeinerten Vielteilchentheorien unter Einbeziehung von nichtlokalen Fluktuationen führt. Im zweiten Teil wird unter Kontrolle durch die Photoelektronenspektroskopie im Detail gezeigt, wie Graphen durch chemische Gasphasenabscheidung auf den Übergangsmetall-Oberflächen Ni(111) und Co(0001) aufgebracht und mit einer Monolage Au interkaliert werden kann. Für beide Systeme wird eine lineare E(k)-Dispersion masseloser Dirac-Fermionen im Graphen-pi-Band in der Nähe der Fermi-Energie beobachtet. Spinaufgelöste Photoemission des Graphen-pi-Bandes zeigt, dass die ferromagnetische Polarisation von Graphen/Ni(111) und Graphen/Co(0001) vernachlässigbar ist und dass Graphen/Ni(111) nach Interkalation mit Au eine Spin-Bahn-Aufspaltung aufgrund des Rashba-Effekts zeigt. Im letzten Teil wird eine zeitaufgelöste Studie des Röntgenzirkulardichroismus mit Photoelektronenmikroskopie präsentiert, die an einer Permalloy-Probe durchgeführt wurde, die drei als Stachelwände ausgebildete Domänenwände enthält. Es wird gezeigt, wie eine schnelle magnetische Antwort auf der Pikosekundenskala in der Präzessionsbewegung der Magnetisierung durch einen laserangesteuerten Photoschalter erzeugt werden kann. Durch Vergleich mit einer mikromagnetischen Rechnung wird gezeigt, dass die relativ hohe Präzessionsfrequenz, die im Experiment beobachtet wird, in unmittelbarer Beziehung steht zu den Eigenschaften der Vortex/Antivortex-Dynamik und ihrer Antwort auf die magnetische Störung. Das schließt die zeitabhängige Umkehr der Vortexkernpolarisation ein, einem Vorgang der jenseits der Nachweisgrenze der gegenwärtigen Experimente liegt.

Neste trabalho de mestrado apresentamos um estudo sobre a manifestação do efeito Rashba em isolantes topológicos na ausência de simetria de inversão estrutural. Os cálculos das propriedades atomísticas, energéticas e as estruturas eletrônicas são abordados através de métodos de primeiros princípios baseados na teoria do funcional da densidade. E seus resultados foram utilizados para o desenvolvimento de hamiltoniana efetiva baseado no modelo de Zhang. Realizamos o estudo de dois sistemas: 1) Bi$_2$Se$_3$ com átomos de Sn depositados na superfície: Este sistema pode ser entendido através da manifestação do efeito Rashba sobre um isolante topológico dada a quebra de simetria de inversão estrutural. Para um sítio de deposição específico, os átomos de Sn causam uma reconstrução da superfície e um terceiro cone de Dirac é observado na estrutura eletrônica. Este terceiro cone é não localizado na superfície e pode ser entendido como a manifestação do efeito Rashba. 2) PbBiI: Reportado aqui como um novo isolante topológico 2D com efeito Rashba. Descobrimos este sistema por um estudo sistemático sobre uma família de materiais formados por átomos tipo IV, V, e VII, cuja estrutura cristalina é hexagonal e não centrossimétrica. Mostramos que o PbBiI possui: i) Estabilidade mecânica, ii) Spin-splitting Rashba de 60 meV, iii) um gap de energia não trivial de 0.14 eV, iv) retroespalhamento proibido entre os estados de borda e v) retroespalhamento proibido entre os estados do bulk no entorno do nível de Fermi. Estas propriedades fazem do PbBiI um candidato para construção de dispositivos de spintrônica que atenua a perda de energia. / In this work, were studied the Rashba effect in topological insulators without structural inversion symmetry. We performed a first principles study based on density functional theory to calculate the atomistic properties, formation energy and electronic structure. These results were used to development a effective Hamiltonian based on Zhang model. They were studied two systems: 1) Bi$_2$Se$_3$ with Sn atoms deposited on the surface: This system can be seen as the Rashba effect manifestation on a topological insulator due to the structural inversion symmetry breaking. For a specific deposition site, the Sn atoms cause a reconstruction of the surface and display a third Dirac cone in the electronic structure. This third cone is not located on the surface and can be understood as the giant Rashba effect manifestation. 2) We propose a new non-centrosymmetric honeycomb-lattice QSH insulator family formed by the IV, V, and VII elements. The system formed by Bi, Pb and I atoms is reported here as a new 2D topological insulator with Rashba effect. We show that this system has: i) Mechanical stability, ii) spin-splitting Rashba of 60 meV, iii) nontrivial energy gap of 0.14 eV, iv) backscattering forbidden for both edge and bulk conductivity channels in the nanoribbon band structure. These properties make PbBiI a good candidate to construct spintronic devices with less energy loss.

abstract: Two dimensional (2D) Janus Transition Metal Dichalcogenides (TMDs) are a new class of atomically thin polar materials. In these materials, the top and the bottom atomic layer are made of different chalcogen atoms. To date, several theoretical studies have shown that a broken mirror symmetry induces a colossal electrical field in these materials, which leads to unusual quantum properties. Despite these new properties, the current knowledge in their synthesis is limited only through two independent studies; both works rely on high-temperature processing techniques and are specific to only one type of 2D Janus material - MoSSe. Therefore, there is an urgent need for the development of a new synthesis method to (1) Extend the library of Janus class materials. (2) Improve the quality of 2D crystals. (3) Enable the synthesis of Janus heterostructures. The central hypothesis in this work is that the processing temperature of 2D Janus synthesis can be significantly lowered down to room temperatures by using reactive hydrogen and sulfur radicals while stripping off selenium atoms from the 2D surface. To test this hypothesis, a series of controlled growth studies were performed, and several complementary characterization techniques were used to establish a process–structure-property relationship. The results show that the newly proposed approach, namely Selective Epitaxy and Atomic Replacement (SEAR), is effective in reducing the growth temperature down to ambient conditions. The proposed technique benefits in achieving highly crystalline 2D Janus layers with an excellent optical response. Further studies herein show that this technique can form highly sophisticated lateral and vertical heterostructures of 2D Janus layers. Overall results establish an entirely new growth technique for 2D Janus.layers, which pave ways for the realization of exciting quantum effects in these materials such as Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) state, Majorana fermions, and topological p-wave superconductors. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2020

La loi de Moore est basée sur l’observation empirique qu’environ chaque deux années, le nombre de transistors dans des circuits denses intégrées double. Cette tendance s'est bien maintenue au cours des dernières décennies (années 1970 et suivantes). Cependant, la miniaturisation continue des transistors entraîne une augmentation significative des pertes d’énergie par le courant de fuite, ce qui augmente la consommation d'énergie de veille. Cette perte d’énergie est devenue un problème majeur dans la microélectronique pendant les dernières années, ce qui rend plus difficile le développement des nouvelles technologies. L’une des solutions est de placer des éléments mémoire non-volatile dans le puce, qui retiennent la configuration du transistor pendant la mise hors tension et permettent de le restaurer à la mise sous tension. Les Magnetic Random Access Memories (MRAM) sont considérées par l'ITRS comme un candidat crédible pour le remplacement potentiel de SRAM et de DRAM au-delà du nœud technologique de 20 nm. Bien que les exigences de base pour la lecture et l'écriture d'un élément de mémoire unique sont remplies, l'approche actuelle basée sur Spin Torque Transfer (STT) souffre d'un manque inné de la flexibilité. Le courant électrique entraine le retournement de l’aimantation de la couche ferromagnétique libre par le transfert du moment angulaire d’une couche ferromagnétique adjacent. Ainsi les éléments de mémoire basées sur STT ont deux terminaux dont les voies de courant pour « écriture » et « lecture » sont définies par la forme de «pillar». L’optimisation indépendant des paramètres d’écriture et de lecture reste, donc, très difficile. Au même temps, la densité de courant trop haute, nécessaire pour écrire, conduit à la vieillissement prémature du jonction tunnel. En conséquence, l’intégration MRAM dans la technologie du semi-conducteur reste, donc, difficile.Démonstrations récentes de reversement d’aimantation entrainées par l’injection d’un courant planaire dans des heterostructures métal lourd/ferromagnet ont attiré l’attention croissante sur les couples de spin basé sur le transfert du moment angulaire par l’effet Hall de spin et les effets d’interface. Contrairement à STT-MRAM, la SOT-MRAM a trois terminaux, dont les voies de courant pour « écriture » et « lecture » sont indépendantes. Cela permet d’améliorer les paramètres « écriture » et « lecture » de manière indépendante. Pour contrôler et optimiser les SOT il est nécessaire de comprendre très bien leur origine. Cela reste l’une des plus importantes questions dont on n’a pas une réponse définitive. Dans ce contexte, plusieurs études ont conclu sur un modèle basé seulement sur l’effet Hall de spin, en même temps que d’autres ont suggéré un modèle basé sur une contribution combiné de l’effet Hall de spin et l’effet d’interface.L’objectif de cette thèse est de réaliser une étude systématique sur les effets d’interface sur les SOT dans des heterostructures métal lourde/ferromagnet a base de Pt, avec aimantation planaire.Dans ce but, cette thèse explore trois voies différentes. Premièrement nous avons modifié le rapport entre les effets d’interface et les effets bulk en changeant l’épaisseur de la couche de Pt et en suivant l’évolution des SOT. En deuxième nous avons exploré des différents empilements métal lourde/ferromagnet afin d’étudier différentes interfaces. Finalement, nous avons changé les propriétés des interfaces soit par changer la structure cristalline soit par oxydation. La technique de mesure, la méthode d’analyse de données associé et les aspects théoriques nécessaires pour l’interprétation des données sont aussi détaillés dans ce manuscrit. / Moore’s law is based on empirical observation and states that every two years approximately, the number of transistors in dense integrated circuits doubles. This trend has held up well in the past several decades (1970s and onwards). However, the continuous miniaturisation of transistors brings about a significant increase in leakage current, which increases the stand-by power consumption. This energy loss has become a major problem in microelectronics during the last several years, making the development of new technologies more difficult. One of the solutions that can address this issue is to place non-volatile memory elements inside the chip, that retain the configuration of the transistor during power-off and allow to restore it at power-on. Magnetic Random Access Memories (MRAM) are considered by the ITRS as a credible candidate for the potential replacement for SRAM and DRAM beyond the 20 nm technological node. Though the basic requirements for reading and writing a single memory element are fulfilled, the present approach based on Spin Transfer Torque (STT) suffers from an innate lack of flexibility. The electric current drives the magnetization switching of a free ferromagnetic layer by transferring angular momentum from an adjacent ferromagnet. Therefore, STT-based memory elements are two terminal devices in which the “pillar” shape defines both the “read” and the “write” current paths. Independent optimisation of the reading and writing parameters is therefore difficult, while the large writing current density injected through the tunnel barrier causes its accelerated ageing, particularly for fast switching. Consequently, the integration of MRAM into semiconductor technology poses significant difficulties.Recent demonstrations of magnetization switching induced by in-plane current injection in heavy metal (HM)/ferromagnet (FM) heterostructures have drawn increasing attention to spin-torques based on orbital-to-spin momentum transfer induced by Spin Hall and interfacial effects (SOTs). Unlike STT-MRAM, the in-plane current injection geometry of SOT-MRAM allows for a three-terminal device which decouples the “read” and “write” mechanisms, allowing the independent tuning of reading and writing parameters. However, an essential first step in order to control and optimise the SOTs for any kind of application, is to better understand their origin. The origin of the SOTs remains one of the most important unanswered questions to date. While some experimental studies suggest a SHE (Spin Hall Effect)-only model for the SOTs, others point towards a combined contribution of the bulk (SHE) and interface (Rashba Effect and Interfacial SHE). At the same time, many studies start with a SHE only hypothesis and do not consider interfacial effects. Furthermore, there are not so many systematic studies on the effects of interfaces. This thesis tries to fill in this gap, by providing a systematic study on the effects of interfaces on the SOTs, in Pt-based NM/FM/HM multilayers with in-plane magnetic anisotropy. For this purpose, this thesis explores three different, but related avenues. First, we changed the interface/bulk effect ratio by modifying the Pt thickness and following the evolution of the SOTs. Second, we explored different HM/FM/NM combinations, in order to study different interfaces. And third, we changed the properties of the interfaces by changing the crystallographic structure of the interface and by oxidation. The measurement technique and associated data analysis method, as well as the theoretical considerations needed for the interpretation of the results are also detailed in this manuscript.

Afin de réduire la consommation de puissance des futures générations de systèmesélectroniques, une solution est d’intégrer de la non-volatilité au sein même des cellulesmémoires. Dans cette optique, l’utilisation du retournement de l’aimantation d’un matériauferromagnétique comme support de l’information a été utilisée initialement dans un conceptde mémoire, la MRAM. La dernière évolution de cette technologie, la SOT-RAM, utilise desphénomènes nouveaux appelés SOTs afin de contrôler la direction de l’aimantation. Parrapport aux générations précédentes (STT-MRAM notamment), elle devrait permettred’améliorer la vitesse d’écriture en conservant une endurance adaptée pour des utilisations enmémoires cache où en mémoire centrale. Le terme SOTs est une dénomination généraledésignant l’ensemble des effets, encore mal connus, liés au couplage spin-orbite et permettantle retournement de l’aimantation d’une cellule mémoire.Ce travail de thèse a eu pour objectif d’étudier les SOTs via un système expérimental demesure quasi-statique basé sur les effets Hall extraordinaires et planaires. Sonimplémentation et la méthode d’analyse associée, ainsi que les considérations théoriquesnécessaires à l’interprétation des résultats sont détaillées dans ce manuscrit. Il a été montréque le retournement de l’aimantation dans des systèmes à aimantation perpendiculaire à basede cobalt-platine ne peut être expliqué par les modèles simples considérés jusqu’à présentdans la littérature. En effet, il a été mis en évidence qu’au moins deux effets simultanés doiventêtre pris en compte pour expliquer les phénomènes observés. Par ailleurs, ceux-ci présententune sensibilité différente à la fois à une altération de la structure cristalline et à une variationde température. / In order to reduce power consumption in next generations’ electronic devices, one potentialsolution is to implement non-volatility in memory cells. In this goal, the magnetizationswitching of a ferromagnetic material has been used in a memory concept: the MRAM. Thelatest development of this technology, called SOT-RAM, is based on new phenomena calledSOTs (Spin-Orbit Torques) in order to control magnetization direction. Contrary to precedentgenerations (STT-MRAM), it should achieve a higher operating speed and an enduranceadapted for cache and main memories applications. SOTs is a generic term referring to all theeffects, linked to the spin-orbit interaction, and that enable magnetization reversal. They areyet not perfectly understood.The main objective of this Ph.D. was then to study these SOTs through a quasi-staticexperimental measurement setup based on anomalous and planar Hall effects. Itsimplementation and the associated analysis method, as well as the required theoreticalconsiderations for data interpretation are detailed in this manuscript. It has been highlightedthat magnetization switching in perpendicularly magnetization cobalt-platinum systemscannot be explained by the simple models considered thus far in the literature. As a matter offact it has been evidenced that at least two effects have to be considered in order to explainobserved phenomena. In addition, they present different susceptibility both to a modificationof the crystal structure and to a temperature change.