There has been significant interest in BiFeO₃ over the past decade. This interest has focused on the magnetic and electrical properties, which in the long term may prove useful in device applications. This thesis focuses on the synthesis, electrical characterisation, and structural origin of the electrical properties of rare earth doped bismuth ferrite. Two systems have been studied: BiFeO₃ doped with lanthanum and neodymium (Bi₁₋ₓREₓFeO₃ RE= La, Nd). Specific examples have been highlighted focusing on a detailed structural analysis of a lanthanum doped bismuth ferrite, Bi₀.₅La₀.₅FeO₃, and a neodymium analogue, Bi₀.₇Nd₀.₃FeO₃. Both adopt an orthorhombic GdFeO₃-type structure (space group: Pnma) with G-type antiferromagnetism. Structural variations were investigated by Rietveld refinement of temperature dependent powder neutron diffraction using a combination of both conventional “bond angle/bond length” and symmetry-mode analysis. The latter was particularly useful as it allowed the effects of A-site displacements and octahedral tilts/distortions to be considered separately. This in-depth structural analysis was complemented with ac-immittance spectroscopy using the multi-formulism approach of combined impedance and modulus data to correlate structural changes with the bulk electrical properties. This approach was essential due to the complex nature of the electrical response with contributions from different electroactive regions. The structural variations occur due to a changing balance between magnetic properties and other bonding contributions in the respective systems. This results in changes in the magnitude of the octahedral tilts, and A-site displacements giving rise to phenomena such as negative thermal expansion and invariant lattice parameters i.e., the invar effect. More specifically, analysis of Bi₀.₅La₀.₅FeO₃ highlights a structural link between changes in the relative dielectric permittivity and changes in the FeO₆ octahedral tilt magnitudes, accompanied by a structural distortion of the octahedra with corresponding A-site displacement along the c-axis; this behaviour is unusual due to an increasing in-phase tilt mode with increasing temperature. The anomalous orthorhombic distortion is driven by magnetostriction at the onset of antiferromagnetic ordering resulting in an Invar effect along the magnetic c-axis and anisotropic displacement of the A-site Bi³⁺ and La³⁺ along the a-axis. This contrasts with the neodymium analogue Bi₀.₇Nd₀.₃FeO₃ in which a combination of increasing A-site displacements in the ac-plane and decrease in both in-phase and anti-phase tilts combine with superexchange giving rise to negative thermal expansion at low temperature. The A-site displacements correlate with the orthorhombic strain. By carefully changing the synthesis conditions, a significant change in bulk conductivity was observed for a number for Bi₁₋ₓLaₓFeO₃ compositions. A series of Bi₀.₆La0.₄FeO₃ samples are discussed, where changes in the second step of the synthesis result in significantly different bulk conductivities. This behaviour is also observed in other compositions e.g. Bi₀.₇₅La₀.₂₅FeO₃. Changes in the electrical behaviour as a function of temperature are discussed in terms of phase composition and concentration gradients of defects. Activation energies associated with the conduction process(es) in Bi₁₋ₓLaₓFeO₃ samples, regardless of composition, fall within one of two broad regimes, circa. 0.5 eV or 1.0 eV, associated with polaron hopping or migration of charge via oxygen vacancies, respectively. The use of symmetry-mode analysis, in combination with conventional crystallographic analysis and electrical analysis using multi-formulism approach, presents a new paradigm for investigation of structure-property relationships in rare earth doped BiFeO₃.

Le travail sur le ZnO:Co rapporté dans ce manuscrit, donne une meilleure compréhension des interactions d'échange dans ce composé. La question des interactions spin-spin dans les DMS est abordée à la fois sur le plan théorique et expérimental. Du point de vue théorique, le modèle du superéchange d'Anderson a été utilisé et étendu, afin d'obtenir les valeurs des constantes d'échange sur l'ensemble de la série des DMS II-VI dopés Mn ou Co. Du point de vue expérimental, la combinaison inédite de trois méthodes expérimentales, la diffusion inélastique de neutrons (ou INS), la résonance paramagnétique électronique (ou EPR), et la méthode de mesure des marches d'aimantation sous champ magnétique intense (ou méthode MST), a permis d'établir, pour la première fois, la valeur des dix plus grandes constantes d'échange du ZnO:Co.Les observations faites par INS permettent de mettre en évidence de façon directe une très forte anisotropie spatiale concernant l'intégrale d'échange des premiers voisins. On établit ainsi J(1)=-25,6K et J(2)=-8,5K, correspondant respectivement à la paire des premiers voisins dans le plan (ab), et à la paire des premeirs voisins hors de ce plan. Ce résultat s'explique, en partie, par la présence dans la structure wurtzite d'une contribution ferromagnétique dans le calcul du superéchange, issue d'un chemin formant une boucle et faisant intervenir deux anions distincts.Les mesures effectuées par EPR et par MST permettent d'établir les constantes d'échange entre voisins à plus grande distance. Ainsi, on obtient: J(3)=-1,07K , J(4)=-0,38K , J(5)=0,35K , J(6)=0,17K , J(7)=-0,16K , J(8)=-0,04K , J(9)=-0,03K , |J(10)|=0,013K. / The work performed on ZnO:Co enables a better understanding of exchange constants. The question of the spin-spin interactions in the Diluted Magnetic Semiconducteur (DMS) is studied from both theoretical and experimental approaches. On the théoretical side, a exchange constants for all the II-VI series doped Mn et CO. On the experimental side, the use of three techniques, Inelastic Neutron Scattering (INS), Electron Paramagnetic Resonance (EPR), and the Magnetization Steps (MST) method, has made it possible to establish, for the first time, the ten largest exchange constants in ZnO:Co.The INS experiments show, in direct way, astrong spatial anisotropy of the nearest enighbor exchange integral J(1)=-25.6 K and J(2)=-8.5 K. This result can be explained, in part, by the presence, in the wurtzite structure, of a looped exchange path which involves two distinct anions and is ferromagnetic. To justify this explanation, our model was expanded to cover the entire II-VI series doped Mn and Co. The concurrent results, for the complete series, between the known experimental data and the theoretical exchange values permit the justification and the validation of our hypotheses.The measures performed by EPR and MST enable, for their part, the establisment of the distant neighbor exchange constants. the two techniques give complementary information, and make it possible to directly observe the exchange constants of ZnO:Co going from the third to the tenth largest value, J(3)=-1.07 K ,J(4)=-0.38 K , J(5)=+0.35 K , J(6)=+0.17 K , J(7)=-0.13 K , J(8)=-0.04 K , J(9)=-0.03 K , |J(10)|=0.01 K.

The use of two different chelating redox active ligands, 2,6-bis(6-methyl-1,2,4,5-3-yl) pyridine (BTZP) and 2,6-bis-(5,6-dialkyl-1,2,4-triazin-3-yl)-pyridine (BTP) in heterometallic first row and second row transition metal chemistry has yielded two new families of redox active metal complexes. These complexes were found to exhibit interesting electrochemical and magnetic properties. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of the ligand design, ligand synthesis and related coordination chemistry literature review. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of discrete molecules and supramolecular arrangements, employing the ligand BTZP, is presented. All of the complexes presented in Chapter 2 are successfully synthesized and characterized with electrochemical and magnetic studies. According to the electrochemical data, it is found that the classic “terpy-like” complexes with [Co(BTZP) 2]2+ formula fosters more stability in the redox process. In Chapter 3, a family of transition metal complexes with [M(BTP) 2]2+ (M=Fe or Co) inorganic cores were obtained through the employment of the ligand BTP with various anions. In addition, dimeric molecules with [CoX4(BTP)2] formula were also obtained by solvothermal synthesis. The complexes were also electrochemically characterized, with all the complexes capable of being reduced, while only [CoII(BTP)2] (ClO4)2 showed reversible redox process. Similar with BTZP, the series of BTP based complexes are also characterized through magnetic measurement. Only cobalt-based BTP complexes are paramagnetic, with [CoII(BTP)2]2+ being spin crossover active when BF4- and ClO4- are present. However, the presence of NCS- and halides lead to either antiferromagnetic interactions and ferromagnetic interactions dominating at different temperature regimes.

No description available.

Semiconductor quantum dot systems offer a promising platform for quantum computation. And these quantum computation candidates are normally based on spin or charge properties of electrons. In these systems, we focus on quantum computation based on electron spins since these systems has good scalability, long coherence times, and rapid gate operations. And this thesis focuses on building a theoretical description of quantum dot systems and the link between theory and experiments. In many quantum dot systems, exchange interactions are the primary mechanism used to control spins and generate entanglement. And exchange energies are normally positive, which limits control flexibility. However, recent experiments show that negative exchange interactions can arise in a linear three-dot system when a two-electron double quantum dot is exchange coupled to a larger quantum dot containing on the order of one hundred electrons. The origin of this negative exchange can be traced to the larger quantum dot exhibiting a spin triplet-like rather than singlet-like ground state. Here we show using a microscopic model based on the configuration interaction (CI) method that both triplet-like and singlet-like ground states are realized depending on the number of electrons. In the case of only four electrons, a full CI calculation reveals that triplet-like ground states occur for sufficiently large dots. These results hold for symmetric and asymmetric quantum dots in both Si and GaAs, showing that negative exchange interactions are robust in few-electron double quantum dots and do not require large numbers of electrons. Recent experiments also show the potential to utilize large quantum dots to mediate superexchange interaction and generate entanglement between distant spins. This opens up a possible mechanism for selectively coupling pairs of remote spins in a larger network of quantum dots. Taking advantage of this opportunity requires a deeper understanding of how to control superexchange interactions in these systems. Here, we consider a triple-dot system arranged in linear and triangular geometries. We use CI calculations to investigate the interplay of superexchange and nearest-neighbor exchange interactions as the location, detuning, and electron number of the mediating dot are varied. We show that superexchange processes strongly enhance and increase the range of the net spin-spin exchange as the dots approach a linear configuration. Furthermore, we show that the strength of the exchange interaction depends sensitively on the number of electrons in the mediator. Our results can be used as a guide to assist further experimental efforts towards scaling up to larger, two-dimensional quantum dot arrays. / Doctor of Philosophy / Semiconductor quantum dot systems offer a promising platform for quantum computation. And these quantum computation candidates are normally based on spin or charge properties of electrons. In these systems, we focus on quantum computation based on electron spins since these systems has good scalability, long coherence times, and rapid gate operations. And this thesis focuses on building a theoretical description of quantum dot systems and the link between theory and experiments. A key requirement for quantum computation is the ability to control individual qubits and couple them together to create entanglement. In quantum dot spin qubit systems, the exchange interaction is the primary mechanism used to accomplish these tasks. This thesis is about attaining a better understanding of exchange interactions in quantum dot spin qubit systems and how they can be manipulated by changing the configuration of the system and the number of electrons. In this thesis, we show negative exchange energy can arise in large size quantum dots. This result holds for symmetric and asymmetric shape of the large dots. And we also provide a quantitative analysis of how large quantum dots can be used to create long-distance spin-spin interactions. This capability would greatly increase the flexibility in designing quantum processors built by quantum dot spins. The interplay of these systems with different geometry can serve as a guide to assist further experiments and may hopefully be the basis to build two-dimensional quantum dot arrays.

<p>Processes where a molecule absorbs visible light and then disposes of the excess energy via electron/energy transfer reactions have an important role both in nature (e.g. in photosynthesis) and in many technical applications (e.g. in photography and photovoltaics). This thesis uses different spectroscopical techniques, mainly ultrafast transient absorption, to study such processes. The thesis can roughly be divided into three parts.</p><p>In the first part, donor-acceptor systems linked by different conjugated bridges are studied. The objective was to see to what extent the conjugated link could enhance excited state energy or electron transfer, via so-called superexchange processes. The studied links do enhance the electron/energy transfer but in the electron transfer study the resulting charge separated state was very short lived.</p><p>The second part explores the possibility of constructing acceptor-donor-acceptor triads where the direction of electron transfer is determined by the electronic state of the donor. Direct evidence of electron transfer in the form of radical absorption was found from both the first and the second excited states of the donor.</p><p>In the last part, two common chromophores were investigated by transient absorption anisotropy. In the case of Ru(bpy)₃²⁺, it was found that the complex lost all memory of the polarization of the exciting light much faster than what was previously thought. This means that electron transfer between ligands is normally not the rate limiting step in electron transfer reactions involving this complex. In the case of zinc porphyrin, it was seen that the measured anisotropy differed depending on which electronic state was excited suggesting differences in the degree of coherence.</p>

Processes where a molecule absorbs visible light and then disposes of the excess energy via electron/energy transfer reactions have an important role both in nature (e.g. in photosynthesis) and in many technical applications (e.g. in photography and photovoltaics). This thesis uses different spectroscopical techniques, mainly ultrafast transient absorption, to study such processes. The thesis can roughly be divided into three parts. In the first part, donor-acceptor systems linked by different conjugated bridges are studied. The objective was to see to what extent the conjugated link could enhance excited state energy or electron transfer, via so-called superexchange processes. The studied links do enhance the electron/energy transfer but in the electron transfer study the resulting charge separated state was very short lived. The second part explores the possibility of constructing acceptor-donor-acceptor triads where the direction of electron transfer is determined by the electronic state of the donor. Direct evidence of electron transfer in the form of radical absorption was found from both the first and the second excited states of the donor. In the last part, two common chromophores were investigated by transient absorption anisotropy. In the case of Ru(bpy)32+, it was found that the complex lost all memory of the polarization of the exciting light much faster than what was previously thought. This means that electron transfer between ligands is normally not the rate limiting step in electron transfer reactions involving this complex. In the case of zinc porphyrin, it was seen that the measured anisotropy differed depending on which electronic state was excited suggesting differences in the degree of coherence.

Synthesis, nuclear structure, and magnetic properties of the perovskites: Nd0.7-xMgxSr0.3MnO3 (x=0.0, 0.1), Nd0.6Mg0.1Sr0.3Mn1-zMgzO3 (z=0.1, 0.2), LaCr1-yMnyO3 (y=0.0, 0.1, 0.2, 0.3) and La1-xNdxFe0.5Cr0.5O3 (x=0.1, 0.15, 0.2) have been studied. The structure of the samples was investigated by X-ray and Neutron powder diffraction and the magnetic properties were investigated by magnetization measurements using SQUID-magnetometry. All compounds have orthorhombic structure with spacegroup Pnma (No. 62). The compounds which had the composition Nd0.7Sr0.3Mn1-yMgyO3 by preparation, were found to attain the composition Nd0.7-xMgxSr0.3MnO3 and Nd0.6Mg0.1Sr0.3Mn1-zMgzO3. The x=0.0 and 0.1 compounds order in a pure ferromagnetic structure at about 200 K, but the Mn moments become slightly tilted and attain an antiferromagnetic component below 20 K. A ferromagnetic Nd moment also appears at low temperatures. The compounds with Mg substitution y=0.2 and 0.3 do not exhibit long range magnetic order, but local ferromagnetic correlations among the Mn moments appear below 200 K. At low temperature, also a local antiferromagnetic ordering of the Nd magnetic moments occurs. In these compounds, the Mn3+/Mn4+ ratio is reduced so that the double exchange interaction is suppressed and the antiferromagnetic superexchange interaction favoured. The samples of composition LaCr1-yMnyO3 have orthorhombic structure at room temperature and below. The magnetic properties of the system are markedly affected by Mn-substitution. The parent compound LaCrO3 is a pure G-type antiferromagnet with Néel temperature 290 K. With incresing Mn-substitution, a ferromagnetic component developes in the ordered phase bcause of canting of the magnetic moments. The degree of canting increases with increasing Mn-substitution and the magnitude of the antiferromagnetic component of the moment decreases. The system La1-xNdxFe0.5Cr0.5O3 has the same antiferromagnetic G-type structure as LaCrO3, but orders already at temperatures above 400 K and develops only a very weak ferromagnetic component of the magnetic moment at low temperatures.

The hole-doped perovskite manganese oxide such as Ln1-xAxMnO3 (Ln = La, Nd, Pr, and A = Ca, Sr, Ba, Pb) is one of the most studied topics in the recent years due to the observation of colossal magnetoresistance (CMR). Basically, LaMnO3 has an almost insulating behavior and on antiferromagnetic arrangement. By substituting a divalent cation (A2+) in place of La3+, LaMnO3 can be driven into metallic and ferromagnetic state. Mixed valence of Mn 3+ / Mn4+ is needed for both metallic behavior and ferromagnetism in these materials. The CMR characteristic occurs in the ferromagnetic state. A systematic investigation of the structural, magnetic and electrical properties in the perovskite colossal magnetoresistance materials La0.7-xLnxPb0.3Mn1-yMeyO3 (Ln=Pr, Nd and Y, Me=Fe and Co) has presented in this thesis. By subatituting Nd, Pr, Y for the La and Co, Fe for the Mn, the substitution effects on the crystallographic deformation, magnetotransport behavior and electrical properties in these compounds have been studied. According to the results of this research, crystallographic distortion is induced by the substitution of smaller ions, Pr or Nd, onto the La-site. Powder $x$-ray diffraction patterns show a crystallographic transition from rhombohedral symmetry (R-3c) to orthorhombic (Pbnm) crystal structure as the doping content is increased. The increase of deformation from R-3c to Pbnm decreases the bond angle of Mn3+¡ÐO2-¡ÐMn4+ , increases the cant of Mn spin, weakens the double-exchange interaction and results in decrease of ferromagnetism, low ferromagnetic transition temperature Tc, eg electron bandwidth and conductivity. However, the great quantity of decrease in resistivity by an external field leads to the increase in the magnetoresistance ratio. We also find that the increase of saturation magnetization results from the contribution of magnetic ion of Pr or Nd. In addition. in contrast to substitution La by magnetic ion of Pr and Nd, the saturation magnetization is decreased as Y content is increased. The zero-field-cool (ZFC) and field-cool (FC) magnetic measurements indicate that the range of spin ordering for Y one is shorter than Pr one or Nd one with the same doping content. It is because of the small ionic radius of Y, which results in larger distortion, increases the bond angle of Mn3+¡ÐO2-¡ÐMn4+, and corresponds low ferromagnetic transition temperature. The distortion induced by Mn-site substitution is not obvious due to the similar radius of Mn, Co and Fe. Powder x-ray diffraction patterns show a single phase of rhombohedral symmetry (R-3c) for Co doped ststem and a slight crystallographic transition from rhombohedral (R-3c) to orthorhombic (Pbnm) symmetry for Fe doped system. Values of temperature dependence of magnetization indicate that the ferromagnetic double-exchange interaction is gradually substituted by the superexchange interaction. The ZFC-FC curves also indicate that long-range spin ordering is progressively substituted by the short-range spin ordering. The substitution of Mn by Co and Fe supresses the double-exchange interaction, decreases the ferromagnetism and the ferromagnetic transition temperature. Due to the synthesis of the substitution of Nd, Pr, Y for La and Co, Fe for Mn, the mechanism of substitution effects are proved different. The substitution of Nd, Pr and Y for La distorts the crystal, decreases the Mn3+¡ÐO2-¡ÐMn4+ bond angle, and results in the transition of properties, while the substitution of Co and Fe for Mn decrease the percentage of ferromagnetic Mn3+¡ÐO2-¡ÐMn4+. The purpose of this thesis is to clear up the role functions of all elements in these compounds and properties of these compounds. Based on the knowledge of these compounds, it would be helpful to control the physical mechanism and improve the characteristics on preparing their thin film devices.

We have modeled some magnetic systems, which consists of a number of sublattices, in the mean field approximation. This is possible in crystalline systems formed by two or more magnetic ions coupled by specific interactions such as the crystal field, exchange, among others. The main idea is to solve the microscopic Hamiltonian that models a given magnetic system in order to obtain their magnetic equation of state: M (H, T). For this, we use the appropriate arrangements to different magnetic (ferro-, ferri- and antiferro- magnetic) scheme sublattices. From the solutions of the Hamiltonian (eigenvalues and eigenvectors), physical quantities of interest were determined. In principle we consider systems with localized magnetism due to 3d and 4f electrons with the participation of non-magnetic ligands including 3d-4f systems with the presence of crystal field. In this dissertation we use the model of two-and three sublattices in order to obtain the equation of state for the following systems: RKKY exchange in RNi2B2C, superexchange in (Y3-zRz)(T1xFe1-x)(T2yFe3-y)O12, LixFe3- xO4 and (NixMn1-x)1.5[Cr(CN)6]. In these formulas, R represents a rare earth ion, T1 and T2 represent non-magnetic ions. Some representative cases are presented to illustrate the different equations of state and behavior of sublattices, metamagnetism, temperature compensation, etc. The extension to other similar systems can be direct or need to incorporate additional phenomenological parameters. / Consideramos neste estudo sistemas magnéticos modeláveis mediante sub- redes na aproximação do campo médio. Isto é possível em sistemas cristalinos formados por dois ou mais íons magnéticos acoplados por interações específicas como as do campo cristalino, troca, entre outros. A ideia central é resolver o hamiltoniano microscópico que modela um determinado sistema magnético de maneira a se obter sua equação de estado magnética: M(H,T). Para isto usamos o esquema de sub- redes adequado a diferentes arranjos magnéticos (ferro-, ferri- e antiferro- magnéticos). Com as soluções do hamiltoniano (autovalores e autovetores), grandezas físicas de interesse foram determinadas. Em princípio, consideramos sistemas com magnetismo localizado devido a elétrons 3d e 4f com participação de ligandos não magnéticos incluindo sistemas 3d-4f com presença de campo cristalino. Neste trabalho de dissertação empregamos o modelo de duas e três sub- redes para obter as equações de estado nos seguintes sistemas: troca tipo RKKY em RNi2B2C, supertroca em (Y3-zRz)(T1xFe1-x)(T2yFe3-y)O12, LixFe3-xO4 e (NixMn1- x)1.5[Cr(CN)6]. Nestas fórmulas, R representa um íon de terra rara, T1 e T2 representam íons não magnéticos. Alguns casos representativos são apresentados para exemplificar as diferentes equações de estado e comportamento das sub- redes, metamagnetismo, temperatura de compensação etc. Em princípio, a extensão para outros sistemas semelhantes, usando os modelos apresentados aqui, pode ser direta ou precisar incorporar parâmetros fenomenológicos adicionais.