Le but de cette thèse est d'explorer la faisabilité d'expériences de diffraction résonante sur des systèmes multiferroïques et en particulier avec un champ/courrant électrique appliqué. Un formalisme de matrices de propagation a été développé pour simuler la réflectivité résonante, en utilisant un ensemble d'ondes propres comme base arithmétique pour le calcul. Des expériences de diffraction résonante ont été menées sur trois oxides de métaux de transition. Cette technique combinant la selectivité chimique et la sensibité à l'espace réciproque, elle a été utilisée sur des films très minces de PbTiO3 pour étudier la structure atomique d'un agencement périodique de domaines ferroélectriques. La signatures spectroscopiques observées par nos expériences de diffraction X durs sont reproduites par des simulations ab-initio FDMNES de super-cellules complexes. Dans le domaine X mous, nous avons étudié la structure antiferromagnétique cycloïdale du multiferroïque BiFeO3, et plus spécialement l'empreinte de la cycloïde sur une couche mince de Co déposée sur le matériau multiferroïque. Nous présentons également une expérience dans laquelle nous avons tenté d'explorer l'effet d'un courant électrique appliqué sur un film mince du composé à ordre de charge Pr(1-x)Ca(x)MnO3. La dernière partie est consacrée à l'instrumentation. Nous passons en revue les lignes synchrotron européennes et les diffractomètres qui permettent de faire des expériences de diffraction résonante de rayons X. Pour finir, nous détaillons un nouveau porte-échantillon que nous avons développé et testé sur le diffractomètre RESOXS, et qui permet d'appliquer un champ/courant électrique. / The aim of this thesis is to explore the capabilities offered by resonant X-ray scattering for the study of multiferroic systems with a special emphasis on the feasibility of such experiments under applied electric field/current. Boundary propagation matrices formalism has been developed for the simulation of resonant reflectivity, using a set of eigenwaves as a basis for the computation. Resonant X-ray experiments were performed on three transition metal oxides. This technique combines chemical selectivity and reciprocal space information, and was used on very thin films of PbTiO3 to solve the atomic structure of a periodic pattern of ferroelectric domains. The spectroscopic signatures observed in our hard X-ray experiments are well reproduced with FDMNES ab-initio simulations of complex super cells. In the soft X-ray range, we studied the cycloidal antiferromagnetic structure of multiferroic BiFeO3 and especially the imprint of the cycloid on a 10 nm-thin layer of Co deposited on top of the multiferroic bulk material. We also present an experiment in which we tried to explore the effect of an electrical current applied on a thin film of charge-ordered Pr(1-x)Ca(x)MnO3. Last part is dedicated to instrumentation. We summarize the state of the art of european synchrotron beamlines and diffractometers which can host resonant X-ray diffraction experiments. Finally, we detail a new sample holder that we developed and tested in the high-vacuum diffractometer RESOXS, which allows for the application of an electric field/current.

After the prediction of magnetoelectric effect in Cr2O3, in early 1960's, D. Asrov became the first to experimentally verify this phenomenon. After the pioneering work on magnetoelectric materials in 1960's and 1970's, the discovery of large magnetoelectric effect in orthorhombic rare-earth manganite TbMnO3 has revived great interest in magnetoelectric materials, especially during the last decade. Magnetoelectric multiferroics have great potential in applications such as novel memory storage devices and sensors. As a result of extensive theoretical and experimental investigations conducted on rare-earth magnetoelectric manganites, TbMnO3 has become a prototype magnetoelectric multiferroic material. Orthorhombic rare-earth manganites RMnO3 (R = Gd, Tb and Dy) exhibit improper ferroelectricity where the origin of ferroelectricity is purely magnetic in nature. RMnO3 exhibit diverse and complex magnetic interactions and phases. Doped manganites of the type R1-xAxMnO3 (A = Ca, Sr and Ba) present a rich magnetic and electronic phase diagram. The doping concentration, average ion-size and size mismatch (i.e. disor-der) at A-site, all contribute to determine the ground state. A variety of magnetic phases, competing with each other, are responsible for many functional properties like magnetoelectric effect, colossal magnetoresistance (CMR), magnetostriction and magnetocaloric effect (MCE). In this context, studies of magnetoelectric materials are of great relevance from technical as well as fundamental aspects. Notably, complexity of electronic (and magnetic) phases and experimental difficulties in acquiring reliable measurement-data easily are the most concerning issues in establishing a clear understanding of magnetoelectric materials. In the magnetic phase diagram of RMnO3, GdMnO3 lies on the border between A-type antiferromagnetic and cycloidal antiferromagnetic ground states. Cycloidal spin arrangement is responsible for the induction of ferroelectricity in these materials. There are disparate opinions about the ground state of GdMnO3 (whether the ground state is ferroelectric or not). Understanding of the influence of rare-earth magnetic sublattice on magnetism in GdMnO3 (at low temperature) lacks clarity till date. Neutron scattering studies on GdMnO3 due to high absorption cross-section of Gd ion, yield little success in determining the nature of complex magnetic phases in this material. Interestingly, an earlier report on strontium-substituted gadolinium manganite Gd0.5Sr0.5MnO3 demonstrated the spontaneous electric polarization and related magnetoelectric effect. It was hypothesized that the observed ferroelectricity could be improper and electronic in nature. Strontium doping facilitates quenched disorder that leads to interesting magnetic phases and phase transitions. In order to understand the physical properties of gadolinium manganites and to unravel the relationship between them, it is essential to investigate high quality single crystals of these materials. This thesis deals with growth and investigation of several important physical phenomena of gadolinium manganites such as magnetic, electric, magnetoelectric and magnetocaloric properties. The thesis is organized in seven chapters. A brief summary of each chapter follows: Chapter:1 This chapter provides general introduction to magnetoelectric effect and multiferroicity. The term multiferroicity refers to simultaneous existence of magnetic and electric ordering in a single phase material. Magnetoelectric multiferroics have shown great potential for several applications. They exhibit cross coupling between the electronic and magnetic order parameters, hence basics of various magnetic interactions (and magnetism) are brie y discussed in the rst section of the chapter. It is followed by a brief discussion about the principle of magnetoelectric effect. Magnetoelctric coupling is broadly classified into two types namely, direct coupling and indirect coupling. In the former, the emphasis is given on linear magnetoelectric effect. The concept of multiferroicity is introduced in the next section followed by a brief overview and application potential of multiferroics. Further, classi cation scheme of multiferroic materials is discussed. The concept of improper ferroelectricity and description of subcategories namely, magnetic ferroelectric, geometric ferroelectric and electronic ferroelectric are documented. Magnetic ferroelectric category is considered the most relevant; featuring the type of ferroelectric material as GdMnO3 referred in this thesis. The microscopic theory for mechanism of ferroelectricity in spiral antiferromagnets is presented. While brie ng the thermodynamic background of the magnetocaloric effect, indirect estimation of two important characteristics namely, isothermal magnetic entropy change (∆SM ) and adiabatic change in temperature (∆Tad) under the application of magnetic field are dealt with. In the last part of the chapter, motivation and scope of the thesis is discussed. Chapter:2 This chapter outlines various experimental methodologies adopted in this work. It describes the basic principles of various experimental techniques and related experimental apparatuses used. The chapter starts with the synthesis tech-niques used in the preparation of different compounds studied. The principle of oat-zone method, employed for single-crystal growth, is described. Orientation of single crystals was determined using a home-built back- reflection Laue set up. The basics of Laue reflection and indexing procedure for recorded Laue photographs are described. Various physical properties (electric, magnetic, thermal, magnetoelectric and magnetocaloric properties) were studied using commercial as well as home-built experimental apparatuses. Design and working principle of all the experimental tools are outlined in this chapter. Fabrication details, interfacing of measurement instruments and calibration (standardization) of equipment used in this work are described in appropriate sections. Chapter:3 Chapter-3 describes the investigation of various physical properties of high quality single crystals of magnetoelectric multiferroics, GdMnO3. Synthesis of GdMnO3 is carried out using solid state synthesis route. Single phase nature of the material is confirmed by X-ray powder diffraction technique. Single crystals of GdMnO3 are grown in argon ambience using oat-zone method. As grown crystals are oriented with the help of back-reflection Laue method. GdMnO3 exhibits incommensurate collinear antiferromagnetic phase below 42 K and transforms to canted A-type antiferromagnetic phase below 23 K. Magnetic and specific heat studies have revealed very sharp features near the magnetic transitions which also confirm the high quality of the single crystal. dc magnetization studies illustrate the anisotropic behavior in canted A-type antiferromagnetic phase and clarifies the influence of rare-earth magnetic sub-lattice on overall magnetism (at low temperature). Application of magnetic field (above 10 kOe) along `b' axis helps formation of the cycloidal antiferromagnetic phase. Here, spontaneous electric polarization is induced along `a' axis. The temperature variation plot of dielectric constant, ϵa (under ap- plied magnetic field along `b' axis) shows sharp anomalies in the vicinity of magnetic ordering transitions suggesting magnetodielectric effects. Magnetic field tuning of electric polarization establish the magnetoelectric nature of GdMnO3. Magnetocaloric properties of single crystals of GdMnO3 are investigated using magnetic and magnetothermal measurements. The magnitude of the giant magnetocaloric effect observed is compared with that of other rare-earth manganite multiferroics. Magnetocaloric studies shed light on magnetic ordering of rare-earth ion Gd3+. The phenomenon of inverse magnetocaloric effect observed at low temperature and under low fields is possibly linked to the ordering of Gd3+ spins. Complex interactions between the 3d and 4f magnetic sublattices are believed to influence magnetocaloric properties. Chapter:4 The details of synthesis and single crystal growth of Gd0.5Sr0.5MnO3 using oat-zone method are presented in Chapter 4. Single phase nature of the material is veri ed by carrying out powder x-ray diffraction analysis and confirmation of single crystallinity and orientation through back-reflection Laue method. Electric transport studies reveal semiconductor-like nature of Gd0.5Sr0.5MnO3 until the lowest temperature achieved. This is due to charge localization process which occurs concurrently with decrease in temperature. Gd0.5Sr0.5MnO3 exhibits charge-ordered insulator (COI) phase below 90 K (ac-cording to an earlier report). It is found that under application of magnetic field above a critical value, charge ordering melts and the phase transforms to ferromagnetic metallic (FMM) phase. This transformation is first-order in nature with associated CMR (109%). The first-order phase transition (FOPT) occurs between competing COI and FMM phases and manifests as hysteresis across the FOPT. Strontium doping at A-site induces a large size mismatch at A-site resulting in high quenched disorder in Gd0.5Sr0.5MnO3. The disorder plays a significant role in CMR as well as glass-like dynamics within the low-temperature magnetic phase. ac susceptibility studies and dynamic scaling analysis reveal very slow dynamics inside the low-temperature magnetic phase (below 32 K). According to an earlier report, spontaneous electric polarization and magnetoelectric effect were pronounced near FOPT (at 4.5 K and 100 kOe) between COI and FMM phases. It is prudent to investigate FOPT across COI and FMM phases in Gd0.5Sr0.5MnO3 to understand complex magnetic phases present. Thermodynamic limits of the FOPT (in magnetic field - temperature (H-T) plane), such as supercooling and superheating, are experimentally determined from magnetization and magnetotransport measurements. Interestingly, thermomagnetic anomalies such as open hysteresis loops are observed while traversing the FOPT isothermally or isomagnetically in the H-T plane. These anomalies point towards incomplete phase transformation while crossing the FOPT. Phenomenological model of kinetic arrest is invoked to understand these anomalies. The model put for-ward the idea that while cooling across the FOPT, extraction of specific heat is easier than that of latent heat. In other words, phase transformation across FOPT is thermodynamically allowed but kinetics becomes very slow and phase transformation does not occur at the conventional experimental time scale. Magnetization relaxation measurements (at 89 kOe) with field-cooled magnetization protocol reveal that the relaxation time constant rst decreases with temperature and later, increases non-monotonically below 30 K. This qualita-tive behavior indicates glass-like arrest of the FOPT. Further, thermal cycling studies of zero field-cooled (ZFC) and eld-cooled (FC) magnetization indicate that a low temperature phase prepared with ZFC and FC protocols (at 89 kOe) is not at equilibrium. This confirms the kinetic arrest of FOPT and formation of magnetic phase similar to glass. Chapter:5 Chapter-5 deals with the investigation of the effect of an electric field on charge ordered phase in Gd0.5Sr0.5MnO3 single crystals. As discussed in the previous chapter, application of magnetic field above a critical value collapses the charge ordered phase which transforms to FMM phase. In this view, it is interesting to investigate effect of electric field on the charge ordering. There are various reports on doped manganites such as Pr1-xCaxMnO3 (x = 0:3 to 0:4) that claim melting of charge ordering under application of electric field (or current) above a critical value. In this thesis work, current - voltage (I - V) characteristics of Gd0.5Sr0.5MnO3 are studied at various constant temperatures. Preliminary measurements show that the I-V characteristics are highly non-linear and are accompanied by the onset of negative differential resistance (NDR) above a critical current value. However, we suspect a major contribution of Joule heating in realization of the NDR. Continual I - V loop measurements for five loops revealed thermal drag and that the onset of NDR shifts systematically towards high current values until it disappeared in the current window. Two strategies were employed to investigate the role of Joule heating in realization of NDR: 1) monitoring the sample surface temperature during electric transport measurement and 2) reducing of the Joule heating in a controlled manner by using pulsed current I - V measuremenets. By tuning the duty cycle of the current pulses (or in other words, by controlling the Joule heating in the sample), it was feasible to shift the onset of NDR to any desired value of the current. At low magnitude of the duty cycle in the current range upto 40 mA, the NDR phenomenon did not occur. These experiments concluded that the NDR in Gd0.5Sr0.5MnO3 is a consequence of the Joule heating. Chapter:6 `Chapter-6 deals with the thermal and magnetocaloric properties of Gd0.5Sr0.5MnO3 oriented single crystals. Magnetocaloric properties of Gd0.5Sr0.5MnO3 have been studied using magnetic and magnetothermal measurements. Tempera-ture variation of ∆SM is estimated for magnetic field change of 0 - 70 kOe. The eld 70 kOe is well below the critical magnetic eld required for FOPT between COI and FMM phases. Magnetzation - field (M-H) loop shows minimal hysteresis for measurements up to 70 kOe. The minimal hysteresis behavior al-lows one to make fairly accurate estimation of magnetocaloric properties. ∆Tad was separately estimated from specific heat measurements at different magnetic fields. Specific heat studies show the presence of Schottky-like anomaly at low temperature. Chapter:7 Finally, Chapter-7 summarizes various experimental results, analyses and conclusions. A broad outlook of the work in general with future scope of research in this area are outlined in this chapter.

This thesis presents the results of investigations of the synthesis, structure and physical properties of multiferroic materials. Multiferroics are materials in which two or all three of ferroelectricity, ferromagnetism and ferroelasticity occur in the same phase. Such materials have the potential applications of their parent materials, as well as new ones because of the interaction between the order parameters. The thesis is organized into four sections. Section 1 gives an overview of multiferroics, explaining the origin of mul-tiferroicity , occurrence of magnetoelectric coupling, their possible technological ap-plications and the challenges involved. Section 2 gives the scope of the investigations. The specific objectives of the present research on yttrium chromite, heavy rare earth chromites, solid solutions of yttrium chromite, rare earth manganites doped with alkaline earth metals, charge-ordered rare earth ferrites and indium manganite are outlined. Experimental aspects of the work carried out are discussed in section 3. It gives details of the experimental set up and the basic operation principles of various structural and physical characterizations of the materials prepared. In section 4, results of the investigations are discussed. Magnetic and di-electric properties of yttrium chromite (YCrO3), heavy rare earth chromites and YCr1-xMnxO3 are reported in section 4.1. These materials show canted antiferro-magnetic behavior below the Nel transition temperatures and dielectric transitions at high temperatures. Role of local non-centrosymmetry is discussed based on high-resolution neutron powder diffraction data. In 4.2 we discuss the results of charge-ordered rare earth ferrites which show good magnetoelectric effect. Magnetic, dielectric and magneto-dielectric properties of YCr1-xMnxO3 (Ln = rare earth) are discussed in 4.3. These materials show magneto-dielectric effect. In 4.4 we discuss the near normal incidence far infrared reflectivity spectra of a single crystal of TbMnO3, in the spectral range of 50cm−1 to 700 cm−1 from 10 K to 300 K. Finally in 4.5, magnetic and dielectric properties of bulk and thin films of indium manganite are discussed.

Organic conjugated systems are attractive because of wide range of applications, which includes stimulated emission from -conjugated polymers, optical switches, organic solar cells and organic light emitting diodes, to name a few. They have the advantage of low cost, ease of processing and tunability of their linear and nonlinear optical properties by functionalization with donor or acceptor groups. In chapter 1, we provide an introduction to the π-conjugated systems and various interesting phenomena observed in these systems, This is followed by a brief description of the application of the above mentioned -conjugated systems for organic light emitting diodes, and organic photovoltaic cells. In the last section of this chapter, we give an introduction to magnetism due to π-electron systems. In chapter 2, we begin with energy band theory in one-dimension and its drawbacks. We introduce various model Hamiltonians which incorporate electron-electron inter-actions like Hubbard model, and Pariser-Parr-Pople (PPP) model. We present numerical techniques like valence-bond (VB) and constant MS techniques that are used to exactly solve the above model Hamiltonian. This is followed by an introduction to density matrix renormalization group method (DMRG) employed for the above model Hamiltonian for larger system in one-dimension and quasi-one-dimension. We give description of linear and nonlinear optical properties followed by the oriented gas model for ensemble of molecules. Various methods for computing polarizabilities and hyperpolarizibilities of molecules includes such as Finite-Field method, Sum-Over-State Method, and Correction Vector (CV) Methods are described in detail. In chapter 3, we look into fused azulene systems as a possible organic multiferroics. Azulene molecule with fused five and seven membered π-conjugated rings has a dipole moment, and the π-framework has geometric frustration. Hence in fused azulenes we can expect both ferroelectric and magnetic ground state. To explore this, we study low-lying correlated electronic states of fused azulenes using the long-range interacting PPP model and the finite DMRG method. The ground state is a singlet for oligomers up to 5 azulene units. For oligomers with more than 5 azulene units and up to 11 azulene units the oligomers have a triplet ground state. From the excitation gaps between the lowest MS = 0 state and the lowest states in MS=1, 2, and 3 sectors we predict that the ground-state spin of the fused azulene increases with the number of azulene units. In the thermodynamic limit, we expect the fused azulene to be a ferromagnet. Charge density calculations show that the ground state of the system has ferroelectric alignment of the dipoles of the monomeric units. Thus, a fused azulene system could be the first example of an organic molecule which is both ferromagnetic and ferroelectric, in the ground state. In chapter 4, we study the linear and nonlinear optical properties of diradical systems. We have studied linear and non-linear optical properties of π-conjugated diradicals because they are expected to exhibit large non-linear responses. The system studied are oligomers of dicyclopenta-fused acenes (DPA) and the s-indaceno[1,2,3-cd;5,6,7-c'd']diphenalene (IDPL) molecule. Spin-spin correlation functions within a correlated PPP model Hamiltonian, using exact diagonalization method, are used to characterize the diradical nature of DPA-2 and similar calculations on Anthracene have been performed to contrast this with a singlet character. The diradical character of DPA-2 is also manifest as low optical gap, low spin gap and large THG coefficients compared to Anthracene molecule. Larger DPA-k, k > 2, oligomers as well as the IDPL molecule have been studied within the DMRG technique. In the DPA-4, we nd a very small spin gap (0.04 eV), while in the oligomers with k > 4, we nd that the ground state is degenerate with the lowest triplet state. The energy of the second excited triplet state decreases with increasing size k and seems to saturate at ~0.36 eV in the thermodynamic limit. The lowest optical gap in DPA-4 is at 1.94 eV and has large transition dipoles, while for DPA-k, 4 < k ≥ 28, we have not been able to access states with large transition dipoles. The weak low-energy excitations seem to saturate at 0.5 eV and the two-photon gap also seems to be saturating at~ 0.3 eV in the thermodynamic limit. These polymers will not be IR uorescent by Kasha rule. The dominant component of the THG coefficient, γxxxx, is highest for DPA-4 which reduces almost by an order of magnitude in DPA-8; for k > 8 it increases up to the largest system with k=20 for which we have computed the coe cient. The variation of the charge gap of DPA oligomer with the increase in system size is small and in the polymer limit the charge gap is 4:24 eV. For IDPL molecule spin gap is 0.20 eV and next excited triplet state is at 1.48 eV. Two lowest singlet states in B space are nearly degenerate and have large transition dipole moments. Optical gaps to the above states are 2.20 eV and 2.22 eV. Two-photon gap in this system is 1.29 eV, hence this system is also non- uorescent. We calculated the dispersion of the major component of the THG coefficient, γxxxx, over a wide frequency range for this molecule, and we observe resonances corresponding to the 21Ag and 11Bu states. Extrapolated value of γxxxx at zero frequency is 15:58 x 106 a.u which is very large and the system does not have any donor or acceptor substituent groups. In chapter 5, we study absorption spectra and two photon absorption coefficient of expanded porphyrins (EPs). We nd that in the 4n+2 EPs there are two prominent low-lying one-photon excitations while in 4n systems there is only one such excitation. The two-photon gaps in both these types of systems are at energies close to the one-photon excitations. The spin gap in 4n+2 EPs are very small although the spin-1/2 Heisenberg calculations show that a pure spin system in this geometry will not have vanishing spin-gap. The charge density rearrangement in the one-photon excited state is most at the aza nitrogen site and at the meso carbon sites. In the two-photon states also the charge density rearrangement occurs mostly at the aza-ring sites. The bond order changes in these states is much more striking. In the one-photon state, the C-C bond length in the aza rings show a tendency to become uniform. Similar qualitative trend is also observed for the two-photon state. In chapter 6, we study linear and nonlinear optical properties of two push-pull polyenes stacked in head to head (HtH) and head to tail con gurations (HtT), at different stacking angles, exactly within the PPP model. Varying the stacking angle between polyenes, we nd that the optical gap varies slightly, but transition dipoles show large variation. The dominant component of first-order hyperpolarizability, βxxx for HtH and βyyy for HtT arrangement strongly depend on the distance between molecules. The βxxx for HtH configuration shows a maximum at a nonzero stacking angle, which varies with inter polyene distance. ZINDO study on two monomers, (4-hydroxy-40-nitro-azobenzene) connected by a conjugated bridge shows that βav is more than twice the monomer value and with a red-shift in the optical gap. In chapter 7, we have calculated the shifts in optical gaps and band edges as a function of the distance between two monomers within a correlated PPP model Hamiltonian for various stacking geometries. We have used as model monomers, both unsubstituted polyenes and push-pull substituted polyenes. We have carried out calculations with and without inter-chain hopping between sites on different molecules. We note that in the absence of inter-chain hopping, the energy level shifts are almost independent of the distances between the chains in all stacking geometries. It is also interesting to note that only electron-electron interactions yield a blue shift in the optical gaps for parallel stacking, but red shift in the gap for all other stacking geometries. We note that most of the shift in the gap is due to shifts in the excited state energy and the ground-state energy remains almost the same. With interchain transfer the shift in the optical gap increases with decrease in the interchain distance. We observe red-shifts in parallel stacking geometry when inter-chain electron hopping is turned on, at small interchain separations. In general interchain hopping increases significantly the red shift in the optical gaps for all geometries. Even for push-pull polyenes of | e| =2.0 eV, we observe the same trend in the shift in the optical gap for various stacking geometries. In this case the shift in optical gap is an order of magnitude higher when interchain hopping is turned on compared to that in the absence of interchain hopping. We find that the optical gap shifts are largest for the parallel stacking geometry, and it also shows stronger distance dependence. This is in close conformity with experimental observation of red-shift in absorption maxima when hydrostatic pressure is applied on the system. The shift in the HOMO (LUMO) level is small in the absence of t?, and the largest shift is in the case of parallel stacking compared to other stacking geometries. The distance dependence of the HOMO shifts is also rather weak. When t? is turned on, the level shifts become large by a factor of five or more. When we have push-pull groups electron-hole symmetry is broken and the shift is different for the HOMO and the LUMO level. Depending upon stacking geometry, the HOMO shifts vary from 0:1 ~ eV to 0.3 eV, which is larger than the shifts observed in unsubstituted polyenes. This large shift in the LUMO reduces the efficiency of exciton dissociation.

Multiferroic materials with a coupled ordering of electric and magnetic moments could be used to build energy-efficient, magnetic computer memory that is written with an electrical field. To understand the interaction between the magnetic and electric ordering in such materials, two examples, namely yttrium manganate YMn2O5 and neodymium iron borate NdFe3(BO3)4, are studied by means of resonant x-ray diffraction. The important role of a pure electronic contribution to the ferroelectric polarization is shown in YMn2O5. Furthermore, substitution of Fe can change the magnetic order of YMn2O5 from antiferromagnetic into ferrimagnetic, allowing the storage of easily readable magnetic information. Therefore the change of the magnetic structure upon small Fe substitution is studied. Although most of the magnetic structure of the parent compound is kept, the Fe moments have larger components along the c-direction. In NdFe3(BO3)4 the microscopic origin of the magnetoelectric coupling is addressed as the consequence of the frustration of the Fe and Nd magnetic sublattices. The application of an electrical field shifts the balance from the helical to the collinear magnetic domains, revealing again the strong magnetoelectric coupling. / Multiferroische Materialien mit einer starken magnetoelektrischen Kopplung können als energieeffizienter, magnetischer Speicher benutzt werden, welcher mit einem elektrischen Feld geschrieben wird. Um die Wechselwirkung der elektrischen mit der magnetischen Ordnung in solchen Materialien zu verstehen, werden hier zwei Beispiele, nämlich Yttriummanganat YMn2O5 und Neodymeisenborat NdFe3(BO3)4, mit resonanter Röntgenbeugung untersucht. In YMn2O5 wird die wichtige Rolle eines rein elektronischen Beitrags zur ferroelektrischen Polarisation gezeigt. Um die magnetische Struktur von YMn2O5 von antiferromagnetisch zu ferrimagnetisch zu verändern, kann Fe substituiert werden. Dies ermöglicht es, leicht zu lesende, magnetische Informationen zu speichern. Daher wurde die Änderung der magnetischen Struktur bei leichter Fe Substituierung untersucht. Auch wenn die magnetische Struktur von Fe im wesentlichen der magnetischen Struktur von Mn folgt, haben die Fe Momente größere Komponenten entlang der c-Richtung. In NdFe3(BO3)4 wird der Ursprung der starken magnetischen Kopplung als Folge der Frustration des Nd und Fe Untergitters erklärt. Das Anlegen eines elektrischen Feldes führt zur Verschiebung des Gleichgewichts von den helikalen zu den kollinearen magnetischen Domänen, welches wieder die starke magnetoelektrische Kopplung veranschaulicht.

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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.

Crystal growth and characterization of few multifunctional materials with perovskite (ABX3) structure are discussed in this thesis. Efforts were made to modify the magnetic and electric behaviour of these materials by selective tuning of A, B and X components. Structural, magnetic and dielectric characterization are detailed in various chapters for doped (A and B site) rare-earth manganites and organometallic compounds with different (Chloride or formate) anions. The relevant aspects of crystal structure and its relationship with ordered ground states are discussed in the introductory chapter. A detailed review of prominent theories pertaining to magnetic and ferroelectric ordering in the literature is provided. Growth of various inorganic compounds by solid-state reaction and floating zone method as well as use of solvothermal techniques for growing organometallic compounds are discussed. Material preparation, optimization of crystal growth processes and results of characterization are addressed in various chapters. The effect of Yttrium doping on structural, magnetic and dielectric properties of rare-earth manganites (RMnO3 where R = Nd, Pr) has been investigated. Neutron diffraction studies (Pr compounds) confirm A-type antiferromagnetic structure and fall in transition temperature as the Yttrium doping level increases. Diffraction experiments in conjunction with dc magnetization and ac susceptibility studies reveal magnetic frustration in excess Yttrium dopedcompounds. When mutliglass properties of 50% B-site doped Nd2NiMnO6 were investigated, evidence of re-entrant cluster glass phase was seen probably due to presence of anti-site disorder. The relaxor-like dielectric behaviour arises from crossover of relaxation time in grain and grain boundary regions. Multiferroic behaviour of the organometallic compound (C2H5NH3)2CuCl4 as well as the ferroelectric transition were investigated in detail. The role of Hydrogen bond ordering in driving structural transitions is elucidated by low temperature dielectric and Raman studies in (C2H5NH3)2CdCl4. It was found possible to tune the magnetic and ferroelectric properties in metal formate compounds (general formula AB(HCOO)3) by selectively choosing organic cations [(CH3)2NH2+; C(NH3)3+] and transition metal ion [B = Mn, Co and Cu]. The nature of magnetic ordering and transition temperature could be altered by the transition metal ion. The effect of reorientation of organic cations which leads to ferroelectric nature is discussed using dielectric and pyroelectric data. Significant results are summarized in the chapter outlining general conclusions. Future prospects of work based on these observations are also provided. The conclusions are corroborated by detailed analysis of experimental data.

Over the last two decades, great progress has been made in the understanding of multiferroic materials, ones where multiple long-range orders simultaneously exist. However, much of the research has focused on bulk systems. If these materials are to be incorporated into devices, they would not be in bulk form, but would be miniaturized, such as in nanoparticle form. Accordingly, a better understanding of multiferroic nanoparticles is necessary. This manuscript examines the multiferroic phase diagram of multiferroic nanoparticles related to system size and surface-induced magnetic anisotropy. There is a particular focus on bismuth ferrite, the room-temperature antiferromagnetic-ferroelectric multiferroic. Theoretical results will be presented which show that at certain sizes, a bistability develops in the cycloidal wavevector. This implies bistability in the ferroelectric and magnetic moments of the nanoparticles. This novel magnetoelectric bistability may be of use in the creation of an electrically-written, magnetically-read memory element. / Graduate