In Chapter 1, I give a basic introduction to the scientific background necessary for understanding the rest of the dissertation. I describe semiconductor nanocrystals and quantum confinement, how nanocrystals grow and a brief description of the various characterization methods. Finally, I provide some of the general considerations and chemical sources for the experiments performed in the thesis as a whole. In Chapter 2, I summarize the journey towards working with molecular precursors and show the advances and challenges in modeling and understanding conversion made a step into nanoplatelets more feasible. The chalcogenourea syntheses are not included and the modeling of the spherical nanocrystals is in a fairly summarized form here. This chapter is intended to give a brief overview of the highlights, key conclusions, and resulting questions upon which I designed my own experiments. In Chapter 3, I discuss applying precursor conversion method to nanoplatelets and focus on 3ML CdE growth. I briefly introduce nanoplatelets, explain the new conditions necessary to adapt the chalcogenourea library, demonstrate my efforts in characterizing the kinetics and growth mechanisms, and finally show the relationship of precursor reactivity and final nanoplatelet size. The “kobs catalogue” which summarizes the kinetics and sizing from STEM is an appendix at the end of the chapter. In this chapter, we put to the test the idea that we can control nanocrystal synthesis through precursor reactivity. The synthesis of nanocrystal heterostructures controlled by precursor conversion was discussed in Chapter 2. In Chapter 4, the same theory is applied to nanoplatelet synthetic conditions, but because nanoplatelet nucleation is fast compared to the total reaction time, the precursors should result in something closer to what is modeled without extraneous products. At the end of the chapter, a nanoplatelet alloy catalogue records many of the modeling and alloy experiments. Chapter 5 attempts to gather the various side projects that working with nanoplatelets has brought about. All these projects come together when thinking about how the solute supply and surface ligands might determine nanoplatelet formation, which I hope to shed some insight on. In the end, I hope to have gathered enough information to provide thoughtful answers for why nanoplatelets form, how they are ideal for studying compositional growth, and how nanocrystal alloying changes the structural and optical properties of these materials.

This thesis explores how the carrier dynamics within semiconductor nanocrystals can be directly engineered through specific core-shell design. Emphasis is placed on how material characteristics, such as strain or alloying at a core-shell interface, can influence the exciton energies and the recombination dynamics within semiconductor nanocrystals. This study synthesises type-II heterojunction ZnTe/ZnSe core-shell nanocrystals via a diethyl zinc-free synthesis method, producing small size distributions and quantum yields as high as 12%. It was found that the 7% lattice mismatch between the core and shell materials places limitations on the range of structures in which coherent growth is achieved. By developing compositional and strained atomistic core-shell models a variety of physical and optical properties could be simulated and has led to a clear picture of the core-shell architecture to be built. This characterisation provides evidence that the low bulk modulus ZnTe cores are compressed by the higher bulk modulus smaller lattice constant ZnSe shells. Further studies show how strain is manifested in structures with 'sharp' core-shell interfaces and how intentional alloying the interface can influence the growth and exciton energies. A (2-6)-band effective mass model was able to distinguish between the as-grown 'sharp' and 'alloyed' interfaces which indicated that strain accentuates the redshift of the excitonic state whilst reduced strain within an alloyed interface sees a reduced redshift. Single nanocrystal spectroscopy investigations of brightly emitting single graded alloyed nanocrystals and of a size series of commercially available CdSe/ZnS nanocrystals showed almost no fluorescence intermittency (nearly 'non-blinking'). These investigations also identified trion recombination as the main mechanism within the blinking 'off' state. Ultimately this thesis adds to the growing understanding of how specific core-shell architectures manipulate the electronic structure and develops techniques to identify specific material characteristics and how these characteristics influence the physical and optical properties within semiconductor nanocrystals.

This work investigates the electronic properties of very small gold and semiconductor particles using Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and Ballistic Electron Emission Spectroscopy (BEES). Complementary theoretical works were also performed. The first theoretical work was to calculate the quantized states in the CdS/HgS/CdS quantum-well-quantum-dot nanocrystals. An eight-band envelope function method was applied to this system. This method treats exactly the coupling between the conduction bands, the light-hole bands, the heavy-hole bands, and the spin-orbit split bands. The contributions of all other bands were taken into account using second order perturbation theory. Gold nanocrystals with diameters of 1.5 nm have discrete energy levels with energy spacings of about 0.2 eV. These values are comparable to the single electron charging energy, which was about 0.5 eV in our experimental configuration. Since bulk gold doesnt have an energy gap, we expect the electron levels both below and above the Fermi level should be involved in the tunneling. Measured spectroscopy data have rich features. In order to understand and relate these features to the electronic properties of the nanocrystals, we developed a tunneling model. This model includes the effect of excited states that have electron-hole pairs. The relaxation between discrete electron energy levels can also be included in this model. We also considered how the nanocrystals affect the BEES current. In this work an ultra-high vacuum and low-temperature STM was re-designed and rebuilt. The BEEM/BEES capabilities were incorporated into the STM. We used this STM to image gold nanocrystals and semiconductor nanocrystals. STS and BEES spectra of gold nanocrystals were collected and compared with calculations.

Some interesting electronic and dynamic properties of semiconductor nanocrystal heterostructures have been investigated using various spectroscopic methods. Semiconductor nanocrystal heterostructures were prepared using colloidal synthesis techniques. Ultrafast transient absorption spectroscopy was used to monitor the relaxation of hot electrons in CdS/HgS/CdS quantum dot quantum wells. Careful analysis of the hot electron relaxation in CdS/HgS/CdS quantum dot quantum wells reveals an energy dependent relaxation mechanism involving electronic states of varying CdS and HgS composition. The composition of the electronic states, combined with the layered structure of the nanocrystal permits the assignment of CdS localized and HgS localized excited states. The dynamic effect of surface passivation is then shown to have the strongest influence on excited states that are localized in the HgS layer. New quantum dot quantum well heterostructures of different sizes and compositions were also prepared and studied. The dynamic properties of CdS/CdSe/CdS colloidal quantum wells suggest simultaneous relaxation of excited electrons within the CdS core and CdSe shell on the sub-picosecond time scale. Despite the very different electronic structure of CdS/CdSe/CdS compared to CdS/HgS/CdS, the time scales of the relaxation and electron localization were very similar. Enhancement of trap luminescence was observed when CdS quantum dots were coated with silver. The mechanism of the enhancement was investigated using time-resolved spectroscopic techniques.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 114-127).

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / In this work the synthesis of MgCdS ternary semiconductor nanocrystal alloys has been carried out by aqueous route through a bottom-up approach, using conventional hydrothermal heating as well as in situ onto graphene matrices. In the synthesis of MgCdS nanocrystals, the effect of each reaction parameter on the spectroscopic properties was studied aiming to understand the possibilities to control the optical properties. Emission spectra of MgCdS samples obtained in the experiments designed to optimize reaction parameters exhibited a single emission band reflecting nanocrystal growth, with quantum yields as high as 85%. Based on the presence of two bands in absorption spectra as well as atomic absorption spectrometry (AAS) data it was possible to propose that nanocrystals are composed of Cd and Mg. Concerning the structural architecture, it has been proposed that nanocrystals show a core-shell structure with a diffuse interface. Data from AAS also showed that the final composition of nanocrystals is generally different from the initial reaction Cd:Mg proportion, as the metal precursors have distinct reactivities. Morphological analyses by transmission electron microscopy (TEM) of nanocrystals evidenced the predominance of spherical shapes and sizes below 4 nm. Studies of the formation of nanocrystal alloys with Mg1-xCdxS and Cd1-xMgxS composition, by ion exchange from the binary components MgS and CdS helped the discussion of spectroscopic behavior of the ternary system MgCdS. It was possible to confirm that the introduction of a second cation (Cd2+ or Mg2+) into each binary structure (MgS or CdS) is consistent with the observation of two absorption bands and only one emission band. The addition of graphene derivatives during the synthesis of MgCdS nanocrystals was carried out aiming to improve the properties of the materials, as well as providing a physical support to the nanocrystals, favoring future applications. The presence of graphene induced shifts in the emission bands to larger wavelengths concomitant with intensity reduction, which can be taken as evidence of interactions between the materials. The morphologies of composites were characterized by typical graphene sheets decorated with spherical nanocrystals. / Neste trabalho foram realizadas as sínteses de nanocristais (NCs) semicondutores ternários de MgCdS via síntese aquosa através da metodologia bottom-up, assistida por tratamento térmico hidrotermal convencional, além da síntese in situ de nanocompósitos de MgCdS em matrizes de grafeno. A síntese do nanocristal de MgCdS foi avaliada através do efeito da variação de cada parâmetro de síntese sobre as propriedades espectroscópicas do material, a fim de se compreender as possibilidades de controle das propriedades ópticas. Os espectros de emissão dos NCs de MgCdS, referente ao estudo de otimização dos parâmetros de síntese, apresentaram uma única banda de emissão intensa que reflete o crescimento do nanocristal, com rendimentos quânticos de fotoluminescência elevados, chegando a 85%. Com base na presença de duas bandas de absorção no espectro de UV-visível, bem como de dados de espectrofotometria de absorção atômica (AAS), pode-se inferir que os nanocristais são compostos pelos metais de Cd e Mg, propondo-se a hipótese de uma arquitetura caroço-casca com interface difusa. Os dados obtidos através de AAS mostraram também que, como os precursores tem reatividades distintas, a composição dos materiais formados tende a diferir da proporção Cd2+:Mg2+ utilizada na reação. As análises morfológicas realizadas por microscopia eletrônica de transmissão (TEM) permitiram verificar o contorno esférico e uniforme das nanoesferas e estimar o tamanho dos nanocristais, sendo abaixo de 4 nm. Estudos de formação de ligas do tipo Mg1-xCdxS e Cd1-xMgxS, por troca iônica a partir dos componentes binários MgS e CdS permitiram compreender melhor os dados espectroscópicos dos nanocristais formados introduzindo ambos precursores simultaneamente. Confirmou-se que a introdução do segundo cátion (Cd2+ ou Mg2+) em cada estrutura binária (MgS ou CdS) de fato causa a formação de duas bandas de absorção e somente uma de emissão. A implementação de derivados de grafeno na síntese do MgCdS foi realizada a fim de aprimorar as propriedades gerais do material, bem como de propiciar um suporte físico aos nanocristais de MgCdS, favorecendo aplicações. A presença do grafeno na síntese do nanocristal proporcionou deslocamento da banda de emissão para maiores comprimentos de onda com redução da intensidade luminescente, evidenciando interações entre os materiais. As morfologias dos compósitos apresentam folhas de grafeno decoradas com nanocristais esféricos. / São Cristóvão, SE

We report on an efficient assembly approach to a variety of electrostatically stabilized all-inorganic semiconductor nanocrystals (NCs) via their linking with appropriate ions into multibranched gel networks. These all-inorganic non-ordered 3D assemblies can combine strong interparticle coupling which facilitates charge transport between the NCs with their diverse morphology, composition, size, and functional capping ligands. Moreover, the resulting dry gels (aerogels) are highly porous monolithic structures, which preserve the quantum confinement of their building blocks. The inorganic semiconductor aerogel made of 4.5 nm CdSe colloidal NCs, capped with iodide ions and bridged with Cd2+ ions, exhibited a surface area as high as 146 m2/g.

Semiconductor nanocrystals, or quantum dots, have attracted significant interest for use in solid state lighting, biological imaging, photovoltaics, catalysis, and displays such as televisions or tablets. Quantum dots excel in these applications because of their narrow emission profiles, high absorptivity at high energies, and optoelectronic properties that can be easily tuned using colloidal chemistry. The last point in particular has driven the development of new synthetic methods for producing a range of semiconducting materials on the nanoscale. Academically, interest in the synthesis of quantum dots has also extended to the mechanism of their formation and its implications for the growth of nanoscale crystals more generally. This thesis addresses facets of both points above, first by developing several novel syntheses for indium and gallium phosphide nanocrystals, and second by leveraging the synthetic control it allows to study the mechanisms of homogeneous crystal growth. Chapter 1 provides a brief overview of the colloidal syntheses, optoelectronic properties, and formation mechanisms of quantum dots. Emphasis is placed on the development of new chemical syntheses for nanoscale materials and how the size, size distribution, and morphology can be carefully controlled by thoughtful reaction design. The progression of quantum dot synthesis is presented and specific innovations to the precursor and surfactant design are highlighted. Next, a brief discussion about nanocrystal surface chemistry and its impact on the photophysical properties of the inorganic core is described along with its proposed influence on the kinetics of nanocrystal growth. Finally, classical theories of homogeneous crystal growth are presented and used to explain the origin of the exceptionally narrow size distributions accessible in a wide range of materials. Chapter 2 introduces two novel synthetic pathways to InP nanocrystals. The first describes a small library of substituted aminophosphines that can control the precursor conversion reactivity by over an order of magnitude. Leveraging the collection of aminophosphines, it is demonstrated that at sufficiently high temperatures, the rate of precursor conversion can be used to vary the final nanocrystal size—disputing previous findings for InP nanocrystals. We show that the reactivity of the phosphine is governed by a pre-equilibrium between the precursor and an intermediate (P(NHR)3) that goes on to form InP. Variations to the initial aminophosphine substitution pattern change the position of the pre-equilibrium, thereby allowing the rate of [InP]i deposition to be controlled. The second synthetic method leverages metal phosphonate salts as a surfactant to synthesize large samples of InP. We find that the nanocrystals grow via a ripening mechanism and display excellent crystallinity as determined by powder X-ray diffraction and pair distribution function analysis. Finally, we demonstrate that the final nanocrystals are bound by both phosphonates and phosphines through the use of 31P nuclear magnetic resonance spectroscopy. Chapter 3 expands on the syntheses of InP in the previous chapter by developing methods to form GaP, InxGa1-xP, and InP-based core-shell structures. At the onset, two distinct syntheses of GaP are introduced, one similar to the metal phosphonate route used to form InP, and one that used a mixture of amines to stabilize GaP colloidally. The phosphonate method results in small GaP with somewhat indistinct scattering patterns, while the amine method results in large GaP whose morphology can be varied depending on the solvent selected. Leveraging the newly developed InP and GaP syntheses we demonstrate that InxGa1-xP alloys could be directly synthesized from mixtures of In3+ and Ga3+ salts. We also show that InxGa1-xP can be accessed indirectly via cation exchange of Zn3P2 or Cd3P2, however attempts at synthesizing alloys via cation exchange with phosphonate bound GaP were found to be largely unsuccessful. Finally, the chapter contains initial attempts at synthesizing GaP/InP core-shells with the intention of producing GaP/InP/GaP spherical quantum well architectures. Preliminary data show that InP can be deposited using several different methods, though it remains unclear whether the optical properties will be suitable for integration in solid state lighting applications. Chapter 4 examines the crystal growth processes that precede the formation of monodisperse ensembles of InP, PbS, and PbSe nanocrystals. Surprisingly, we find that nucleation persists for a substantial portion of the total reaction time—a stark departure from the canonical “burst” of nucleation proposed originally by Victor LaMer. We go on to measure the nucleation period for a variety of different reaction conditions and find that the fraction of reaction time nucleation extends over is sensitive to both the material and reaction temperature. This is consistent with a mechanism where faster kinetics of monomer attachment reduce the duration of crystal nucleation—a conclusion that can be surmised by nucleation mass balance models that show a clear material and temperature dependence on the rate of nanocrystal growth. We also interrogate the claim that solute molecules accumulate prior to the formation of mature nanostructures. In situ X-ray experiments clearly corroborate the appearance of solute-like species at early reaction times that build up prior to the appearance of crystals with extended structure. Finally, we propose a novel size-focusing mechanism predicated on a size dependent growth rate. Using population mass balance modeling we show that the measurements of size and size distribution are qualitatively consistent with a growth rate inversely proportional to nanocrystal size.

No description available.

Cette thèse a pour but d'étudier le transport de charges pho- togénérées dans des matériaux hybrides composés de polymères π-conjugués et de nanocristaux de semi- conducteurs, conçus pour des applications en opto-électronique. La synthèse chimique permet d'obtenir des nanocristaux de CdSe à l'échelle du gramme ayant une faible polydispersité et des formes contrôlées (sphériques, branchées). Les ligands de surface des nanocristaux de CdSe sont échangés par de petites molécules (pyridine, éthanedithiol, phénylènediamine, butylamine, benzènedithiol) afin d'augmenter leur conductivité. L'échange de ligands modifie les niveaux énergétiques des nanocristaux, comme le montrent des études optiques et électrochimiques. Le poly(3-hexylthiophène) déposé sous forme de couches minces présente différents degrés de couplage intermoléculaire et de désordre énergétique selon la méthode de dépôt et le solvant utilisé. Dans les films hybrides, des mesures de diffraction de rayons X en incidence rasante montrent que la structuration cristalline de la matrice organique est modifiée par la présence des nanocristaux. Les mesures de Temps-de-Vol dans les couches hybrides montrent que les mobilités des trous et des électrons varient avec le contenu en nanocristaux, ainsi qu'avec leur forme et leurs ligands. De faibles fractions de nanocristaux provoquent une amélioration de la mobilité des trous, tandis que de plus grandes fractions la détériorent. Les mobilités électroniques sont soumises à une fraction-seuil, as- similable à un seuil de percolation. La fraction optimale de nanocristaux, du point de vue des mobilités des trous et des électrons, est de 36% en volume pour les nanocristaux sphériques avec les ligands de synthèse. Enfin, les simulations Monte-Carlo des courants transitoires photo-générés, dans un échantillon de poly(3-hexylthiophène) et dans un hybride, montrent d'une part que la distribution énergétique du poly(3-hexylthiophène) domine l'allure des courants simulés et d'autre part que les nanocristaux peuvent être assimilés à des sites difficilement accessibles du réseau cubique. / The aim of this work is the study of photogenerated charge transport in hybrid films composed of π-conjugated polymers and of semiconductor nanocrystals, designed for applications in optoelectronics. Chemical synthesis provides gram-scale samples of CdSe nanocrystals, of low polydispersity and con- trolled shapes (spherical, branched). In order to enhance their conductivity, the surface ligands of CdSe nanocrystals (stearic acid, oleylamine) are exchanged by smaller molecules, namely pyridine, ethanedithiol, phenylenediamine, butylamine and benzenedithiol. Optical and electrochemical studies show that the lig- and exchange modifies the nanocrystals' energy levels. Poly(3-hexylthiophene) thin films exhibit varying degrees of energetical disorder and of intermolecular coupling, depending on the processing method and on the solvent used. In hybrid films, the crystallinity of P3HT, probed by grazing incidence X-ray diffraction, is modified by the presence of nanocrystals. Time-of-Flight measurements of hybrid films show that elec- tron and hole mobilities vary with the content of nanocrystals, with their shape, and with their ligands. Small volume fractions of nanocrystals enhance the hole mobility, and large fractions degrade it. Electron mobilities are percolation-limited: they reach a stable value for a threshold fraction of nanocrystals. The optimal fraction of nanocrystals for electron and hole mobilities is 36 vol% in hybrids made of spherical nanocrystals with their synthesis synthesis ligands. Finally, Monte Carlo simulations of photogenerated current transients in pristine poly(3-hexylthiophene) and in a hybrid sample show on one hand that the energy distribution of poly(3-hexylthiophene) rules the shape of the simulated transients, and on the other hand that nanocrystals can be described as little accessible sites of the hopping lattice.