This thesis presents an exploration of the photophysics of colloidal semiconductor nanocrystals using both linear and non-linear optical measurement techniques. These optical methodologies are used to follow population dynamics in both singly and multiply excited nanocrystal systems as well as determine material properties of the ensemble. Topics covered in the thesis include, the identification and characterization of bulk-like nanocrystals, study of the fine structure states of the lowest energy exciton, single and multiexciton population dynamics, acoustic phonon modes, elasticity and surface stress properties of a colloidal ensemble in solution.Through linear spectroscopy, the properties of both quantum confined and bulk-like colloidal semiconductor nanocrystals are compared. The identification of a model system of bulk-like nanocrystals with a non-standard absorption profile serves to resolve an ambiguity in literature concerning their characterization. The remainder of the thesis is focused on the size-dependent properties of quantum confined CdSe colloidal nanocrystals. The population dynamics and material properties of these systems are studied using a nonlinear optical technique called transient grating. A third order transient grating measurement with a cross-polarized configuration, which follows the relaxation within the fine structure levels of the lowest energy exciton state, is demonstrated and used to compare systems with different crystal field splittings. Transient grating experiments performed with specific polarization sequences allow for selective observation of the dynamics amongst nearly degenerate levels at room temperature. Cross-polarized transient grating is also used to observe a quantized acoustic phonon mode in a series of nanocrystal samples. The observation of this mode allows experimental determination of the elasticity and surface stress of the nanocrystal ensemble in solution. The anisotropic origin of the acoustic phonon is discussed using a combination of theoretical analysis, modelling and experimental data. In addition, third- and fifth-order transient grating experiments are used to study exciton and multiexciton population relaxation dynamics. The work presented here spans the optical and material properties of quantum confined and `bulk' nanocrystals. This thesis attempts to illustrate the broad scope of the observed behaviour of colloidal nanocrystal systems and to contribute to a greater understanding of their physical properties.

This thesis presents an exploration of the photophysics of colloidal semiconductor nanocrystals using both linear and non-linear optical measurement techniques. These optical methodologies are used to follow population dynamics in both singly and multiply excited nanocrystal systems as well as determine material properties of the ensemble. Topics covered in the thesis include, the identification and characterization of bulk-like nanocrystals, study of the fine structure states of the lowest energy exciton, single and multiexciton population dynamics, acoustic phonon modes, elasticity and surface stress properties of a colloidal ensemble in solution.Through linear spectroscopy, the properties of both quantum confined and bulk-like colloidal semiconductor nanocrystals are compared. The identification of a model system of bulk-like nanocrystals with a non-standard absorption profile serves to resolve an ambiguity in literature concerning their characterization. The remainder of the thesis is focused on the size-dependent properties of quantum confined CdSe colloidal nanocrystals. The population dynamics and material properties of these systems are studied using a nonlinear optical technique called transient grating. A third order transient grating measurement with a cross-polarized configuration, which follows the relaxation within the fine structure levels of the lowest energy exciton state, is demonstrated and used to compare systems with different crystal field splittings. Transient grating experiments performed with specific polarization sequences allow for selective observation of the dynamics amongst nearly degenerate levels at room temperature. Cross-polarized transient grating is also used to observe a quantized acoustic phonon mode in a series of nanocrystal samples. The observation of this mode allows experimental determination of the elasticity and surface stress of the nanocrystal ensemble in solution. The anisotropic origin of the acoustic phonon is discussed using a combination of theoretical analysis, modelling and experimental data. In addition, third- and fifth-order transient grating experiments are used to study exciton and multiexciton population relaxation dynamics. The work presented here spans the optical and material properties of quantum confined and `bulk' nanocrystals. This thesis attempts to illustrate the broad scope of the observed behaviour of colloidal nanocrystal systems and to contribute to a greater understanding of their physical properties.

<p>In the growing field of spintronics there is a strong need for development of flexible lightweight semi-conducting magnets. Molecular organic-based magnets are attractive candidates since it is possible to tune their properties by organic chemistry, making them so-called “designer magnets”. Vanadium tetracyanoethylene, V(TCNE)_x, is particularly interesting since it is a semiconductor with Curie temperature above room temperature (T_C~400 K). The main problem with these organic-based magnets is that they are extremely air sensitive. This thesis reports on the frontier electronic structure of the V(TCNE)_x by characterization with photoelectron spectroscopy (PES) and near edge x-ray absorption fine structure (NEXAFS) spectroscopy. It also presents a new and more flexible preparation method of this class of organic-based thin film magnets. The result shows improved air stability of the V(TCNE)_x prepared with this method as compared to V(TCNE)_x prepared by hitherto used methods.</p>

Presently, Planck’s constant is a fundamental constant that can not be derived from other onstants. Assis developed a model based on an extended Weber-type potential energy, that allows calculating gravitational-type forces from neutral oscillating electric dipoles. Here we show that the maximum possible point-mass in his model equals the Planck mass which allows us to derive Planck’s constant and the fine-structure constant. We match the exact order of magnitude only requiring a pre-factor that is present in all Weber-type theories and has to be determined empirically. This classical model allows to link electromagnetic, gravitational and quantum properties with one approach.

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity.

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-22T16:42:56Z No. of bitstreams: 0 / Made available in DSpace on 2016-12-22T16:42:56Z (GMT). No. of bitstreams: 0 / Neste trabalho foi desenvolvido um Espectrômetro de Correlação Angular Gama- Gama Perturbada Diferencial em Tempo (CAP) constituído por seis detectores cintiladores de BaF2, para realização de medidas de interações hiperfinas (campo hiperfino magnético e gradiente de campo elétrico) em diversos materiais e propiciar estudos na área da física da matéria condensada. O espectrômetro desenvolvido possui um sistema de aquisição não convencional em comparação aos demais equipamentos destinados a medidas de CAP. Ao invés do tradicional Analisador Multicanal (MCA), este espectrômetro utiliza um sistema de aquisição de dados constituído, basicamente, por um Conversor Analógico Digital (ADC) rápido, uma placa digital (I/O) convencional e um roteador construído no laboratório de Interações Hiperfinas (LIH) do IPEN. Este versátil e eficiente sistema, controlado por um software também criado no LIH em LabVIEW, permite a geração simultânea de 30 espectros de coincidências &gamma; - &gamma; atrasadas, número superior em comparação aos 12 espectros do antigo espectrômetro de quatro detectores. Além de medidas de linearidade, resolução em tempo e tempo morto, o funcionamento e o desempenho do espectrômetro foram comprovados através de medidas de CAP utilizando os núcleos de prova 111In -> 111Cd e 181Hf -> 181Ta, cujos resultados são bem conhecidos da literatura. Foram feitas medidas de interação quadrupolar do 181Ta em háfnio metálico e do 111Cd em cádmio metálico, e de campo hiperfino magnético do 111Cd e do 181Ta em níquel. Os resultados destas medidas se mostraram em concordância com a literatura. Adicionalmente foram realizadas medidas inéditas de interações hiperfinas magnéticas no composto intermetálico LaMnSi2 utilizando os núcleos de prova 111Cd e 140Ce. As medidas foram realizadas na faixa de temperatura de 10 K a 400K. No caso das medidas utilizando a sonda 111In -> 111Cd, os resultados mostram uma variação do campo magnético com a temperatura que segue a função de Brillouin. Já no caso das medidas com o núcleo de prova 140La -> 140Ce, o resultado apresentou um comportamento anômalo do campo hiperfino em função de temperatura. Os resultados evidenciam uma forte hibridização da banda 4f do Ce com a banda 3d do Mn, fato verificado e estudado em trabalhos anteriores com compostos semelhantes. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Orientador: Francisco das Chagas Marques / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T16:01:42Z (GMT). No. of bitstreams: 1 OliveiraJunior_MyrianoHenriquesde_M.pdf: 3252159 bytes, checksum: a130bcbe767628c40a0600e14112a2a4 (MD5) Previous issue date: 2005 / Resumo: Neste trabalho foi preparada uma série de filmes de carbono amorfo pelo processo de IBAD (Ion Beam Assisted Deposition), onde foi utilizado um feixe iônico de Xe com energia fixa para todas as amostras em 1500eV para realizar sputtering em um alvo de grafite e, um segundo feixe de Xe + responsável pelo bombardeio do filme durante o crescimento. Para cada amostra foi utilizada uma energia de bombardeio diferente, de 0 a 400eV. Esse bombardeio, além de gerar uma compactação da matriz induzindo uma pressão na rede (stress intrínseco), faz com que uma certa quantidade de Xe seja incorporada pelo filme. Por medidas de RBS foram observadas concentrações de 3 a 4% desse gás nobre na matriz, que são as concentrações nas quais são observadas formações de aglomerados sólidos desse elemento quando implantado em metais ou semicondutores cristalinos. Por medidas de XAS realizadas com radiação com energias no intervalo que envolve a borda L3 do xenônio foi verificada a formação de tais aglomerados sólidos e, em conjunto com resultados obtidos por simulações computacionais obtivemos um entendimento melhor sobre a estrutura fina na região de XANES dessa borda de absorção. A partir da técnica de SAXS foram encontradas estruturas com dimensões características de cerca de 10 a 25nm de forma achatada. Como os filmes de a-C crescidos por essa técnica são altamente grafíticos, contendo uma concentração de cerca de 90% de ligações do tipo sp 2 essas estruturas parecem ser aglomerados grafíticos, cujas dimensões mostraram-se dependentes da energia de bombardeio utilizada na deposição / Abstract: In this work it was prepared a series of amorphous carbon thin films using the ion beam assisted deposition technique. We used a xenon ion beam in order to sputter a graphite target with a fixed energy of 1500eV for all samples set up. A second ion beam was used as an ion assisting beam during the deposition with different energy for each film but, always in the range of 0 to 400eV. As the bombardment energy is varied the film produced can have a structure more or less compact which implies in a pressure rising along the amorphous net, called intrinsic stress. Another consequence of the bombardment is the xenon incorporation. By RBS measurements it was observed a concentration of about 3 to 4% of this noble gas inside the films, which belong to the same range where is observed a condensation of this element in solid clusters when implanted in crystalline metals or semiconductors. From XAS measurements, with radiation energy within a range involving the Xe L3 absorption edge, those solid clusters formation were observed. With some computational simulations compared to those experimental results we were able to have a better comprehension about XANES fine structure. We used SAXS measurements to try to determine some geometrical parameters beyond those obtained by XAS. As the xenon clusters dimensions are too small (probably of about ten atoms) it is difficult to detect them by this technique with the experimental parameters used but, it was observed some structures that seem to be shaped and have characteristics dimensions varying from 10 to 25nm. What seem to be graphitic planes clusters, once amorphous carbon thin films prepared by IBAD are graphitic-like / Mestrado / Física da Matéria Condensada / Mestre em Física

Designing novel nanostructures which exploit the self-assembly capabilities of biomolecules yields a promising approach to control matter at the nanoscale. Here, the homochiral molecular self-assemblies of the methionine and tyrosine amino acids on the monocrystalline Ag(111) and Cu(111) surfaces are characterized by means of scanning tunneling microscopy (STM) and spectroscopy (STS), helium atom scattering (HAS), x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) in ultrahigh vacuum (UHV). On Ag(111), methionine self-assembles into supramolecular chains following the <110> substrate axis, forming regular nanogratings with tunable periodicity. Within the nanowires, a zwitterionic dimerization scheme is revealed. STS shows that the biomolecular nanostructures act as tunable one-dimensional quantum resonators for the surface state electrons. Zero-dimensional electronic confinement is achieved by positioning single iron atoms in the molecular trenches. This shows a novel approach to control the dimensionality of surface state electrons. The nanogratings were exploited to steer the spontaneous one-dimensional ordering of cobalt and iron atoms. For T > 15 K, the metal species self-align into homogeneously distributed chains in between the biomolecular trenches with ~25 Å interatomic distace. For Co, the dynamics of the self-alignment was monitored, revealing a reduced mobility in comparison with isolated Co atoms on bare Ag(111). On Cu(111), the self-assembly of methionine is influenced by the substrate reactivity and its temperature during molecular deposition. For T < 273 K, the biomolecules assemble in anisotropic extended clusters oriented with a -10° rotation off the <110> substrate orientations, whereas above 283 K a regularly ordered 1D phase arises with a +10° rotation off these high-symmetry axis. XPS reveals a structural transformation triggered by a thermally activated deprotonation of the zwitterionic ammonium group. On Ag(111), tyrosine self-assembles above a critical temperature into linear structures primarily following the substrate crystalline symmetry. A zwitterionic non-covalent molecular dimerization is demonstrated, NEXAFS data providing evidence of a non-flat adsorption of the phenyl ring. This recalls the geometrical pattern of methionine on Ag(111) and supports a universal self-assembling scheme for amino acids on close-packed noble metal surfaces, the different mesoscopic ordering being determined by the side chain reactivity. / Science, Faculty of / Chemistry, Department of / Graduate

Presently, Planck’s constant is a fundamental constant that can not be derived from other onstants. Assis developed a model based on an extended Weber-type potential energy, that allows calculating gravitational-type forces from neutral oscillating electric dipoles. Here we show that the maximum possible point-mass in his model equals the Planck mass which allows us to derive Planck’s constant and the fine-structure constant. We match the exact order of magnitude only requiring a pre-factor that is present in all Weber-type theories and has to be determined empirically. This classical model allows to link electromagnetic, gravitational and quantum properties with one approach.