Disertacijos santraukoje reziumuojamas sužadinimo energijos pernašos eksitoniniame dimere tyrimas. Nagrinėjamas kvantinio koherentiškumo vaidmuo energijos pernašos procesų hierarchijoje: virpesinėje relaksacijoje, sužadinimo pernašoje vieneksitoninėje juostoje bei relaksacijoje į pagrindinę būseną. Glaustai aprašomas naujas metodas, išplėtotas koherentiniams efektams silpnos rezonansinės sąveikos riboje aprašyti. Pristatomas eksitoninio dimero tyrimas įvariuose sistemos ir termostato sąveikos režimuose, kuomet stebima tiek koherentinė, tiek nekoherentinė sužadinimo evoliucija. Nustatyta, jog esant skirtingoms chromoforų reorganizacijos energijoms ir stipriam eksitoniniam maišymuisi, eksitoninių būsenų potencinės energijos paviršių minimumai gali susikeisti vietomis lygininat su nesąveikaujančių chromoforų minimumais. Pristatomas relaksacijos į pagrindinę būseną eksitoniniame dimere tyrimas, kuris atskleidė, jog rezonansinė sąveika ir būsenų energijų skirtumas daugiausia turi įtakos procesų spartai, bet ne pobūdžiui. Darbe paaiškintas disipacijos mechanizmas sintetinėse karotenoido-ftalocianino diadose; gauti rezultatai naudingi aiškinant apsauginį fotosintezės mechanizmą, vadinamą nefotocheminiu gesimu. / The summary of doctoral dissertation presents the investigation of excitation energy transfer, studied in an excitonic dimer under various conditions of inter-chromophore resonance interaction and in different regimes of the system-bath coupling. The manifestation of quantum coherence in the energy transfer in molecular dimer is considered within the hierarchy of the relaxation processes: vibrational relaxation, energy redistribution within single exciton manifold and relaxation to the ground state. A new method to capture the coherence effects in the limit of weak resonance interaction is presented. The study of an excitonic heterodimer under various system-bath coupling conditions, which revealed both coherent and incoherent excitation evolutions, is summarized. An outline of the study of the relaxation of the excitonic dimer to the ground state is given, which revealed that the resonance coupling strength and the energy gap between the states control the rate of the process but not the character. The dissipation mechanism in the artificial carotenoid-pthalocyanine dyads is explained, and the results may be helpful in determining the mechanism of energy dissipation during photosynthesis, known as the non-photochemical quenching.

In the dissertation, excitation energy transfer was studied in an excitonic dimer under various conditions of inter-chromophore resonance interaction and in different regimes of the system-bath coupling. We examine the manifestation of quantum coherence in the energy transfer in molecular dimer, within the hierarchy of the relaxation processes: vibrational relaxation, energy redistribution within single exciton manifold and relaxation to the ground state. In order to capture the coherence effects in the limit of weak resonance interaction a novel technique has been presented. We are able to reproduce the coherence effects in the simulation of static and dynamic spectroscopic experiments. The study of an excitonic heterodimer under various system-bath coupling conditions revealed both coherent and incoherent excitation evolutions. In the situation of different reorganization energies, in the case of strong excitonic mixing, the vibrationally relaxed excited state energy levels may become swapped with respect to the monomeric counterparts. The study of the relaxation of the excitonic dimer to the ground state revealed that the resonant coupling strength and the energy gap between the states control the rate of the process but not the character. We have explained the dissipation mechanism in the artificial carotenoid-pthalocyanine dyads, and the results may be helpful in determining the mechanism of energy dissipation during photosynthesis, known as the non-photochemical... [to full text] / Šioje disertacijoje nagrinėjama sužadinimo energijos pernaša eksitoniniame dimere, esant įvairaus stiprio rezonansinei sąveikai tarp chromoforų skirtinguose sistemos ir termostato sąveikos režimuose. Nagrinėjamas kvantinio koherentiškumo vaidmuo energijos pernašos procesų hierarchijoje: virpesinėje relaksacijoje, sužadinimo pernašoje vieneksitoninėje juostoje bei relaksacijoje į pagrindinę būseną. Koherentiniams efektams silpnose rezonansinės sąveikos riboje aprašyti buvo išplėtotas naujas metodas. Juo remiantis modeliuojami koherentiškumo nulemti efektai statinės ir dinaminės spektroskopijos eksperimentuose. Tiriant eksitoninį dimerą įvariuose sistemos ir termostato sąveikos režimuose stebima tiek koherentinė, tiek nekoherentinė sužadinimo evoliucija. Nustatyta, jog esant skirtingoms chromoforų reorganizacijos energijoms ir stipriam eksitoniniam maišymuisi, eksitoninių būsenų potencinės energijos paviršių minimumai gali susikeisti vietomis lygininat su nesąveikaujančių chromoforų minimumais. Relaksacijos į pagrindinę būseną eksitoniniame dimere tyrimas atskleidė, jog rezonansinė sąveika ir būsenų energijų skirtumas daugiausia turi įtakos procesų spartai, bet ne pobūdžiui. Darbe paaiškintas disipacijos mechanizmas sintetinėse karotenoido-ftalocianino diadose; gauti rezultatai naudingi aiškinant apsauginį fotosintezės mechanizmą, vadinamą nefotocheminiu gesimu.

In this work, organic solar cells of the configuration ITO/Pedot:PSS/CuPc/PTCBI/Al (Indium tin oxide/poly(3,4-ethylenedioxythiophene): polystyrene sulfonic acid/copper phthalocyanine/3,4,9,10-perylenetetracarboxylic bisbenzimidazole/aluminum) were investigated. A high open-circuit voltage (Voc) of 1.15 V was obtained when the PTCBI layer was 7 nm thick. Lower Voc values were observed for the same structure with silver, copper and gold electrodes instead of aluminum. However, short-circuit current density (Jsc) with these electrodes was much higher (4 mA/cm2) than in the case of aluminum (0.12 mA/cm2). Results were interpreted in terms of a modified CuPc/Al Schottky diode for the thin PTCBI case and a CuPc/PTCBI heterojunction for the thick PTCBI case. Also, the formation of a thin, protective aluminum oxide layer under the aluminum electrode was postulated. For devices with silver, copper and gold electrodes, absence of this protective layer was thought to be the cause of a relatively lower Voc and higher Jsc.

Orientador: Eliermes Arraes de Meneses / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-01T15:17:20Z (GMT). No. of bitstreams: 1 Laureto_Edson_D.pdf: 1405302 bytes, checksum: c968370a0a1573efd8fecf84d420629c (MD5) Previous issue date: 2002 / Resumo: Não informado / Abstract: Not informed. / Doutorado / Física / Doutor em Ciências

Orientador: Fernando Iikawa / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-03T21:39:11Z (GMT). No. of bitstreams: 1 Gomes_PauloFreitas_M.pdf: 1146621 bytes, checksum: b7f76e8d642550fddb547a7ed86d00e3 (MD5) Previous issue date: 2004 / Resumo: Estudamos a influência de uma pressão biaxial externa sobre a estrutura de banda de poços quânticos de GaAs / AlGaAs por medidas ópticas. A aplicação de uma pressão externa é uma técnica bastante útil no estudo de efeitos da mistura das bandas em heteroestruturas, principalmente da banda de valência. A sua grande vantagem é de ter controle externo utilizando uma mesma amostra. Utilizamos técnicas de medidas de fotoluminescência e fotoluminescência de excitação. A medida da deformação (tensão) foi feita a partir do pico de luminescência da camada espessa de GaAs da própria amostra. Os poços quânticos investigados têm uma largura nominal de 107Å, onde a separação de energia entre a subbanda de buraco pesado e leve no centro da zona de Brillouin é de 12 meV. A célula de pressão utilizada aplica uma tração biaxial suficiente para deslocar as subbandas com energias maiores que essa separação. Realizamos cálculos numéricos das dispersões de energia da banda de valência utilizando o Hamiltoniano 6x6 de Luttinger-Kohn e de Bir-Pikus, para analisar os dados experimentais. Uma propriedade interessante observada nos resultados experimentais, que fora previsto nos cálculos, é o anti-cruzamento entre as subbandas nos estados fundamentais do buraco leve e pesado. O "gap" indireto também previsto teoricamente, não foi observado devido ao efeito de localização que alarga a linha de emissão e absorção da ordem da diferença de energia entre o topo da banda de valência e o centro da zona. Este trabalho abre possibilidades de realizar estudos futuros de efeitos da mudança na estrutura de bandas em poços quânticos, como por exemplo, sobre a dinâmica e formação de éxcitons, como também magneto-éxcitons. A aplicação simultânea de uma pressão biaxial e um campo magnético permite investigar o fator-g de Landé ( efeito Zeeman ) influenciado pela mistura das bandas em poços quânticos / Abstract: We have studied the influence of external biaxial stress in GaAs / AlGaAs quantum wells heteroestructures by optical measurements. For this purpose, we have used photoluminescence and excitation photoluminescence measurement techniques. Biaxial stress application is a extremelly useful technique to study the valence band mixing in heterostructures, and its greatest advantage is the external control of the sample strain.. The measurement of strain (stress) was carried out measuring the photoluminescence peak of the thick GaAs layer. The quantum wells have nominal width of L = 107 Å, and the energy difference between the heavy and light hole subband is about 12 meV, in k = 0 (center of first Brillouin zone). The pressure cell used applies a biaxial stress enough to dislocate the subbands more than 12 meV (the energy difference between the heavy and light hole subbands). We have numerically calculated the valence band energy dispersion using the Bir-Pikus and Luttinger-Kohn 6x6 hamiltonian to analyze the experimental data. An interesting property observed in the experimental data and theoretically simulation, is the anti-crossing between the heavy and light hole subband in the ground state. The indirect gap, also theoretically predicted, was not observed due the localization effect. This effect extends the emission and absorption line in amount of the energy difference between the valence band top and the center of the zone. This work opens possibilities for future studies about the effects of changes in the quantum well band structure, like dynamics and formation of excitons, also magnetic-excitons. The simultaneous application of biaxial stress and magnetic field permits to investigate the Landé g-factor (Zeeman effect) influenced by the band mixing in quantum wells / Mestrado / Física / Mestre em Física

Orientador: Jose Antonio Brum / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-07-25T14:07:23Z (GMT). No. of bitstreams: 1 Aguiar_MariaCarolinadeOliveira_M.pdf: 2381669 bytes, checksum: b013d15f300f2b381b2c5d4cdf9c7c9c (MD5) Previous issue date: 1999 / Resumo: O objetivo principal do nosso trabalho é estudar o processo de formação de éxcitons em poços quânticos de semicondutores. Iniciamos esta dissertação com uma discussão dos diferentes processos de espalhamento, dentre eles a formação de éxcitons, envolvidos quando um semicondutor é excitado por um pulso de laser ultracurto. Em seguida, apresentamos uma revisão de alguns resultados experimentais presentes na literatura, através dos quais fica evidente a dificuldade encontrada para se extrair das medidas realizadas informações sobre o processo de formação de éxcitons. No nosso modelo, descrevemos a formação de um éxciton como a transição de um par elétron-buraco no limiar do contínuo do éxciton para o estado excitônico fundamental via espalhamento com fônons acústicos longitudinais. Este é um processo bimolecular, caracterizado por uma taxa bimolecular de formação. Calculamos esta taxa tanto na aproximação parabólica para as dispersões das subbandas de valência como levando em consideração o acoplamento das subbandas de buraco pesado e buraco leve, que torna não-parabólicas as dispersões das subbandas de valência e do centro de massa do éxciton. Na aproximação parabólica, os resultados mostram que a maior parte dos éxcitons é formada com energia cinética em torno da energia de ligação do estado excitônico fundamental. Isto deve-se à pouca energia dos fônons que efetivamente participam do processo de formação de éxcitons. No caso não-parabólico, a contribuição não nula dos espalhamentos com troca de paridade abre mais um canal para processos que envolvem troca de spin. Apresentamos ainda nesta dissertação o estudo do processo de captura de portadores por um fio quântico na forma de T. A pequena diferença entre as energias dos estados quase-bidimensionais do contínuo e o estado ligado quase-unidimensional do fio faz com que haja uma competição entre o processo de captura e o processo de formação de éxcitons nestes sistemas / Abstract: The main goal of this work is to study the exciton formation process in semiconductor quantum wells. First, we discuss the different scattering processes, besides the exciton formation, involved when a semiconductor is excited by an ultrashort laser pulse. Next, we review the main experimental results from the literature. It shows the difficulty in extracting from the experiments the information about the exciton formation process. In our model, we describe the formation of an exciton by the transition of an electron-hole pair in the threshold of the exciton continuum to the ground exciton state through scattering with longitudinal acoustical phonons. This is a bimolecular process, caracterized by a bimolecular formation rate. We calculate this rate considering the parabolic and the non-parabolic dispersions for the valence subbands and the exciton center-of- mass. In the parabolic approximation, the results show that most of the excitons are formed with an excess of kinetic energy of the order of the exciton ground state binding energy. This is a consequence of the low energy of the phonons which effectively participate in the process. In the non-parabolic case, there is a finite probability of scattering involving the change of parity in symmetric quantum wells. This opens a channel for spin-flip transitions We also discuss the carrier capture process in T-shaped quantum wires. The small difference between the energies of the quasi-two-dimensional continuous states and the quasi-unidimensional bound state makes the exciton formation process to compete with the capture process / Mestrado / Física / Mestre em Física

Orientador: Eliermes Arraes Meneses / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-07-14T21:40:07Z (GMT). No. of bitstreams: 1 Mendonca_CesarAugustoCurvellode_M.pdf: 1779771 bytes, checksum: d1a5e39ca7e4da8c9f3213d9f403a4db (MD5) Previous issue date: 1987 / Resumo: Foram feitas medidas de fotoluminescência em regime de baixo nível de excitação ótica e baixas temperaturas (< 2K). Os objetivos deste trabalho foram a caracterização e o estudo de algumas amostras de Arseneto de Gálio(GaAs), crescidas por Epitaxia por Feixe Molecular(MBE) não dopadas, e outras crescidas por Epitaxia de Fase Líquida(LPE) dopadas com Estanho(Sn). Nas primeiras, a baixa eficiência quântica de emissão das linhas excitônicas foram associadas à possível existência de grande concentração de defeitos gerados no processo de crescimento. Por outro lado, observamos alta Intensidade para linhas atribuídas a transições envolvendo impurezas aceitadoras, as quais apontaram para a presença de altas concentrações de Carbono no material. Nas últimas verificamos, através do espectro, a presença de impurezas aceitadoras de Zinco, Carbono e Estanho. Focalizamos principalmente o nível aceitador profundo introduzido no "gap" do GaAs, pelo Sn, através das transições ocorridas a partir do complexo exciton ligado à impureza (Snº, X) e banda impureza (e, Snº). Um cálculo para energia de ligação do complexo foi proposto, considerando-se uma renormalização dos valores da massa efetiva de buraco, m*b, e da constante dielétrica / Abstract: Photoluminescence measurements have been performed under low excitation levels and low temperatures (< 2K). The main goals in this work has been the characterization and the study of some samples of undoped Gallium Arsenide (GaAs), grown in a Molecular Bean Epitaxy (MBE) system, and Liquid-Phase-Epitaxy(LPE) GaAs, which were intentionally doped with Tin(Sn). In the former the low emission quantum efficiency of the excitonic lines has been related to the possible existence of a high concentration of defects, generated in the growth process. On the other hand, the high intensity observed in those lines attributed to transitions involving acceptor impurities, pointed to the presence of high concentrations of Carbon in this material. In the latter, the presence of acceptor impurities as Zinc, Carbon and Tin has been verified. We foccused most of our attention at the deep acceptor level, in the gap, due to Sn in GaAs through the transitions from the excitonic complex (Snº, X) and band impurity (e, Snº). A calculation of the binding energy of this complex has been proposed, taking into account a renormalization of the hole effective mass, m*h, and dielectric constant / Mestrado / Física / Mestre em Física

2D materials like graphene and MoS_2 are atomically thin, extremely strong and flexible, making them attractive for integration into strain engineered devices. Strain on these materials can change physical properties, as well as induce exotic physics, not typically seen in solid-state systems. Here, we probe the novel physics arising from distorted lattices of 2D materials, strained by nanopillars indentation and microelectromechanical systems (MEMS), using Raman and photoluminescence (PL) spectroscopy. From nanopillars strained multilayer MoS_2, we observe exciton and charge carrier funneling due to strain, inducing dissociation of excitons in to free electron-hole pairs in the indirect material. Using MEMS devices, we were able to dynamically strain monolayer and multilayer graphene. Multilayer graphene under MEMS strain showed signatures of loss in Bernal stacking due to shear of the individual layers, indicating that MEMS can be used to tune the layer commensuration with tensile strain. We further explore simulation of pseudo-magnetic fields (PMFs) generated in monolayer graphene strained by MEMS, using machine learning, to accelerate and optimize the strength and uniformity of the PMF in new graphene geometries. Nanopillars provide non-uniform, centrally biaxial strain to multilayer MoS_2 transferred on top. Raman E^1_2g and PL redshift across the pillar confirms 1-2% strain in the material. We also observe a softening in the A_1g Raman mode and an enhancement in the overall PL with an increase in radiative trions, under strain. The changes in these charge-dependent features indicates funneling of charge carriers and neutral excitons to the apex of the pillar, as strain locally deforms the band structure of the conduction and valence bands. DFT calculations of the band structure in bilayer MoS_2 under biaxial strain shows the conduction band is lowered, further increasing the indirectness of multilayer MoS_2. This should cause the PL intensity to decrease, whereas we observe an increase in MoS_2 PL intensity under strain. We theorize that this is due to a dissociation of excitons into free electron-hole pairs. The increase in charge carrier densities due to strain leads to a renormalization of the local band structure and increased dielectric screening, supporting free electron-hole recombination at the K-point without momentum restrictions. In turn, electron-hole recombination occurs around the K-point inducing a high intensity PL, which opens attractive opportunities for utilization in optoelectronic devices. MEMS chevron actuators can dynamically strain 2D materials, which we demonstrate through uniaxial strain in CVD and exfoliated graphene. We use a novel microstructure assisted transfer technique which can deterministically place materials on non-planar surfaces like MEMS devices. Building on previously reported 1.3% in monolayer MoS2 from our group, we report tunable 0.3% strain in CVD monolayer graphene and 1.2% strain in multilayer exfoliated graphene using MEMS chevron actuators, detected by Raman spectroscopy. The asymmetric-to-symmetric strain evolution of the 2D phonon line shape in multilayer graphene is evidence of changes in interlayer interactions, caused by shearing between layers. This demonstrates that MEMS can be used to tune the commensuration in few layer 2D materials, which is a promising avenue towards Moiré engineering. Using machine learning, we also simulate optimal monolayer graphene geometries for generating strong, uniform pseudo-magnetic fields by MEMS strain. The coupled use of finite-element methods, variational auto-encoder, and auxiliary neural network accelerates the search for PMFs in strained graphene, while optimizing the graphene shape for fabrication through electron-beam lithography. Our experimental and simulated work creates a road-map for rapid advancement in zero-field quantum Hall effect devices using graphene-integrated MEMS actuators.

In this thesis, Density Functional Theory and Time-Dependent Density-Functional Theory approaches are applied to study the optical and magnetic properties of several types of nanostructures. In studies of the optical properties we mainly focused on the plasmonic and excitonic effects in pure and transition metal-doped noble metal nanochains and their conglomerates. In the case of pure noble metal chains, it was found that the (collective) plasmon mode is pronounceable when the number of atoms in the chain is larger than 5. The plasmon energy decreases with further with increasing number of atoms (N) and is almost N-independent when N is larger than 20. In the case of coupled pure chains it was found that the plasmon energy grows as square root of the number of chains, and reaches the visible light energy 1.8eV for the case of three parallel chains. Doping of pure Au chains with transition-metal atoms leads in many cases to formation of additional plasmon peaks close in energy to the undoped chain peak. This peak comes from the local charge oscillations around the potential minima created by the impurity atom. The effect is especially pronounced for Ni-doped chains. In the multiple-chain case, we find an unusual hybridization of the two different (local and collective) plasmon modes. Changing the chain size and chemical composition in the array can be used to tune the absorption properties of nanochains. The case of coupled finite (plasmonic) and infinite (semiconductor, excitonic) chains was also analyzed. We find that one can get significant exciton-plasmon coupling, including hybridized modes and energy transfer between these excitations, in the case of doped chains. The impurity atoms are found to work as attraction centers for excitons. This can be used to transform the exciton energy into local plasmon oscillations with consequent emission at desired point (at which the impurity is located). In a related study the optical properties of single layer MoS2 was analyzed with a focus on the possibility of ultrafast emission, In particular, it was found that the system can emit in femto-second regime under ultrafast laser pulse excitations. Finally, we have studied the magnetic properties of FeRh nanostructures to probe whether there is an antiferromagnetic to ferromagnetic transition as a function of the ratio of Fe and Rh atoms, as in the bulk alloy.. Surprisingly, the ferromagnetic phase is found to be much more stable for these nanostructures as compared to the bulk, which suggests that band-type effects may be responsible for this transition in the bulk, i.e. the transition cannot be described in terms of modification of the Heisenberg model parameters.

<p> The interaction of light with semiconductors provides essential insight into their electronic and photonic properties. Excitons, excited electron-hole pairs, determine the optical response of nanomaterials and act as nanoscale energy carriers, making excitonic materials excellent candidates for optoelectronic, photovoltaic, and quantum devices. Unique phenomena can be brought about by using excitonic materials as building blocks in designing new systems and taking advantage of excitons’ dimensionality. For example, growing quantum dots into highly ordered arrays enhances exciton transport due to the strong dipolar coupling between excitons. Alternatively, forming vertical heterostructures between monolayer transition metal dichalcogenides introduces moiré superlattices, which localize the excitons introducing nonlinear interactions that be exploited for quantum information processing. Understanding these complex excitonic systems requires experimental tools capable of high spatial and temporal resolutions.</p> <p><br></p> <p>This thesis aims to contribute to understanding the complex excitons and charges formed at nanoscale interfaces with ultrafast techniques. In the discussed work, we take advantage of the 100s of fs time resolution and 10s of nm spatial precision to visualize exciton migration and dynamics associated with complex excitonic systems. First, we introduce the optical techniques needed to help us understand the fundamental photophysics of the studied systems (Chapter 2). Next, we provide an example of how we can use these methods to understand exciton coherence in perovskite quantum dot solids exhibiting superradiance (Chapter 3) and enhanced exciton transport (Chapter 4) due to low disorder and strong dipolar coupling. We also characterize and explore the behavior of highly excited excitons, Rydberg states, in transition metal dichalcogenides (Chapter 5). Then, we examine the properties of heterostructures formed between two monolayers of transition metal dichalcogenides exhibiting moiré superlattices and investigate the nonlinear exciton-exciton interactions modulated by the moiré potentials (Chapter 6). We also explore charge carrier behavior at interfaces of two different excitonic materials in molybdenum disulfide-single-wall carbon nanotube heterojunctions containing one- and two-dimensional excitons (Chapter 7). Finally, we visualize and quantify charge carrier migration across an alloyed cadmium sulfide and cadmium selenide lateral heterojunction (Chapter 8). We hope to give the reader a better understanding of these complex systems and open up new possibilities for their efficient use through the results presented in this thesis. </p>