Os nitretos do grupo III (BN, AIN,Gan e InN) e suas ligas ternárias Al-GaN e InGaN proporcionam, recentemente, um extraordinário avanço na fabricação de dispositivos opto-eletrônicos operando na região do espectro correspondente ao verde-azul-UV e na produção de dispositivos eletrônicos de alta frequência, alta temperatura e alta potência. Estes materiais semicondutores de gap largo atraíram enorme atenção dos pesquisadores nos últimos anos. O objetivo desta tese é o estudo das propriedades vibracionais dos nitretos do grupo III referente tanto ao cristal perfeito, quanto ao cristal com defeito. Utilizamos como base a Teoria Clássica do Crital Harmônico e o Método das Funções de Green. Com a Teoria Clássica do Cristal Harmônico, juntamente com o Método do Valence Force Filed e o Método da Soma de Ewald, que permitem gerar a matriz dinâmica do sistema, determinamos o comportamento vibracional dos nitretos binários e das ligas ternárias. A utilização destes métodos permitiu a obtenção do espectro de fônons dos nitretos binários, e o estudo do comportamento dos modos ópticos em para as ligas ternárias. A partir da Função de Green do cristal perfeito e da Função de Green do cristal com defeito, obtivemos as frequências e os modos vibracionais localizados e ressonantes introduzidos pela impureza de C e As em GaN. A partir das densidades de estados do cristal perfeito e do cristal com defeito, calculamos a entropia de formação da vacância de N em GaN. Os resultados obtidos foram usados na interpretação de dados experimentais disponíveis na literatura, relativos às propriedades vibracionais dos nitretos na estrutura wurtzita, e na predição e análise de dados experimentais obtidos pelo grupo do Laboratório de Novos Materiais Semicondutores do Instituto de Física da USP para os nitretos zincblende. / The group-III nitrides (BN, AIN, GaN and InN) and their ternary alloys AlGaN and InGaN generated recently an extraordirlary progress in the production of optoelectronic devices operating in the green-blue-UV region of the spectrum, and in the production of electronic devices of high frequency, high temperature and high power. These wide gap semiconductor materials attracted enormous attention in the last years. The objective of this Thesis was to study the vibrational properties of the bulk III nitrides, without and with defects. To accomplish this study we used the Classic Theory of the Harmonic Crystal and the Method of the Green\'s Functions. With the Classic Theory of the Harmonic Crystal, together with the Valence Force Field Method and the Method of the Ewald\'s Sum, that allow to generate the dynamic matrix of the system, we determined the vibrational behavior of the binary nitrides and of the ternary alloys. The use of these methods allowed us to obtain the phonon spectra of the binary nitrides and to study the behavior of the optical modes at of the ternary alloys. Starting from the Green\'s Function of the perfect crystal and the Green\'s Function of the crystal with defect, we obtained the frequencies and the localized and resonant vibrational modes introduced by the C and As impurities in GaN. Starting from the densities of states of the perfect crystal and of the crystal with defect, we calculated the formation entropy of the N vacancy in GaN. The obtained results were used in the interpretation of experimental data related to the vibrational properties of the wurtzite nitrides available in the literature, and in the prediction and analysis of experimental results obtained for zincblende nitrides by the group of the New Semiconductors Materials Laboratory of t11c Physics Institute at USP.

Värmelära upplevs ofta som ett abstrakt område i gymnasiefysiken och elever tenderar att tolka känseln som en termometer. Värmelära kan därmed bli en tuff utmaning för många elever. Genom att introducera värmekameror i undervisningen ges elever möjligheten att se annars osynliga värmefenomen. Eftersom värmekameran inte ännu blivit etablerad i undervisningen finns det ett intresse att studera elevernas interaktion med värmekameran. Syftet med studien är att undersöka hur interaktionen ser ut och hur värmekameran kan hjälpa elever i begreppsbildandet av värmerelaterade fenomen. Denna studie har gjorts på ca 140 elever som går sitt första år på det naturvetenskapliga programmet på en gymnasieskola i Mellansverige. Eleverna fick utföra en laboration designad enligt prediction-observation-explanation-metoden. Laborationen innehöll tre stationer där de centrala begreppen var värmeledning, stöt och friktion. Eleverna använde en värmekamera som hjälpmedel för att förklara de olika fenomenen. Elevernas interaktioner vid laborationen dokumenterades med video- och ljudupptagning i syfte att ge grund för en kvalitativ analys. Analysen av materialet kom att handla om tre delar: hur eleverna resonerar kring värmeledning, respektive friktion och stöt, och hur värmekameran kan stimulera det kreativa tänkandet hos eleverna. Det visade sig att många elevgrupper kom långt i det makroskopiska och en bra bit i det mikroskopiska resonemanget kring värmeledning genom att tillämpa en modell av fria elektroner i metall de hade lärt sig från kemin. De flesta grupperna hade svårt att resonera kring energiomvandlingar vid stöt både på en makroskopisk och mikroskopisk nivå. Det kreativa undersökandet resulterade i en röra. Värmekameran lockar elevernas nyfikenhet, ger ”disciplinary affordance” och stimulerar dem till ”instant inquiry”. När eleverna gick utanför instruktionerna och bedrev egna undersökningar resulterade det i en röra då de prioriterade bort sina nykonstruerade hypoteser. / Thermodynamics is often perceived as an abstract field in secondary school physics. Thermodynamics can thus be a tough challenge for many students. By including thermal imaging cameras in teaching, students are given the opportunity to see otherwise invisible thermal phenomena. Since the infrared camera has not yet been established in teaching, there is an interest in studying the interaction between students and the thermal imaging camera. The purpose of this study is to investigate the interaction between student and the infrared camera and to see how the infrared camera can help students in the conceptual formation of heat-related phenomena. The study included about 140 students attending their first year on the science program at an upper secondary school in central Sweden. The students had to perform laboratory experiments designed according to the prediction-observation-explanation method. The laboratory experiments consisted of three stations where the key concepts were heat conduction, collision and friction. Students took help of an infrared camera to explain the various phenomena. The students' interactions at the lab were documented with video and audio recording in order to set the basis of a qualitative analysis. The analysis of the material consisted of three parts: how students reason concerning heat conduction, their reasoning concerning dissipative processes as friction and collision, and how the infrared camera can stimulate the students' creative thinking. Many student groups were successful in the macroscopic and quite successful in the microscopic reasoning regarding heat conduction by applying a model of free electrons in the metal which they had learned in chemistry class. Other studies have shown that students find it hard explaining heat conduction and that they tend to interpret the physical touch as a thermometer. The group that examined friction and collision found it difficult explaining the transformation from kinetic energy into thermal energy in collision at both the macroscopic and microscopic level. The creative investigation resulted in a mess. The infrared camera attracts students' curiosity, gives ”disciplinary affordance” and stimulates them to ”instant inquiry”. When the students went beyond their instructions and conducted own investigations it resulted in a mess when they prioritized away the recently created hypotheses.

The Casimir interaction is the fundamental physical phenomenon which emerges due to modification of vacuum fluctuations by boundaries in a confined area of space. It arises in many fields of physics, including condensed matter. Recently, substantial interest in the Casimir effect has revived as a result of the significant progress in the experimental techniques in cold atoms. In this thesis, we develop the description of the phonon-mediated Casimir interaction taking into account multiple phonon-impurity scatterings, that strongly renormalize the resulting interaction between the impurities. Our results, formulated in terms of the T-matrix formalism, generalize previous studies of the Casimir interaction between different kind of impurities and allow estimation of the expected phonon-induced Casimir interaction in various systems. Further, we consider a propagation of a singe hole in a two-dimensional ferromagnet accompanied by spin-flip processes. We show that an external magnetic field can be used to manipulate the properties of the single-layer system. For easy plain ferromagnets, at saturation value of the external field perpendicular to the easy axis, the Green’s function demonstrates the branch cut behavior. It is contrasted to the systems of an itinerant quasiparticle in the antiferromagnetic background where the quasiparticle retains the finite quasiparticle weight. The considered magnon scattering processes on a single itinerant electron (hole) in a two-dimensional ferromagnet can be used further for the magnon-mediated Casimir interaction in quasi-two-dimensional ferromagnets.

<div>The recent decades have witnessed increased efforts to push the efficiency of energy systems beyond existing limits in order to keep pace with the rising global energy demands. Such efforts involve finding bulk materials and nanostructures with desired thermal properties such as thermal conductivity (k). For example, identifying high k materials is crucial in thermal management of vertically integrated circuits (ICs) and flexible nanoelectronics, which will power the next generation personal computing devices. On the opposite end of the spectrum, designing ultra-low k materials is essential for improving thermal barrier coatings in turbines and creating high performance thermoelectric (TE) devices for waste heat harvesting. In this dissertation, we identify nanostructures with such extreme thermal transport properties and explore the underlying phonon and photon transport mechanisms. Our approach follows two main avenues for evaluating potential candidates: (a) high fidelity atomistic simulations and (b) rapid machine learning-based property prediction and design optimization. The insight gained into the governing physics enables us to theoretically predict new materials for specific applications requiring high or low k, propose accelerated design optimization pathways which can significantly reduce design time, and advance the general understanding of energy transport in semiconductors and dielectric materials.</div><div><br></div><div>Bi2Te3, Sb2Te3 and nanostructures have long been the best TE materials due to their low κ at room temperatures. Despite this, computational studies such as molecular dynamics (MD) simulations on these important systems have been few, due to the lack of a suitable interatomic potential for Sb2Te3. We first develop interatomic potential parameters to predict thermal transport properties of bulk Sb2Te3. The parameters are fitted to a potential energy surface comprised of density functional theory (DFT) calculated lattice energies, and validated by comparing against experimental and DFT calculated lattice constants and phonon properties. We use the developed parameters in equilibrium MD simulations to calculate the thermal conductivity of bulk Sb2Te3 at different temperatures. A spectral analysis of the phonon transport is also performed, which reveals that 80% of the total cross-plane k is contributed by phonons with mean free paths (MFPs) between 3-100 nm. </div><div><br></div><div>We then use MD simulations to calculate phonon transport properties such as thermal conductance across Bi2Te3 and Sb2Te3 interface, which may account for the major part of the total thermal resistance in nanostructures. By comparing our MD results to an elastic scattering model, we find that inelastic phonon-phonon scattering processes at higher temperatures increases interfacial conductance by providing additional channels for energy transport. Finally, we calculate the thermal conductivities of Bi2Te3/Sb2Te3 superlattices (SLs) of varying period. The results show the characteristic minimum thermal conductivity, which is attributed to the competition between incoherent and coherent phonon transport regimes. Our MD simulations are the first fully predictive studies on this important TE system and pave the way for further exploration of nanostructures such as SLs with interface diffusion and random multilayers (RMLs).</div><div><br></div><div>The MD simulations described in the previous section provide high-fidelity data at a high computational cost. As such, manual intuition-based search methods using these simulations are not feasible for searching for low-probability-of-occurrence systems with extreme thermal conductivity. In view of this, we use machine learning (ML) techniques to accelerate and efficiently perform nanostructure design optimization within such large design spaces. First, we use a Genetic Algorithm (GA) based optimization method to efficiently search the design space of fixed length Si/Ge random multilayers (RMLs) for the structure with lowest k, which is found to be lower than the SL k by 33%. By comparing thermal conductivity and interface resistances between optimal and sub-optimal structures, we identify non-intuitive trends in design parameters such as average period and degree of randomness of layer thicknesses. </div><div><br></div><div>While machine learning (ML) has shown increasing effectiveness in optimizing materials properties under known physics, its application in discovering new physics remains challenging due to its interpolative nature. We demonstrate a general-purpose adaptive ML-accelerated search process that can discover unexpected lattice thermal conductivity (k) enhancement in aperiodic superlattices (SLs) as compared to periodic superlattices, with implications for thermal management of multilayer-based electronic devices. We use molecular dynamics simulations for high-fidelity calculations of k, along with a convolutional neural network (CNN) which can rapidly predict k for a large number of structures. To ensure accurate prediction for the target unknown SLs, we iteratively identify aperiodic SLs with structural features leading to locally enhanced thermal transport and include them as additional training data for the CNN. The identified structures exhibit increased coherent phonon transport owing to the presence of closely spaced interfaces.</div><div><br></div><div>We also demonstrate the application of ML in optimization of photonic multilayered structures with enhanced reflectivity to radiation heat flux, which is required for applications such as high temperature thermal barrier coatings (TBCs). We first perform a systematic variation of design parameters such as total thickness and average layer thickness of CeO2-MgO multilayers, and quantify their influence on the spectral and total reflectivity. The effect of randomization of layer thicknesses is also studied, which is found to increase the reflectivity due to localization of photons in certain spatial regions of the multilayer structure. Next, we employ a GA search method which can efficiently identify RML structures with reflectivity enhancements of ~22%, 20%, 20% and 10% over that obtained in randomly generated RML structures for total thicknesses of 5,10,20 and 30 microns respectively. We also calculate the spectral reflectivity and the field intensity distribution within the optimal and sub-optimal RML structures. We find that the electric field intensity can be significantly enhanced within certain spatial regions within the GA-optimized RMLs in comparison to non-optimized and periodic structures, which implies the high degree of randomness-induced photon localization leading to enhanced reflectivity in the GA-optimized structures.</div><div><br></div><div>In summary, our work advances the design or search for materials and nanostructures with targeted thermal transport properties such as low and high thermal conductivity and high reflectivity. The new insights provided into the underlying physics will guide the design of promising nanostructures for high efficiency energy systems. </div><div><br></div>

Ce manuscrit porte sur l’étude de cuprates de basse dimensionnalité, les systèmes à chaînes de spins SrCuO₂ et Sr₂CuO₃. Un des intérêts de ces deux composés est qu’ils présentent des conductions thermiques fortement anisotropes. Celles-ci comportent une contribution magnétique due au transport de la chaleur via les excitations de spinons qui se manifeste uniquement dans la direction des chaînes de spins. Notre étude a pour objectif la mise en évidence des mécanismes qui gouvernent ces propriétés de transport, notamment à travers l’étude des interactions entre les spinons, les phonons et les défauts. Les interactions spinons (phonons)-défauts ont été sondées par l’introduction intentionnelle de dopants (1-2%) non-magnétiques sur le site du cuivre : Mg²⁺, Zn²⁺, Pd²⁺ ou Ni²⁺, ou encore par l’introduction d’éléments possédant des degrés d’oxydation différents sur le site du strontium : La³⁺ ou K⁺. Les composés ont été synthétisés sous leur forme monocristalline par la méthode de fusion de la zone solvante. Des caractérisations structurales, magnétiques et thermiques des composés purs et dopés ont été réalisées. Les spectres d’excitations magnétiques de ces cuprates ont été déterminés par diffusion inélastique de neutrons, spectroscopie RMN et spectroscopie de photoémission résolue en angle afin de révéler l’impact de la substitution. L’étude des spectres de phonons a également été réalisée par diffusion inélastique de neutrons. Les résultats de ces mesures sont corrélés aux propriétés de conduction thermique des composés purs et dopés.. / This manuscript deals with the study of low dimensional cuprates, namely, the spin chains systems SrCuO₂ and Sr₂CuO₃. These two compounds exhibit highly anisotropic thermal conduction properties along the spin-chains direction, where magnetic thermal conduction contributes to the heat transport process via spinon excitations. Our study aims to highlight the mechanisms that govern the heat transport properties, particularly through the study of the scattering channels involving spinon, phonon and defects. The spinon (phonon)–defect scattering was probed by the intentional introduction of nonmagnetic dopants (1-2%) on the copper site, by: Mg²⁺, Zn²⁺, Pd²⁺ or Ni²⁺, or by the introduction of elements carrying different oxidation level on the strontium site, by: La³⁺ or K⁺. Single crystals of the pure and doped materials have been grown by the travelling solvent floating zone method. The structural, magnetic and thermal characterizations of the pure and doped compounds were performed. The magnetic excitation spectra of the compounds were determined by inelastic neutron scattering, NMR spectroscopy, and angle resolved photoemission spectroscopy to reveal the impact of the substitution on the spin dynamics of the doped compounds. The study of phonon spectra has also been performed by inelastic neutron scattering. Results from inelastic neutron scattering have been correlated to the heat transport properties of the pristine and substituted materials.

Diese Arbeit untersucht den Zusammenhang von elektronischer und nukleare Anregung beim Raman-Effekt mit der Methode der zeitaufgelösten harten UV-Spektroskopie. Wir verwenden kohärente stimulierte Raman-Streuung, ein Spezialfall der Standard-Raman-Streuung. Bei dieser regt ein hinreichend kurzer kohärenter Lichtimpuls Schwingungen der Kerne an, bei denen die Kerne messbar ausgelenkt werden, wohingegen die Auslenkungen bei normaler Raman-Streuung, wegen deren inkohärenten spontanen Natur, nicht messbar sind. Wir konnten Auslenkung kleiner als 10^-4 A in Echtzeit durch ihren Effekt auf das harte UV-Spektrum nachweisen. Diese Ergebnisse konnten mit Lithiumborhydrid als Probe und nicht-resonanter naher Infrarotstrahlung als Anrege-und harter UV-Strahlung als Abfrageimpuls erzielt werden. Zum Nachweis dieses Prozesses verwenden wir harte UV-Absorptionsspektroskopie an der Lithium K-Kante von Lithiumborhydrid bei 60 eV. Das Absorptionsspektrum besteht aus einem starken exzitonischen Anteil zu Beginn der Absorption und einem Plateau bei höheren Energien. Bei Anregung durch einen NIR-Impuls beobachteten wir eine oszillatorische Änderung des Absorptionsspektrums mit einer Frequenz von 10 THz, was wir der Modulation der interatomaren Abständen durch kohärente Phononen, und die damit einhergehende Modulation der chemischen Umgebung des absorbierenden Atoms, zuschreiben. Harte UV-Spektroskopie, insbesondere bei niedrigen Energien und nahe der Kante, ist hoch sensitiv auf die chemische Umgebung des jeweiligen absorbierenden Atoms. Unsere Resultate erlauben einen faszinierenden, neuen Einblick in die mikroskopische Natur des Raman-Effekts. Sie verbinden einen direkten Nachweis des antreibenden Mechanismus, der induzierten Polarisation, mit einer direkten Beobachtung des Resultats, die oszillatorische Auslenkung der Kerne. Dabei konnten mit harter UV-Spektroskopie nukleare Auslenkungen in der Größenordnung von 10-4 A mit Subpicosekundenzeitauflösung aufgelöst werden. / This thesis explores the subtle interplay between electronic and nuclear excitation in the Raman effect with time resolved XUV absorption spectroscopy. Coherent stimulated Raman scattering, the type of Raman interaction we induce, is a variant of the well known Raman scattering, where a sufficiently short pulse excites nuclear vibrations coherently, i.e. with actual displacement of the nuclei. In standard Raman scattering, due to its incoherent, spontaneous nature, there is no displacement of nuclei. We were able to observe nuclear displacements as small as 10^-4 in real time by their effect on the XUV absorption spectrum. Specifically we studied non-resonant NIR pump XUV probe absorption spectroscopy on lithium borohydride (LiBH_4). In the XUV absorption experiments in this thesis we concentrate on the Lithium K-edge absorption spectrum around 60 eV which consists of a strong excitonic peak at the onset of absorption and a plateau at higher energies. Upon excitation with a NIR pulse we observe oscillatory changes in the absorption spectrum with a frequency of 10 THz, which we identify as the effect of coherent phonon excitations of an external A_g phonon mode. The coherent oscillation changes the distance between Li^+ anions and BH_4^- cations, which modifies the electronic environment around the Li anion. XUV absorption spectroscopy, especially XANES, is highly sensitive to such changes of the chemical environment around the absorbing atom. We use two different approaches to derive the absolute displacement, which are observed in the experiment. Our results allow for a fascinating new insight into Raman scattering as they connect a direct observation of the driving mechanism, the induced polarization, with a direct observation of the outcome the oscillatory nuclear displacement. With XUV absorption spectroscopy nuclear displacements in the order of 10^-4 A were resolved with sub picosecond accuracy in the time domain.

The rapid progress on developing new and improved multifunctional materials, for optoelectronic and spin based phenomena/devices, have increased the importance of the fundamental understanding of their coherent states and nonlinear optical properties. This study is aimed at characterizing, modeling, and controlling the fundamental electronic, phononic, and spin properties of several classes of materials through nonequilibrium and nonlinear light-matter interactions, coupled with a novel design of the material phases, interfaces, and heterostructures. This research directly addresses the Grand Challenges identified in the Basic Energy Sciences Advisory Committee report "Directing Matter and Energy: Five Challenges for Science and the Imagination" (Hemminger, 2007) [1], in particular, the area: "Matter far beyond equilibrium" and addresses the questions, "How do remarkable properties of matter emerge from complex correlations of the atomic or electronic constituents and how can we control these properties?" and "How do we design and perfect atom- and energy-efficient synthesis of revolutionary new forms of matter with tailored properties?". The knowledge gained from these fundamental studies can provide new information for a broad community to provide concepts for the next generation of multifunctional materials and devices, and resulted in several publications and conference presentations. The materials studied in this dissertation included multiferroic BaTiO3-BiFeO3 [2], ferroelectric Pb0.52Zr0.48TiO3 (PZT), InAs/AlAsSb multi-quantum-well [3], lead halide perovskite [4], n-type InAsP films [5, 6], and nanolaminate plasmonic crystals [7]. Probing multiferroics, which are materials that can exhibit ferromagnetic, ferroelectric, and ferroelastic orders simultaneously in a single phase, was a main focus of this study. BiFeO3 (BFO) is the most widely investigated multiferroic due to its high Neel and Curie temperatures and has antiferromagnetic and ferroelectric properties [8]. An inherent drawback of BFO is its large leakage currents. In this project, (1 − x)BaTiO3-(x)BiFeO3, x = 0.725 (BTO-BFO) heterostructures were investigated [9], where the conductivity of the solid solution can be reduced by adding another perovskite material, BaTiO3 [2]. We aimed to study optically induced coherent states in our BTO-BFO structures. Time resolved pumpprobe spectroscopic measurements were performed at room temperature as well as at low temperature (100 K) up to 10 T. Coherent acoustic phonons were observed both in a film and nanorods, resulting in coherent phonon frequencies of 27 and 33 GHz, respectively [2]. Coherent phonon spectroscopy is a sensitive tool to characterize the interfaces and can be employed as an effective ultrasensitive quantum sensor [10]. Furthermore, in the nanorods arrays of BTO-BFO, an additional oscillation with frequency in the range of 8.1 GHz was observed. This frequency is close to a theoretically predicted magnon frequency which could indicate the coexistence of coherent phonons and magnons in the nanorods arrays [2]. In an analogy to photonics which relies on electromagnetic waves, magnonics utilizes spin waves to carry and process information, offering several advantages such as an operation frequency in the THz range. Recently, "a quantum tango" [11] was reported where coupled coherent magnon and phonons modes were formed on a surface patterned ferromagnet. Furthermore, BTO-BFO heterostructures were probed using transient birefringence and magneto-optical Kerr effect spectroscopy. The results demonstrated that the magnetic field dependence of coherent phonons, measured by these two techniques, exhibits more sensitivity to the external magnetic fields compared to the differential reflectivity technique [2]. Moreover, nonlinear optical properties of this structure were investigated via second harmonic generation spectroscopy, where wavelength and polarization dependence of this nonlinear observation will be discussed in this dissertation. As part of this study, another class of multiferroic materials, with strong ferroelectric and piezoelectric properties, Pb0.52Zr0.48TiO3 (PZT) was studied [12]. In this project, the nonlinear optical properties of PZT nanorod arrays were investigated. Clear signatures of second harmonic generations from 490-525 nm (2.38-2.53 eV) at room temperature, were observed. Furthermore, time resolved differential reflectivity measurements were performed to study dynamical properties in the range of 690-1000 nm where multiphoton processes were responsible for the photoexcitations. We compared this excitation scheme, which is sensitive mainly to the surface states, to when the photoexcited energy (∼ 3.1 eV) was close to the bandgap of the nanorods. Our results offer promises for employing these nanostructures in nonlinear photonic applications. Furthermore, the established techniques during my research provided new insights on optical properties of InAs/AlAsSb multi-quantum-well [3], lead halide perovskite [4], n-type InAsP films [5, 6], and nanolaminate plasmonic crystals [7], and the results will be briefly presented in this dissertation. / Doctor of Philosophy / My research activities have explored multifunctional materials and heterostructures with strongly enhanced coupled electric and magnetic orders and optical properties. In particular, pursuing novel heterostructure designs such as multiferroics can provide control over electric and magnetic ordering in mixed dimensionality. This, together with control at the level from lattice structure to electron spin states can give rise to improved or even qualitatively new and robust materials properties. For example, a better understanding of the phenomena associated with the spin degree of freedom of electrons allows for advancement in spintronic device applications such as storage, logic, and sensors, which are associated with quantum computers and quantum communications [13, 14, 15]. Overarching questions and goals of my activities included: What are the microscopic origins and mechanisms of nonlinear response in strongly coupled nanostructured materials and its relationship to electronic, spin, and lattice degrees of freedom? (2) What are the effects of dimensionality and quantum confinement on optical properties? (3) How do we control and manipulate the coherent states, such as coherent phonons and magnons using external and internal fields, material composition, and morphology to achieve maximal efficiency and tunability? Addressing many of the challenges in the fast-paced technological world requires continued developments of new materials with enhanced optical properties. The knowledge gained from my fundamental studies can provide new information for the next generation of multifunctional materials and devices with advanced optical properties and resulted in several publications and conference presentations.

Phonon anharmonicity is critical for describing various phenomena in crystals, including lattice thermal conductivity, thermal expansion, structural phase transitions, and many others. Including anharmonicity in the calculation of condensed matter observables developed rapidly in the past decade. First-principles computation of cubic phonon interactions have been performed in many systems, and the quartic interactions have begun to receive more attention. In this study, reliable Hamiltonians are constructed purely in terms of quadratic, cubic, and quartic irreducible derivatives, which are calculated efficiently and precisely using the lone and bundled irreducible derivative approaches (LID and BID). The resulting Hamiltonians give rise to a nontrivial many-phonon problem which requires some approximation in order to compute observables. We implemented self-consistent diagrammatic approaches to evaluate the phonon self-energy, including the Hartree-Fock approximation for phonons and quasiparticle perturbation theory, where both the 4-phonon loop and the real part of the 3-phonon bubble are employed during self-consistency. Additionally, we implemented molecular dynamics in order to yield the numerically exact solution in the classical limit. The molecular dynamics solution is robust for directly comparing to experimental results at sufficiently high temperatures, and for assessing our diagrammatic approaches in the classical limit. Anharmonic vibrational Hamiltonians were constructed for CaF₂, ThO₂, and UO₂. Diagrammatic approaches were used to evaluate the phonon self-energy, yielding the phonon lineshifts and linewidths and the thermal conductivity within the relaxation time approximation. Our systematic results allowed us to resolve the paradox of why first-principles phonon linewidths strongly disagree with results extracted from inelastic neutron scattering (INS). We demonstrated that the finite region in reciprocal space required in INS data analysis, the 𝑞-voxel, must be explicitly accounted for within the calculation in order to draw a meaningful comparison. We also demonstrated that the 𝑞-voxel is important to properly compare the spectrum measured in inelastic X-ray scattering (IXS), despite the fact that the ?-voxel is much smaller. Accounting for the 𝑞-voxel, we obtained good agreement for the scattering function linewidths up to intermediate temperatures. Additionally, good agreement was obtained for the thermal conductivity. Another topic we addressed is translation symmetry breaking caused by factors such as defects, chemical disorders, and magnetic order. These phenomena will lead to shifts and a broadening of the phonon spectrum, and formally the single-particle Green’s function encodes these effects. However, it is often desirable to obtain an approximate non-interacting spectrum that contains the effective shifts of the phonon frequencies, allowing straightforward comparison with experimentally measured scattering peak locations. Such an effective phonon dispersion can be obtained using a band unfolding technique, and in this study, we formulated unfolding in the context of irreducible derivatives. We showcased the unfolding of phonons in UZr₂, where chemical disorder is present, and compared the results with experimental IXS data. Additionally, we extended the unfolding technique to anharmonic terms and demonstrated this using 3rd and 4th order terms in the antiferromagnetic phase of UO₂.

No description available.

No description available.