xx, 134 p. : ill. (some col.) / Solar energy is a green alternative to fossil fuels but solar technologies to date have been plagued by low conversion efficiencies and high input costs making solar power inaccessible to much of the developing world. Semiconductor nanoparticles (NPs) may provide a route to efficient, economical solar devices through a phenomenon called multiple exciton generation (MEG). Through MEG, semiconductor NPs use a high-energy input photon to create more than one exciton (electron-hole pair) per photon absorbed, thereby exhibiting large photoconversion efficiencies. While MEG has been studied in many NP systems, and we understand some of the factors that affect MEG, a rigorous analysis of the NP-ligand interface with respect to MEG is missing. This dissertation describes how the NP ligand shell directly affects MEG and subsequent charge carrier recombination. Chapter I describes the motivation for studying MEG with respect to NP surface chemistry. Chapter II provides an in-depth overview of the transient absorption experiment used to measure MEG in the NP samples. Chapter III highlights the effect of oleic acid and sodium 2, 3-dimercaptopropane sulfonate on MEG in PbS NPs. The differences in carrier recombination were accounted for by two differences between these ligands: the coordinating atom and/or the secondary structure of the ligand. Because of these hypotheses, experiments were designed to elucidate the origin of these effects by controlling the NP ligand shell. Chapter IV details a viable synthetic route to thiol and amine-capped PbS NPs using sodium 3-mercaptopropane sulfonate as an intermediate ligand. With the versatile ligand exchange described in Chapter IV, the MEG yield and carrier recombination was investigated for ligands with varying headgroups but the same secondary structure. The correlation of ligand donor atom to MEG is outlined in Chapter V. Finally, Chapter VI discusses the conclusions and future outlook of the research reported in this dissertation. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Geraldine L. Richmond, Chairperson; Dr. David R. Tyler, Advisor; Dr. Mark C. Lonergan, Member; Dr. Catherine J. Page, Member; Dr. Hailin Wang, Outside Member

This work summarizes results of about ten years of the author’s own research activities in the field of colloidal synthesis of semiconductor nanoparticles, their postsynthetic chemical modification, assembly, and applications. I attempted to provide a concise yet comprehensive overview presenting my own results as a part of the knowledge framework created in close collaboration with many colleagues from all over the world. This habilitation thesis consists of an introduction, explaining the motivation of the research accomplished, followed by a main part which briefly presents key achievements of the author with links to appropriate annexes, i.e. original published articles in peer review journals which are attached to this cumulative script, and completed by conclusions.

Semiconductor nanostructures such as CdSe quantum dots and colloidal nanoplatelets exhibit remarkable optical properties, making them interesting for applications in optoelectronics and photocatalysis. For both areas of application a detailed understanding of the electronic structure is essential to achieve highly efficient devices. The electronic structure can be probed using the fact that optical properties of semiconductor nanoparticles are found to be extremely sensitive to the presence of excess charges that can for instance be generated by means of an electrochemical charge transfer via an electrode. Here we present the use of EMAS as a versatile spectroelectrochemical method to obtain absolute band edge positions of CdSe nanostructures versus a well-defined reference electrode under ambient conditions. In this, the spectral properties of the nanoparticles are monitored with respect to an applied electrochemical potential. We developed a bleaching model that yields the lowest electronic state in the conduction band of the nanostructures. A change in the band edge positions caused by quantum confinement is shown both for CdSe quantum dots and for colloidal nanoplatelets. In the case of CdSe quantum dots these findings are in good agreement with tight binding calculations. The method presented is not limited to CdSe nanostructures but can be used as a universal tool. Hence, this technique allows the determination of absolute band edge positions of a large variety of materials used in various applications

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-27T20:21:11Z No. of bitstreams: 1 marcelinocordeironeto.pdf: 92399516 bytes, checksum: 0d59ef50bab71144a1450179047a4f30 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-07T21:07:35Z (GMT) No. of bitstreams: 1 marcelinocordeironeto.pdf: 92399516 bytes, checksum: 0d59ef50bab71144a1450179047a4f30 (MD5) / Made available in DSpace on 2017-08-07T21:07:35Z (GMT). No. of bitstreams: 1 marcelinocordeironeto.pdf: 92399516 bytes, checksum: 0d59ef50bab71144a1450179047a4f30 (MD5) Previous issue date: 2014-05-06 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo desta tese é analisar se as propriedades ópticas apresentadas neste trabalho qualificam o sistema vítreo PZABP, com composição nominal 60P2O5.15ZnO.5Al2O3.10BaO.10PbO (% mol), dopado com íons terras-raras trivalentes, itérbio (Yb3+) e európio (Eu3+) e, também, com nanopartículas semicondutoras de telureto de zinco (ZnTe) como potencialmente útil para construção de dispositivos de emissão de luz na região de 920 nm a 1060 nm. A teoria de Judd-Ofelt é usada nos cálculos dos parâmetros de intensidade Ωλ(λ = 2,4,6). Técnicas de microscopia de força atômica (AFM), absorção óptica (AO), fotoluminescência (FL) e fotoluminescência resolvida no tempo (FLRT) caracterizam o sistema vítreo. A finalidade do ZnTe é aumentar a seção de choque de absorção do sistema vítreo PZABP e transferir energia para os íonsEu3+ e/ouYb3+. A formação de dois tipos de nanopartículas semicondutoras de telureto de zinco ZnTe-propriedades de bulk e pontos quânticos – foram identificados. FL e FLRT sugerem transferência de energia dos íons de Eu3+ e/ou ZnTe para os íons deYb3+. / The aim of this thesis is to analyze if the optical properties presented in this work qualify the glass system PZABP, with nominal composition 60P2O5.15ZnO.5Al2O3.10BaO.10PbO(% mol), doped with trivalent rare earth ions, ytterbium (Yb3+) and europium (Eu3+) as well as zinc telluride (ZnTe) as potentially useful for light emission devices in the infrared region from 920 nm to 1060 nm. The Judd-Ofelt theory is used to calculate the intensity parameters Ωλ(λ = 2,4,6). Atomic force microscopy (AFM), optical absorption (OA), photoluminescence (PL) and time-resolved photoluminescence (TRPL) techniques characterized the vitreous system. The formation of two kinds of ZnTe semiconductor nanoparticles - bulk-like and quantum dots –were identified. PL and TRPL suggest the energy transfer from Eu3+ ions and/orZnTetoYb3+ ions.