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Multiferroic Bismuth Ferrite-Lead Titanate and Iron-Gallium Crystalline Solutions: Structure-Property InvestigationsWang, Naigang 20 July 2005 (has links)
Recently, multiferroics-defined as materials with coexistence of at least two of the ferroelectric, ferroelastic and ferromagnetic effects-have attracted enormous research activities. In this thesis, the structure and properties of multiferrioic BiFeO3-x%PbTiO3 and Fe-x%Ga crystalline solutions were investigated.
First, the results show that modified BiFeO3-PbTiO3 based ceramics have significantly enhanced multiferroic properties, relative to BiFeO3 single crystals. The data reveal: (i) a dramatic increase in the induced polarization; and (ii) the establishment of a remnant magnetization by a breaking of the translational invariance of a long-period cycloidal spin structure, via substituent effects. In addition, temperature dependent magnetic permeability investigations of BiFeO3-xPbTiO3 crystalline solutions have shown that aliovalent La substitution results in a significant increase in the permeability.
Second, room temperature high-resolution neutron and x-ray diffraction studies have been performed on Fe-x%Ga crystals for 12<x<25at%. It has been observed that the structures of both Fe-12%Ga and Fe-25%Ga are tetragonal; however, near the phase boundary between them, an averaged-cubic structure was identified. In addition, an unusual splitting along the transverse direction indicates that the crystals are structurally inhomogeneous. / Master of Science
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An investigation of the structural and magnetic properties of Ho substituted BiFeO3Ncube, Mehluli 18 September 2012 (has links)
The doping of BiFeO3 with lanthanide elements like Ho, with a radius smaller than Bi, is ideal to improve the ferroelectric and magnetic properties of BiFeO3, which in principle can cause structural distortions of the lattice that improve the electrical and magnetic properties. In this work, we report on the temperature dependence of the structural and magnetic properties of Ho substituted BiFeO3 (BHFO) samples, which have been investigated by X-ray diffraction (XRD) and Mössbauer spectroscopic techniques. The XRD and Mössbauer measurements were done at room temperature on the as-synthesized BHFO samples and after annealing the samples in Argon up to 1073 K. The resultant XRD patterns have shown that BHFO is of rhombohedral R3m space group, with a majority Bi25FeO90 phase and a minority Bi2Fe4O9 phase. These two phases are attributed to the local stoichometry fluctuations in BiFeO3 (BFO). A new phase was evident in the XRD spectra after annealing the sample between 673 – 873 K; this has been assigned to the octahedral B-site of Fe3O4.
The Mössbauer spectra were characterized by broadened features and the magnetic hyperfine splitting patterns were indicative of magnetic ordering mostly probably screwed or slightly antiferromagnetic ordering. The spectra were fitted with two symmetric sextets (S1 & S2) which were present in all annealed samples, a symmetric sextet (S3) which was observable at annealing temperatures greater than 673 K, a Lorentzian doublet (D) and a single line (SL) which were present in all spectra. The extracted hyperfine parameters of sextet S1 are consistent with those of rhombohedral BiFeO3 and are characteristic of magnetically ordered Fe3+. At TA > 673 K, a third sextet S3 was assigned to the high symmetry cubic spinel phase. The paramagnetic doublet D was attributed to the Bi25FeO40 phase and the singlet line SL to the Bi2Fe4O9 phase which has been observed previously in the studies of BiFeO3 and other BiFeO3 doped systems. The isomer shift and quadrupole splitting values of the paramagnetic doublet D corresponds to an oxidation state of Fe3+, while the isomer shift of S1 remained fairly constant up to TA = 623 K then decreased gradually after the appearance of S3 indicating an increase of the s-electron density at the Fe nucleus. The quadrupole splitting of S2 showed no systematic change with annealing temperature, however at TA > 623 K this parameter changed dramatically to a negative value with a slightly larger magnetic field. The distribution of the isomer shift and the difference in the quadrupole splitting values and signs are due the variation in the angles between the principal axis of the electric field gradient (EFG) and the spin direction. The hyperfine fields of S1 and S2 remained fairly constant for all measured samples, however at TA > 623 K the hyperfine field of S3 showed a slight increase which could be due to Ho being substituted at the Fe site in BiFeO3. In addition, in-situ Mössbauer measurements at temperatures in the range 300 – 748 K were made on the BHFO samples. The room temperature spectrum showed similar features as observed on the annealing series of measurements. The hyperfine magnetic fields of the two sextet components (S1 and S2) decreased with increasing temperature and finally collapsed at T > 588 K. The hyperfine fields of both the S1 and S2 components decreased systematically with temperature to a field distribution just below the Néel temperature. From our measurements, we estimated the Néel temperature for BHFO to be in the range 598 – 617 K. The isomer shift for all spectral components showed a linear decrease with increasing temperature which closely followed the usual second order Doppler shift variation with temperature. The S1 and S2 spectral components present at room temperature disappeared just before the Néel temperature resulting in the area fraction of the paramagnetic doublet D dominating the spectrum. From the site populations, an average Debye temperature (θD) was estimated to be 240 ± 81 K for BHFO which is lower than the value of 340 ± 50 K cited for BiFeO3.
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Deposição de filmes BiFeO3 via spray pirólise e caracterização microestrutural e de propriedades elétricas e ópticasOliveira, Felipe Fernandes de January 2015 (has links)
Este trabalho investigou a deposição de filmes finos de ferrita de bismuto (BFO) através da técnica spray pirólise utilizando sais inorgânicos como precursores em diferentes solventes e silício como substrato, visando a deposição em menor temperatura e a obtenção de diferentes morfologias de superfície. Para tanto, foram utilizados água, etilenoglicol e etanol/butil carbitol (1:1) como solventes na preparação da solução a ser aspergida. Foram realizadas deposições com diferentes temperaturas do substrato: 200, 250, 300 e 350ºC para cada solvente utilizado. A deposição de filmes BFO em baixas temperaturas (200ºC) favoreceu a formação de filme. Para o solvente etilenoglicol (maior ponto de ebulição), verifica-se a formação de filmes porosos, já para o solvente etanol/butil carbitol (1:1) foi verificada a formação de filmes densos com a presença de trincas. As análises termogravimétricas (ATG) e termodiferenciais (ATD) foram realizadas para os filmes como-depositados a 200ºC com diferentes solventes. Após a deposição, as amostras foram tratadas termicamente a 550ºC por 1h, visando a formação da fase cristalina BiFeO3 com estrutura romboédrica. Os filmes foram analisados por difração de raios X (DRX) e microscopia eletrônica de varredura (MEV). Os resultados mostraram a obtenção da fase cristalina do BiFeO3 após o tratamento térmico a 550ºC/1h com a presença de fase secundária. As imagens de MEV evidenciaram a formação de filmes independente do solvente utilizado para a temperatura de 200ºC. Contudo, o aumento da temperatura promoveu a formação de partículas sobre o substrato e não uma formação contínua de filme, evidenciada pela composição elementar medida através de espectroscopia por energia dispersiva de raios X (EDX). A caracterização elétrica dos filmes foi realizada utilizando espectroscopia de impedância (EI) em função da temperatura, sendo observada maior condutividade para o filme depositado com etilenoglicol. A fase BFO não estequiométrica evidenciada por DRX pode explicar as diferentes condutividades elétricas mensuradas por EI quando utilizado diferentes solventes. As propriedades ópticas foram medidas utilizando-se espectroscopia de reflectância difusa, encontrando-se um band gap entre 2,23 – 2,26 eV. / This research investigated the deposition of thin films of bismuth ferrite (BFO) on silicon substrate using the spray pyrolysis technique based on inorganic salts as precursors. For this purpose water, ethylene glycol and ethanol/butyl carbytol (1:1) were used as solvents to prepare the solution for spraying. The depositions were carried out with different substrate temperatures for each solvent used: 200, 250, 300 and 350ºC. The film deposition at low temperatures (200°C) promotes the formation of cracks due to the arrival of the liquid state from droplets sprayed by the atomizer. When using solvent ethanol/butyl carbytol (1:1) the formation of dense films was verified for the different depositions. The thermal gravimetric (TGA) and differential thermal analysis (DTA) were performed for the as-deposited films at 200°C with different solvents for the study of possible reactions of thermal decomposition. The BFO films were heated at 550°C for one hour aiming to the formation of the crystalline state BiFeO3 with rhombohedral structure. The films were analyzed by Xray diffraction (XRD) and scanning electron microscopy (SEM) before and after treatment. The XRD showed the crystalline state obtained after the heat treatment at 550°C/1h. It was observed the formation of non-stoichiometric composition on the film. The SEM images showed formation of films regardless of the solvent used for the temperature to 200°C. However, the increase temperature promotes the formation of particles on the substrate. Applying the ethylene glycol solvent the formation of porous films appeared, since for ethanol/butyl carbytol (1:1) was observed the formation of dense films with the presence of cracks. The electrical characterization of the films will be performed using impedance spectroscopy (IS) coupled to a furnace in order to vary the temperature of the measures. The film deposited with ethylene glycol presents a major electrical conductivity than films deposited using ethanol/butyl carbytol or water. This behavior can be associated with a non-stoichiometric composition of BFO. Moreover, the optical properties were obtained by diffuse reflectance spectroscopy. The films present a band gap between 2.23 and 2.26 eV, approximately.
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Deposição de filmes BiFeO3 via spray pirólise e caracterização microestrutural e de propriedades elétricas e ópticasOliveira, Felipe Fernandes de January 2015 (has links)
Este trabalho investigou a deposição de filmes finos de ferrita de bismuto (BFO) através da técnica spray pirólise utilizando sais inorgânicos como precursores em diferentes solventes e silício como substrato, visando a deposição em menor temperatura e a obtenção de diferentes morfologias de superfície. Para tanto, foram utilizados água, etilenoglicol e etanol/butil carbitol (1:1) como solventes na preparação da solução a ser aspergida. Foram realizadas deposições com diferentes temperaturas do substrato: 200, 250, 300 e 350ºC para cada solvente utilizado. A deposição de filmes BFO em baixas temperaturas (200ºC) favoreceu a formação de filme. Para o solvente etilenoglicol (maior ponto de ebulição), verifica-se a formação de filmes porosos, já para o solvente etanol/butil carbitol (1:1) foi verificada a formação de filmes densos com a presença de trincas. As análises termogravimétricas (ATG) e termodiferenciais (ATD) foram realizadas para os filmes como-depositados a 200ºC com diferentes solventes. Após a deposição, as amostras foram tratadas termicamente a 550ºC por 1h, visando a formação da fase cristalina BiFeO3 com estrutura romboédrica. Os filmes foram analisados por difração de raios X (DRX) e microscopia eletrônica de varredura (MEV). Os resultados mostraram a obtenção da fase cristalina do BiFeO3 após o tratamento térmico a 550ºC/1h com a presença de fase secundária. As imagens de MEV evidenciaram a formação de filmes independente do solvente utilizado para a temperatura de 200ºC. Contudo, o aumento da temperatura promoveu a formação de partículas sobre o substrato e não uma formação contínua de filme, evidenciada pela composição elementar medida através de espectroscopia por energia dispersiva de raios X (EDX). A caracterização elétrica dos filmes foi realizada utilizando espectroscopia de impedância (EI) em função da temperatura, sendo observada maior condutividade para o filme depositado com etilenoglicol. A fase BFO não estequiométrica evidenciada por DRX pode explicar as diferentes condutividades elétricas mensuradas por EI quando utilizado diferentes solventes. As propriedades ópticas foram medidas utilizando-se espectroscopia de reflectância difusa, encontrando-se um band gap entre 2,23 – 2,26 eV. / This research investigated the deposition of thin films of bismuth ferrite (BFO) on silicon substrate using the spray pyrolysis technique based on inorganic salts as precursors. For this purpose water, ethylene glycol and ethanol/butyl carbytol (1:1) were used as solvents to prepare the solution for spraying. The depositions were carried out with different substrate temperatures for each solvent used: 200, 250, 300 and 350ºC. The film deposition at low temperatures (200°C) promotes the formation of cracks due to the arrival of the liquid state from droplets sprayed by the atomizer. When using solvent ethanol/butyl carbytol (1:1) the formation of dense films was verified for the different depositions. The thermal gravimetric (TGA) and differential thermal analysis (DTA) were performed for the as-deposited films at 200°C with different solvents for the study of possible reactions of thermal decomposition. The BFO films were heated at 550°C for one hour aiming to the formation of the crystalline state BiFeO3 with rhombohedral structure. The films were analyzed by Xray diffraction (XRD) and scanning electron microscopy (SEM) before and after treatment. The XRD showed the crystalline state obtained after the heat treatment at 550°C/1h. It was observed the formation of non-stoichiometric composition on the film. The SEM images showed formation of films regardless of the solvent used for the temperature to 200°C. However, the increase temperature promotes the formation of particles on the substrate. Applying the ethylene glycol solvent the formation of porous films appeared, since for ethanol/butyl carbytol (1:1) was observed the formation of dense films with the presence of cracks. The electrical characterization of the films will be performed using impedance spectroscopy (IS) coupled to a furnace in order to vary the temperature of the measures. The film deposited with ethylene glycol presents a major electrical conductivity than films deposited using ethanol/butyl carbytol or water. This behavior can be associated with a non-stoichiometric composition of BFO. Moreover, the optical properties were obtained by diffuse reflectance spectroscopy. The films present a band gap between 2.23 and 2.26 eV, approximately.
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Deposição de filmes BiFeO3 via spray pirólise e caracterização microestrutural e de propriedades elétricas e ópticasOliveira, Felipe Fernandes de January 2015 (has links)
Este trabalho investigou a deposição de filmes finos de ferrita de bismuto (BFO) através da técnica spray pirólise utilizando sais inorgânicos como precursores em diferentes solventes e silício como substrato, visando a deposição em menor temperatura e a obtenção de diferentes morfologias de superfície. Para tanto, foram utilizados água, etilenoglicol e etanol/butil carbitol (1:1) como solventes na preparação da solução a ser aspergida. Foram realizadas deposições com diferentes temperaturas do substrato: 200, 250, 300 e 350ºC para cada solvente utilizado. A deposição de filmes BFO em baixas temperaturas (200ºC) favoreceu a formação de filme. Para o solvente etilenoglicol (maior ponto de ebulição), verifica-se a formação de filmes porosos, já para o solvente etanol/butil carbitol (1:1) foi verificada a formação de filmes densos com a presença de trincas. As análises termogravimétricas (ATG) e termodiferenciais (ATD) foram realizadas para os filmes como-depositados a 200ºC com diferentes solventes. Após a deposição, as amostras foram tratadas termicamente a 550ºC por 1h, visando a formação da fase cristalina BiFeO3 com estrutura romboédrica. Os filmes foram analisados por difração de raios X (DRX) e microscopia eletrônica de varredura (MEV). Os resultados mostraram a obtenção da fase cristalina do BiFeO3 após o tratamento térmico a 550ºC/1h com a presença de fase secundária. As imagens de MEV evidenciaram a formação de filmes independente do solvente utilizado para a temperatura de 200ºC. Contudo, o aumento da temperatura promoveu a formação de partículas sobre o substrato e não uma formação contínua de filme, evidenciada pela composição elementar medida através de espectroscopia por energia dispersiva de raios X (EDX). A caracterização elétrica dos filmes foi realizada utilizando espectroscopia de impedância (EI) em função da temperatura, sendo observada maior condutividade para o filme depositado com etilenoglicol. A fase BFO não estequiométrica evidenciada por DRX pode explicar as diferentes condutividades elétricas mensuradas por EI quando utilizado diferentes solventes. As propriedades ópticas foram medidas utilizando-se espectroscopia de reflectância difusa, encontrando-se um band gap entre 2,23 – 2,26 eV. / This research investigated the deposition of thin films of bismuth ferrite (BFO) on silicon substrate using the spray pyrolysis technique based on inorganic salts as precursors. For this purpose water, ethylene glycol and ethanol/butyl carbytol (1:1) were used as solvents to prepare the solution for spraying. The depositions were carried out with different substrate temperatures for each solvent used: 200, 250, 300 and 350ºC. The film deposition at low temperatures (200°C) promotes the formation of cracks due to the arrival of the liquid state from droplets sprayed by the atomizer. When using solvent ethanol/butyl carbytol (1:1) the formation of dense films was verified for the different depositions. The thermal gravimetric (TGA) and differential thermal analysis (DTA) were performed for the as-deposited films at 200°C with different solvents for the study of possible reactions of thermal decomposition. The BFO films were heated at 550°C for one hour aiming to the formation of the crystalline state BiFeO3 with rhombohedral structure. The films were analyzed by Xray diffraction (XRD) and scanning electron microscopy (SEM) before and after treatment. The XRD showed the crystalline state obtained after the heat treatment at 550°C/1h. It was observed the formation of non-stoichiometric composition on the film. The SEM images showed formation of films regardless of the solvent used for the temperature to 200°C. However, the increase temperature promotes the formation of particles on the substrate. Applying the ethylene glycol solvent the formation of porous films appeared, since for ethanol/butyl carbytol (1:1) was observed the formation of dense films with the presence of cracks. The electrical characterization of the films will be performed using impedance spectroscopy (IS) coupled to a furnace in order to vary the temperature of the measures. The film deposited with ethylene glycol presents a major electrical conductivity than films deposited using ethanol/butyl carbytol or water. This behavior can be associated with a non-stoichiometric composition of BFO. Moreover, the optical properties were obtained by diffuse reflectance spectroscopy. The films present a band gap between 2.23 and 2.26 eV, approximately.
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Propriedades estruturais e controle da estequiometria de filmes finos de BiFeO3 /Sena, Wellington Adriano Fernandes January 2019 (has links)
Orientador: Eudes Borges de Araújo / Resumo: O objetivo do trabalho foi estudar as propriedades estruturais dos filmes finos de ferrita de bismuto (BFO) ao se adicionar excesso de nitrato de ferro ao invés de nitrato de bismuto conforme muitas referências na literatura vêm praticando com a intenção de obter um BFO puro. Filmes finos de BFO foram preparados sobre substratos Pt/TiO2/SiO2/Si(100) usando o método de Pechini pertencente a rota química sol-gel polimérica. Foram produzidos filmes de estequiometria nominal e de variação de 2, 4, 6, 8, 10 e 12 mol% de excesso de nitrato de Ferro. O processo de síntese dos filmes passou por quatro deposições, quatro pirólises a 300 ºC por 20 minutos e cristalização a 600 ºC por 40 minutos. As propriedades físicas dos filmes foram investigadas usando técnicas de MEV, DRX, Raman e EDS. Rietveld foi usado para calcular os parâmetros de rede e o modelo de Williamson-Hall foi usado para calcular o tamanho do cristalito e o microstrain. Resultados do DRX revelaram o aparecimento da fase secundária Bi2O3, ela aparece quando há o excesso de bismuto. Resultados do EDS confirmam o excesso de Bi. A técnica de EDS apontou uma maior At% do bismuto em relação ao ferro em todas as amostras, sendo que, a de 12 mol% foi a que apresentou características mais próxima de uma estequiometria desejável para a produção de um BFO puro. / Abstract: The objective of this work was to study the structural properties of bismuth ferrite (BFO) thin films by adding excess iron nitrate instead of bismuth nitrate as many references in the literature have been practicing with the intention of obtaining a pure BFO. BFO thin films were prepared on Pt / TiO2 / SiO2 / Si (100) substrates using the Pechini method belonging to the polymeric sol-gel chemical route. Films of nominal stoichiometry and variation of 2, 4, 6, 8, 10 and 12 mol% of iron nitrate excess were produced. The synthesis process of the films went through four depositions, four pyrolysis at 300 ºC for 20 minutes and crystallization at 600 ºC for 40 minutes. The physical properties of the films were investigated using SEM, XRD, Raman and EDS techniques. Rietveld was used to calculate lattice parameters and the Williamson-Hall model was used to calculate crystallite size and microstrain. XRD results revealed the appearance of the secondary phase Bi2O3, it appears when there is excess bismuth. EDS results confirm excess Bi. The EDS technique showed a higher At% of bismuth in relation to iron in all samples, and the 12 mol% was the one that presented characteristics closer to a desirable stoichiometry for the production of a pure BFO. / Mestre
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Theoretical determination of electric field-magnetic field phase diagrams of the multiferroic bismuth ferriteAllen, Marc Alexander 28 August 2014 (has links)
Bismuth ferrite (BFO) is a multiferroic material with cross-correlation between magnetic and electric orders. With no applied external fields the spin structure of BFO is anitferromagnetic and cycloidal. This ordering prevents the detection of the weak ferromagnetism known to exist in the material. The application of magnetic and electric fields of suitable strength and direction is capable of compelling the Fe3+ spins to align in a homogeneous, antiferromagnetic fashion. This report details how numerical methods were used to simulate the spin alignment of a BFO system under different fields. The results were compiled into electric field-magnetic field phase diagrams of BFO to show the divide between cycloidal and homogeneous systems. / Graduate / 0607 / 0611 / marca@uvic.ca
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Thermal Expansion And Related Studies In Cordierite Ceramics And Relaxor FerroelectricsSai Sundar, V V S S 09 1900 (has links) (PDF)
The following investigations have been carried out in this thesis
1)Cordierite is already well known for its low thermal expansion behaviour. Chemical substitutions at various octahedral and tetrahedral sites have been done and their thermal expansion characteristics have been studied Synthesis of cordierite in more reactive environment provided by AlF3 used as sintering aid has been attempted
2) Diffuse ferroelectric phase transition of lead based perovskite materials leads to low expansion region. Solid solutions of lead iron niobate with lead titanate is investigated to increase the structural distortion and see it this low expansion region can be extended to wider temperature Preparation of materials with higher tetragonal distortion In PbTi03- BlFeO3 system is undertaken to study the thermal expansion anisotropy.
3) Composites between lead iron niobate(+(x) and lead titanate (-(x below Tc) has been undertaken to prepare low expansion hulk over a wide temperature range
4) Acoustic emission has been employed as a tool to detect the microcracking in solid solutions between PFN1-x, PTx, and PT1-x, ,BFx, It is hoped to understand relation between magnitude of lattice distortion transition temperature and microcracking in ceramics of the class of materials.
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Phonon Anomalies And Phase Transitions In Pyrochlore Titanates, Boron Nitride Nanotubes And Multiferroic BiFeO3 : Temperature- And Pressure-Dependent Raman StudiesSaha, Surajit 10 1900 (has links) (PDF)
This thesis presents experimental and related theoretical studies of pyrochlore titanate oxides, boron nitride nanotubes, and multiferroic bismuth ferrite. We have investigated these systems at high pressures and at low temperatures using Raman spectroscopy. Below, we furnish a synoptic presentation of our work on these three systems.
In Chapter 1, we introduce the systems studied in this thesis, viz. pyrochlores, boron nitride nanotubes, and multiferroic BiFeO3, with a review of the literature pertaining to their structural, electronic, vibrational, and mechanical properties. We also bring out our interests in these systems.
Chapter 2 includes a brief description of the theory of Raman scattering and infrared absorption. This is followed by a short account of the experimental setups used for Raman and infrared measurements. We also present the technical details of high pressure technique including the alignment of diamond anvil cells, gasket preparation, calibration of the pressure, etc.
Chapter 3 furnishes the results of our pressure-and temperature-dependent studies of pyrochlore oxides which has been divided into eight different parts.
In recent years, magnetic and thermodynamic properties of pyrochlores have received a lot of attention. However, not much work has been reported to address the quasiparticle excitations, e.g., phonons and crystal-field excitations in these materials. A material that shows exotic magnetic behavior and high degree of degenerate ground states can be expected to have low-lying excitations with possible couplings with phonons, thereby, finger-printing various novel properties of the system. Raman and infrared absorption spectroscopies can, therefore, be used to comprehend the novel role of phonons and their role in various phenomena of frustrated magnetic pyrochlores. Recently, there have been reports on various novel properties of these systems; for example, Raman and absorption studies [Phys. Rev. B 77, 214310 (2008)] have revealed a loss of inversion symmetry in Tb2Ti2O7 at low temperatures which has been suggested as the key reason for this frustrated magnet to remain in spin-liquid state down to 70 mK. Powder neutron-diffraction experiments [Nature 420, 54 (2002)] have shown that an application of isostatic pressure of about 8.6 GPa in spin-liquid Tb2Ti2O7 induces a long-range magnetic order of the Tb3+ spins coexisting with the spin-liquid phase ascribing this transition to the breakdown of the delicate balance among the various fundamental interactions. Moreover, Raman and x-ray studies have shown that Tb2Ti2O7,Sm2Ti2O7,and Gd2Ti2O7 undergo a structural transition followed by an irreversible amorphization at very high pressures (~ 40 GPa or above) [Appl. Phys. Lett. 88, 031903 (2006)].
In this chapter, therefore, we present our temperature-and pressure-dependent Raman studies of A2Ti2O7 pyrochlores, where ‘A’ is a trivalent rare-earth element (A = Sm, Gd,Tb, Dy,Ho, Er,Yb, and Lu; and also Y). Since all the group theoretically predicted Raman modes of this cubic lattice are due to oxygen vibrations only, in Part (A), we revisit the phonon assignments of pyrochlore titanates by performing Raman measurements on the O16 /O18 − isotope based Dy2Ti2O7 and Lu2Ti2O7 and find that the vibrations with frequencies below 250 cm−1 do not involve oxygen atoms. Our results lead to a reassignment of the pyrochlore Raman phonons thus proposing that the mode with frequency ~ 200 cm−1, which has earlier been known as an F2g phonon due to oxygen vibration, is a vibration of Ti4+ ions. Moreover, we have performed lattice dynamical calculations using Shell model that help us to assign the Raman phonons.
In Part (B), we have explored the temperature dependence of the Raman phonons of spin-ice Dy2Ti2O7 and compared with the results of two non-magnetic pyrochlores, Lu2Ti2O7 and Y2Ti2O7. Our results reveal anomalous red-shift of some of the phonons in both magnetic and non-magnetic pyrochlores as the temperature is lowered. The phonon anomalies can not be understood in terms of spin-phonon and crystal field transition-phonon couplings, thus attributing them to phonon-phonon anharmonic interactions. We also find that the anomaly of the disorder activated Ti4+ Raman vibration (~ 200 cm−1) is unusually high compared to other phonons due to the large vibrational amplitudes of Ti4+-ions rendered by the vacant Wyckoff sites in their neighborhood. Later, we have quantified the anharmonicity in Dy2Ti2O7.
We have extended our studies on spin-ice compound Dy2Ti2O7 by performing simultaneous pressure-and temperature-dependent Raman measurements, presented in Part (C). We show that a new Raman mode appears at low temperatures below TC ~ 110 K, suggesting a structural transition, also supported by our x-ray measurements. There are reports [Phys. Rev. B 77, 214310 (2008), Phys.Rev.B 79, 214437 (2009)] in the literature where the new mode in Dy2Ti2O7 at low temperatures has been assigned to a crystal field transition. Here, we put forward evidences that suggest that the “new” mode is a phonon and not a crystal field transition. Moreover, the TC is found to depend on pressure with a positive coefficient.
In Part (D), we have presented our results of temperature-and pressure-dependent Raman and x-ray measurements of spin-frustrated pyrochlores Gd2Ti2O7, Tb2Ti2O7,and Yb2Ti2O7. Here, we have estimated the quasiharmonic and anharmonic contributions to the anomalous change in phonon frequencies with temperature. Moreover, we find that Gd2Ti2O7 and Tb2Ti2O7 undergo a subtle structural transition at a pressure of ~ 9 GPa which is absent in Yb2Ti2O7. The implication of this structural transition in the context of a long-range magnetically ordered state coexisting with the spin-liquid phase in Tb2Ti2O7 at high pressure (8.6 GPa) and low temperature (1.5 K), observed by Mirebeau et al. [Nature 420, 54 (2002)], has been discussed.
As we have established in the previous parts that the anomalous behavior of pyrochlore phonons is due to phonon-phonon anharmonic interactions, we have tuned the anharmonicity in the first pyrochlore of the A2Ti2O7 series, i.e., Sm2Ti2O7,by replacing Ti4+-ions with bigger Zr4+-ions, presented in Part (E). Our results suggest that the phonon anomalies have a very strong dependence on the ionic size and mass of the transition element (i.e., the B4+-ion in A2B2O7 pyrochlores). We have also observed signatures of coupling between a phonon and crystal-field transitions in Sm2Ti2O7.
In Part (F), we have studied spin-ice compound Ho2Ti2O7 and compared the phonon anomalies with the stuffed spin-ice compounds, Ho2+xTi2−xO7−x/2 by stuffing Ho3+ ions into the sites of Ti4+ with appropriate oxygen stoichiometry. We find that as more and more Ho3+-ions are stuffed, there is an increase in the structural disorder of the pyrochlore lattice and the phonon anomalies gradually disappear with increasing Ho3+-ions. Moreover, a coupling between phonon and crystal field transition has also been observed.
In Part (G), we have examined the temperature dependence of phonons of “dynamical spin-ice” compound Pr2Sn2O7 and compared with its non-pyrochlore (monoclinic) counterpart Pr2Ti2O7. Our results conclude that the anomalous behavior of phonons is an intrinsic property of pyrochlore structure having inherent vacant sites. We also find a coupling between phonon and crystal-field transitions in Pr2Sn2O7.
In the last part of this chapter, Part (H), we present our Raman studies of Er2Ti2O7. Here, we show that in addition to the anomalous phonons, there are modes that originate from photoluminescence transitions and some of these luminescence lines show anomalous temperature dependence which have been understood using the theory of optical dephasing in crystals, developed by Hsu and Skinner [J. Chem. Phys. 81, 1604 (1984)]. Temperature dependence of a few Raman modes and photoluminescence bands suggest a phase transition at 130 K.
In Chapter 4, we furnish our pressure-dependent Raman studies of boron nitride multi-walled nanotubes (BNNT) and hexagonal boron nitride (h-BN) and compare the results with those of their carbon counterparts.
Using Raman spectroscopy, we show that BNNT undergo an irreversible transition at ~ 12 GPa while the carbon counterpart, multi-walled carbon nanotubes, show a similar transition at a much higher pressure of ~ 51 GPa. In sharp contrast, the layered form of both the systems (i.e. h-BN and graphite) undergo a hexagonal to wurtzite phase at nearly similar pressure (~ 13 GPa of h-BN and ~ 15 GPa for graphite). A molecular dynamical simulation on boron nitride single-walled nanotubes has also been undertaken that suggests that the polar nature of the B−N bonds may be responsible for the irreversibility of the pressure-induced transformations. It is interesting to see that in hexagonal phase both the systems have almost similar mechanical property, but once they are rolled up to make nanotubes, the property becomes quite different.
Chapter 5 presents the temperature dependence of the Raman modes of multiferroic thin films of BiFeO3 and Bi0.7Tb0.2La0.1O3. Though there have been several Raman investigations of BiFeO3 in literature, here we emphasize the observation of unusually intense second order Raman phonons. Our results have motivated Waghmare et al. to suggest a theoretical model to explain the anomalously large second order Raman tensor of BiFeO3 in terms of an incipient metal-insulator transition.
In Chapter 6, we summarize our findings on the three different systems, namely, pyrochlores, boron nitride nanotubes, and BiFeO3 and highlight a few possible experiments that may be undertaken in future to have a better understanding of these systems.
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Theoretical investigation of size effects in multiferroic nanoparticlesAllen, Marc Alexander 05 August 2020 (has links)
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
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