xv, 153 p. : ill. (some col.) / Lead sulfide nanocrystals (PbS-NCs) are an important class of semiconductor nanomaterials that are active in the near-infrared and exhibit unique properties distinct from their bulk analogues, notably, size tunability of the band gap and solution processability. One factor influencing PbS-NC properties is the presence of an organic ligand shell, which forms the interface between the nanocrystal core and its environment. The specific focus of this dissertation is how ionic functionalization of the ligand shell alters the physical and chemical properties of the resulting PbS-NC/ligand complex. Short-chain ligands can improve photoconductivity in PbS-NC thin films, but there are few solution-based preparations available. Chapter II demonstrates how ionic groups can enable functionalization of PbS-NCs with two short- chain thiol ligands - sodium 3-mercaptopropanesulfonate (MT) and sodium 2,3-dimercaptopropanesulfonate (DT) - via a solution-phase exchange procedure. Despite a structural similarity, DT-functionalized PbS-NCs (PbS-DT) are more stable to oxidation than MT-functionalized PbS-NCs (PbS-MT). The relative stabilities are explained in terms of different binding modes to the nanocrystal surface (bidentate vs. monodentate) and oxidation pathways (intermolecular vs. intramolecular). Toxicology studies on nanomaterials have been limited by the availability of water-soluble samples with systematically controlled structures. As examples of such materials, PbS-DT and PbS-MT nanocrystals are studied in Chapter III for their toxicological impacts on embryonic zebrafish. PbS-DT solutions induce less toxicity than PbS-MT solutions, which is explained in terms of the relative stabilities of the nanocrystal solutions. Finally, Chapter IV investigates the hitherto unexplored effects of ionic functionalization on the optical/electrical properties of PbS-NC thin films, with an emphasis on understanding how counter ions affect the photoconductivity of PbS-DT thin films. Films containing small counter ions exhibit increased dark conductivity and responsivity with time under an applied bias, whereas films containing larger or multivalent counter ions show a suppression of this behavior. These results are discussed in terms of ion motion and ion-assisted carrier injection at the PbS-NC/electrode interface. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: David R. Tyler, Chair; Mark C. Lonergan, Advisor; Catherine J. Page, Inside Member; Andrew Marcus, Inside Member; Hailin Wang, Outside Member

One-dimensional (1D) nanomaterials are of great importance for a number of potential applications. However, in order to realize this potential a thorough understanding of the charge-carrier dynamics in these materials is required, since these largely determine the optoelectronic properties of the materials in question. This thesis investigates the charge-carrier dynamics of two 1D nanomaterials, single-walled carbon nanotubes (CNTs) and tungsten-oxide nanowires (WOxNWs), with the goal of better understanding the nature of their optoelectronic responses, and how nanomaterial geometry and morphology influence these responses. We do this using terahertz time-domain spectroscopy (THz-TDS) and optical pump - terahertz probe time-domain spectroscopy (OPTP). Firstly, we discuss how to properly analyse and interpret the data obtained from these experiments when measuring 1D nanomaterials. While the data obtained from THz-TDS is fairly straight-forward to analyse, OPTP experimental data can be far from trivial. Depending on the relative size of the sample geometry compared to the probe wavelength, various approximations can be used to simplify the extraction of their ultrafast response. We present a general method, based on the transfer matrix method, for evaluating the applicability of these approximations for a given multilayer structure, and show the limitations of the most commonly used approximations. We find that these approximations are only valid in extreme cases where the thickness of the sample is several orders of magnitude smaller or larger than the wavelength, which highlight the danger originating from improper use of these approximations. We then move on to investigate how the charge-carrier dynamics of our CNTs is influenced by nanotube length and density. This is done through studying the nature of the broad THz resonance observed in finite-length CNTs, and how the nanotube length and density affects this resonance. We do this by measuring the conductivity spectra of thin films comprising bundled CNTs of different average lengths in the frequency range 0.3-1000 THz and temperature interval 10-530 K. From this we show that the observed temperature-induced changes in the terahertz conductivity spectra depend strongly on the average CNT length, with a conductivity around 1 THz that increases/decreases as the temperature increases for short/long tubes. This behaviour originates from the temperature dependence of the electron scattering rate, which results in a subsequent broadening of the observed THz conductivity peak at higher temperatures and a shift to lower frequencies for increasing CNT length. Finally, we show that the change in conductivity with temperature depends not only on tube length, but also varies with tube density. We record the effective conductivities of composite films comprising mixtures of WS2 nanotubes and CNTs vs CNT density for frequencies in the range 0.3-1 THz, finding that the conductivity increases/decreases for low/high density films as the temperature increases. This effect arises due to the density dependence of the effective length of conducting pathways in the composite films, which again leads to a shift and temperature dependent broadening of the THz conductivity peak. Next, we investigate the conflicting reports regarding the ultrafast photoconductive response of films of CNTs, which apparently exhibit photoconductivities that can vastly differ, even in sign. Here we observe explicitly that the THz photoconductivity of CNT films is a highly variable quantity which correlates with the length of the CNTs, while the specific type of CNT has little influence. Moreover, by comparing the photo-induced change in THz conductivity with heat-induced changes, we show that both occur primarily due to heat-generated modification of the Drude electron relaxation rate, resulting in a broadening of the plasmonic resonance present in finite-length metallic and doped semiconducting CNTs. This clarifies the nature of the photo-response of CNT films and demonstrates the need to carefully consider the geometry of the CNTs, specifically the length, when considering them for application in optoelectronic devices. We then move on to consider our WOxNWs. We measure the terahertz conductivity and photoconductivity spectra of thin films compromising tungsten-oxide (WOx) nanowires of average diameters 4 nm and 100 nm, and oxygen deficiencies WO2.72 and WO3 using THz-TDS and OPTP. From this we present the first experimental evidence of a metal-to-insulator transition in WOx nanowires, which occurs when the oxygen content is increased from x=2.72 -> 3 and manifests itself as a massive drop in the THz conductivity due to a shift in the Fermi level from the conduction band down into the bandgap. Furthermore we present the first experimental measurements of the photoexcited charge-carrier dynamics of WOx nanowires on a picosecond timescale and map the influence of oxygen-content and nanowire diameter. From this we show that the decay-dynamics of the nanowires is characterized by a fast decay of < 1 ps, followed by slow decay of 3-10 ps, which we attribute to saturable carrier trapping at the surface of the nanowires.

Neste trabalho, a estrutura eletrônica de poços quânticos de GaAs/In IND.0.15 Ga IND.0.85As/GaAs com dopagem planar de silício na barreira superior foi investigada utilizando-se medidas de Shubnikov-de Haas em função do tempo de iluminação, observou-se que uma quantidade significativa de elétrons estava faltando na região ativa (formada pela camada de InGaAs e pela região delta-dopada) de todas as estruturas analisadas. Um efeito fotocondutivo persistente (que persiste pelo menos 27 horas depois que a excitação óptica é desligada) foi observado em todas as amostras. Durante o processo de iluminação, portadores são liberados pela iluminação e fortes modificações nas mobilidades quânticas das sub-bandas foram observadas. Uma analise fenomenológica dos dados é apresentada, baseada em cálculos autoconsistentes da estrutura eletrônica dos sistemas analisados. / In this work, the sub-band electronic structure of de GaAs/In IND.0.15 Ga IND.0.85As/GaAs quantum wells with a Si delta-doped layer in the top barrier was investigated by Shubnikov-de Haas measurements as a function of the illumination time of the samples. Before the exposure of the heterostructure to any illumination time, we observed that a significant quantity of electrons was missing in the active region (consisting of the quantum well formed by the InGaAs layer and the Si delta-doped region) of all the analyzed structures. A persistent photoconductivity effect (which persisted at least for 27 hours after the optical excitation was turned off) was observed in all samples. During the illumination process, carriers are released by illumination and strong modifications on the quantum mobilities of the sub-bands were observed. A phenomenological analysis of the data is presented based on the self-consistent calculations of the electronic structure of the analyzed systems.

Os polímeros conjugados têm sido objeto de estudo nos últimos vinte anos devido à grande variação observada em sua condutividade quando sob dopagem química. A maioria dos polímeros dessa família passa de isolante, quando não dopados ou fracamente dopados, a bons condutores de eletricidade quando fortemente dopados. Em dopagens intermediárias apresentam um comportamento semicondutor, inclusive efeitos de fotocondução, fotovoltagem e luminescência. Nesse trabalho exploramos algumas dessas propriedades, mais comuns aos semicondutores inorgânicos, e mostramos que é possível obter dispositivos eletrônicos e/ou optoeletrônicos com os polímeros orgânicos. Em estruturas de diodos, tipo Schottky e pin, fabricamos e caracterizamos dispositivos fotovoltaicos com polianilina e poli(o-metoxianilina). Nesses materiais, sob fraca dopagem foi observado um efeito de fotocondução negativa. Já com o poli(2-metoxi, 5-hexiloxi-1,4fenileno vinileno) fabricamos e caracterizamos células fotovoltaicas e mostramos que esse tipo de estrutura permite a fabricação de um dispositivo reversível: fotovoltaico e eletroluminescente. / Conjugated polymers have been extensively studied in the last twenty years due to their high conductivity variation under doping. They are insulating materials when non-doped or weakly doped and good conductors when strongly doped. In intermediate doping concentration they behave as semiconductors, exhibiting photoconduction, photovoltaic and luminescent effects. In this work we explore some of these properties and we show that metoxyaniline), using Schottky and pin structures, were fabricated and characterized. These materiaIs, when weakly doped, showed a negative photoconductivity. Schottky diodes were also fabricated with poly (2¬methoxy, 5-hexyloxy, 1-4 phenylene-vynilene) and besides the photovoltaic effect this device exhibited the reversible eletroluminescent effect.

Made available in DSpace on 2014-10-09T12:32:05Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:51Z (GMT). No. of bitstreams: 1 02301.pdf: 3265642 bytes, checksum: ef5be621c56bae7b751bf5bc812f0c07 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Orientador: Jaime Frejlich Sochaczewsky / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T07:16:03Z (GMT). No. of bitstreams: 1 Pereira_RenataMontenegro_M.pdf: 1833986 bytes, checksum: f8a736d33723868af878beb3568ddc63 (MD5) Previous issue date: 2006 / Resumo: O objetivo desta tese foi a caracterização de materiais fotocondutores e fotorrefrativos utilizando técnicas ópticas e elétricas. A propriedade mais importante nestes materiais é a fotocondutividade e por isso nos centramos na medida dessa quantidade. Um dos materiais mais estudados em nosso laboratório, o Bi12TiO20, é pouco fotocondutor e por isso, a técnica clássica, que utiliza uma lâmpada "branca" seguida de um monocromador, para selecionar o comprimento de onda com que a amostra vai ser iluminada, mostrou-se pouco sensível. Para melhorar a sensibilidade da medida, desenvolvemos um sistema baseado num conjunto de LEDs (light-emitting diodes) quase monocromáticos, de diferentes comprimentos de onda, capazes de fornecer maior intensidade de luz do que o sistema clássico. Também propomos uma sistemática diferente para a coleta e processamento dos dados, que leva em consideração, a distribuição exponencial da luz no interior da amostra, devido à absorção¸ característica de cada material. Os resultados mostraram que o novo instrumento e o novo método de processamento de dados permitem obter mais informações sobre os materiais analisados do que seria possível utilizando a técnica clássica. A nova técnica foi aplicada ao estudo de amostras de Bi12TiO20 puro e dopado assim como de Bi12GaO20 e CdTe. Os resultados, junto com outras informações disponíveis por outras técnicas (holografia e fotocorrente modulada), permitiram detectar alguns estados localizados dentro da banda proibida destes materiais, o que é muito importante no estudo da fotocondutividade / Abstract: The objective of this work was the characterization of photoconductive and photo-refractive materials using optical and electrical techniques. The most important property of these materials is photoconductivity so that we concentrated in the measurement of this quantity. One of the most studied materials in our laboratory, Bi12TiO20, is poorly photoconductive and, because of that, the standard technique using a white lamp followed by a monochromator, to select the illumination wavelength on the sample, has shown a very poor sensistivity. In order to improve the measurement we have therefore developed a system based on an array of almost monochromatic LEDs (Light-Emitting Diodes) with different wavelengths, which are able to provide with greater light intensity than with the classical system. We also propose a different system for the data collection and processing, which considers the exponential distribution of light along the sample¿s thickness, due to the characteristic bulk absorption of these materials. Our results have shown that the new instrument and the new data processing method allow us to obtain much more information about the materials under analysis than would be possible with the classical method. The new technique was applied to the study of pure and doped B i12TiO20, as well as Bi12Ga O20 and CdTe. The results, together with further information obtained from other techniques (holography and modulated photocurrent), have allowed us to detect some localized states inside the bandgap of the materials and therefore get a better insight of their structure that is very important for the understanding of their photoconductivity properties / Mestrado / Propriedades Óticas e Espectroscopia da Matéria Condensada / Mestre em Física

The Shubnikov-de Haas magneto-resistance oscillations and photoconductivity were experimentally studied in order to investigate the interaction of CO laser radiation with n-InSb at liquid helium temperatures. The roles of various absorption mechanisms on these effects were considered, particularly near the intrinsic band edge. From these measurements an effective electron temperature Tₑ was defined that increased or decreased under illumination, depending upon the strength of the applied electric field.

Esta tese de doutorado é resultado do estudo da fotocondutividade em materiais poliméricos, com particular enfoque em diodos poliméricos com camada ativa de derivados do poli (p-fenileno vinileno) (PPV): OC10-PPV, SY e MEH-PPV, em estrutura tipo sanduíche (ITO/polimérico/Metal) de camada única, utilizando eletrodos metálicos com diferentes funções trabalho depositados sobre o mesmo filme. Para isso, foi necessária a realização de todas as etapas de fabricação de dispositivos orgânicos, como descritas neste trabalho, para obter resultados com o máximo de reprodutibilidade, bem como o domínio das técnicas de caracterização. As propriedades ópticas dos filmes poliméricos foram analisadas através dos espetros de absorção e de fluorescência estacionária na região do visível. O comportamento fotocondutivo dos dispositivos foi realizado através de medidas de corrente-tensão (I-V) e da espectroscopia de fotocorrente no estado estacionário em regime dc sob incidência de luz com diferentes comprimentos de onda, ora através do ITO, ora através dos eletrodos metálicos semitransparente, para o dispositivo sob diferentes valores de tensões aplicadas. A variação desses parâmetros permitiu verificar como estes influenciam na fotogeração e no transporte de portadores de cargas e assim adaptar e aplicar um modelo teórico que levasse em consideração o campo elétrico aplicado para ajustar a fotocorrente obtida experimentalmente, obtendo informações sobre as propriedades de fotocondutividade dos materiais estudos. / This thesis is a study about photoconductivity in polymeric materials, in particular diodes with single-layer sandwich structure derivates of poly(para-phenylene vinylene) (PPV): OC10-PPV, SY and MEH-PPV. Different metallic electrodes were deposited on the same polymeric layer. Therefore, it was necessary to realize the devices fabrication process step by step as well to dominate the characterization techniques. The optical properties of polymeric film were analyzed through the absorption and emission spectrum in the visible region. The photoconductivity behavior was studied by dc current-voltage (I-V) and photocurrent action spectra through the absorption and emission spectrum in the visible region. The photoconductivity behavior was studied by dc current-voltage (I-V) and photocurrent action spectra through the both side of device under applied voltages. The variation of these parameters allowed verifying how are influencing in the charge carrier photo-generation and the charge transport and then to adapt and apply a theoretical model wich considers the electric field applied to fit the photocurrent action spectra of devices. The values of the parameters allow to survey important about photoconductivity properties of the materials

Electron transfer processes are investigated through conductance measurements of single molecules. Measurements are performed on metal-molecule-metal junctions using a modified scanning tunneling microscope technique. Through a series of experimental measurements, and accompanying theoretical models, the influence of the molecule on the measured current is explored. These explorations are presented in five separate chapters. In chapter two, the molecular orbitals of sp-hybridized carbon chains are discussed in detail. It is demonstrated that the molecular orbitals can assume an intriguing helical shape. In chapter three, the length-dependent conductance of sp²-hybridized carbon chains is investigated. Experiment and theory demonstrate that the conductance of odd-numbered chains is nearly uniform with length. In chapter four, a new theoretical scheme to calculate quantum interference is developed. Using this scheme, it is demonstrated that quantum interference yields the decay in conductance with length for molecular wires. In chapter five, current-voltage measurements of redox-active molecular clusters are shown to agree with a hopping transport model. In chapter six, a novel experimental setup is presented that can be used to investigate photoconductivity in single-molecule junctions. This thesis provides a broad, yet rigorous, survey of electron transfer processes in single-molecule junctions.

This work is focused to study organic materials for solar energy conversion into electricity and characterization of conversion processes. Materials and their blends with semiconducting properties such as photoconductivity were studied. Thin films of organic materials and their blends were prepared by spin-coating method and characterized by optical methods (UV-VIS and photoluminiscence spectroscopy), by current-voltage characteristics, by impedance spectroscopy method, spectral response measurement of photocurrent and method of transient photoconductivity. Structural factors influences the conversion of solar energy into electricity were observed. Based no these results, the materials and their blends useful for photovoltaic applications were determined. The dependence between photoconductivity of thin films and theirs structure was also discussed.