The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

Thesis (Ph.D.)--University of Washington, 2016-08

Investigation of the Nucleation and Growth of Colloidal Indium Phosphide: from Molecular Precursors to Semiconductor Nanocrystals through In37P20(O2CR)51 as a Magic-Size Intermediate

Thesis (Ph.D.)--University of Washington, 2016-06

Measurements of small ice crystals in arctic cirrus: observations from the Indirect and Semi-Direct Aerosol Campaign (ISDAC)

In-situ observations on the size and shape of particles in arctic cirrus are less common than those in mid-latitude and tropical cirrus with considerable uncertainty about the contributions of small ice crystals (maximum dimension D<50 µm) to the mass and radiative properties that impact radiative forcing. In situ measurements of small ice crystals in arctic cirrus were made during the Indirect and Semi-Direct Aerosol Campaign (ISDAC) in April 2008 during transits of the National Research Council of Canada Convair-580 between Fairbanks and Barrow, Alaska and during Mixed Phase Arctic Cloud Experiment (MPACE) in October 2004 with the University of North Dakota (UND) Citation over Barrow, Alaska. Concentrations of small ice crystals with D < 50 μm from a Cloud and Aerosol Spectrometer (CAS), a Cloud Droplet Probe (CDP), a Forward Scattering Spectrometer Probe (FSSP), and a two-dimensional stereo probe (2DS) were compared as functions of the concentrations of crystals with D > 100 μm measured by a Cloud Imaging Probe (CIP) and two-dimensional stereo probe (2DS) in order to assess whether the shattering of large ice crystals on protruding components of different probes artificially amplified measurements of small ice crystal concentrations. The dependence of the probe comparison on other variables as CIP N>100 (number concentrations greater than diameter D>100 μm),temperature, relative humidity respect to ice (RHice), dominant habit from the Cloud Particle Imager (CPI), aircraft roll, pitch, true air speed and angle of attack was examined to understand potential causes of discrepancies between probe concentrations. Data collected by these probes were also compared against the data collected by a CAS, CDP and CIP during the Tropical Warm Pool-International Cloud Experiment (TWP-ICE) and by a CAS and 2DS during the Tropical Composition, Cloud and Climate Coupling (TC4) missions. During ISDAC, the CAS and FSSP both overestimated measurements of small ice crystals compared to both the CDP and 2DS by 1-2 orders of magnitude. Further, the amount of overestimation increased with the concentrations from the CIP2 (N>100 > 0.1 L-1). There was an unexplained discrepancy in concentrations of small crystals between the CDP and 2DS during ISDAC. In addition, there was a strong dependence on RHice of the average ratios of the N3-50, CAS/N3-50,CDP, N3-50, FSSP096/N3-50,CDP, N3-50, CAS/N3-50,FSSP096, N10-50, CDP/N3-50,2DS, N10-50, FSSP096/N10-50,2DS. Continued studies are needed to understand the discrepancy of these probes.

Single particle motion of polymeric, colloidal, and biological materials

Small particles and their dynamics are of widespread interest due both to their unique properties and their ubiquity. Here, we investigate several classes of small particles: colloids, polymers, and liposomes. All these particles, due to their size on the order of microns, exhibit significant similarity in that they are large enough to be visualized in microscopes, but small enough to be significantly influenced by thermal (or Brownian) motion. Further, similar optical microscopy and experimental techniques are commonly employed to investigate all these particles. In this work, we develop single particle tracking techniques, which allow thorough characterization of individual particle dynamics, observing many behaviors which would be overlooked by methods which time or ensemble average. The various particle systems are also similar in that frequently, the signal-to-noise ratio represented a significant concern. In many cases, development of image analysis and particle tracking methods optimized to low signal-to-noise was critical to performing experimental observations. The simplest particles studied, in terms of their interaction potentials, were chemically homogeneous (though optically anisotropic) hard-sphere colloids. Using these spheres, we explored the comparatively underdeveloped conjunction of translation and rotation and particle hydrodynamics. Developing off this, the dynamics of clusters of spherical colloids were investigated, exploring how shape anisotropy influences the translation and rotation respectively. Transitioning away from uniform hard-sphere potentials, the interactions of amphiphilic colloidal particles were explored, observing the effects of hydrophilic and hydrophobic interactions upon pattern assembly and inter-particle dynamics. Interaction potentials were altered in a different fashion by working with suspensions of liposomes, which, while homogeneous, introduce the possibility of deformation. Even further degrees of freedom were introduced by observing the interaction of particles and then polymers within polymer suspensions or along lipid tubules. Throughout, while examination of the trajectories revealed that while by some measures, the averaged behaviors accorded with expectation, often closer examination made possible by single particle tracking revealed novel and unexpected phenomena.

Shape and chemically anisotropic colloidal particles: A theoretical study of their structure, phase behavior, and slow dynamics

A detailed non-equilibrium state diagram of shape-anisotropic particle fluids is constructed. The effects of particle shape are explored using Naive Mode Coupling Theory (NMCT), and a single particle Non-linear Langevin Equation (NLE) theory. The dynamical behavior of non-ergodic fluids are discussed. We employ a rotationally frozen approach to NMCT in order to determine a transition to center of mass (translational) localization. Both ideal and kinetic glass transitions are found to be highly shape dependent, and uniformly increase with particle dimensionality. The glass transition volume fraction of quasi 1- and 2- dimensional particles fall monotonically with the number of sites (aspect ratio), while 3-dimensional particles display a non-monotonic dependence of glassy vitrification on the number of sites. Introducing interparticle attractions results in a far more complex state diagram. The ideal non-ergodic boundary shows a glass-fluid-gel re-entrance previously predicted for spherical particle fluids. The non-ergodic region of the state diagram presents qualitatively different dynamics in different regimes. They are qualified by the different behaviors of the NLE dynamic free energy. The caging dominated, repulsive glass regime is characterized by long localization lengths and barrier locations, dictated by repulsive hard core interactions, while the bonding dominated gel region has short localization lengths (commensurate with the attraction range), and barrier locations. There exists a small region of the state diagram which is qualified by both glassy and gel localization lengths in the dynamic free energy. A much larger (high volume fraction, and high attraction strength) region of phase space is characterized by short gel-like localization lengths, and long barrier locations. The region is called the attractive glass and represents a 2-step relaxation process whereby a particle first breaks attractive physical bonds, and then escapes its topological cage. The dynamic fragility of fluids are highly particle shape dependent. It increases with particle dimensionality and falls with aspect ratio for quasi 1- and 2- dimentional particles. An ultralocal limit analysis of the NLE theory predicts universalities in the behavior of relaxation times, and elastic moduli. The equlibrium phase diagram of chemically anisotropic Janus spheres and Janus rods are calculated employing a mean field Random Phase Approximation. The calculations for Janus rods are corroborated by the full liquid state Reference Interaction Site Model theory. The Janus particles consist of attractive and repulsive regions. Both rods and spheres display rich phase behavior. The phase diagrams of these systems display fluid, macrophase separated, attraction driven microphase separated, repulsion driven microphase separated and crystalline regimes. Macrophase separation is predicted in highly attractive low volume fraction systems. Attraction driven microphase separation is charaterized by long length scale divergences, where the ordering length scale determines the microphase ordered structures. The ordering length scale of repulsion driven microphase separation is determined by the repulsive range. At the high volume fractions, particles forgo the enthalpic considerations of attractions and repulsions to satisfy hard core constraints and maximize vibrational entropy. This results in site length scale ordering in rods, and the sphere length scale ordering in Janus spheres, i.e., crystallization. A change in the Janus balance of both rods and spheres results in quantitative changes in spinodal temperatures and the position of phase boundaries. However, a change in the block sequence of Janus rods causes qualitative changes in the type of microphase ordered state, and induces prominent features (such as the Lifshitz point) in the phase diagrams of these systems. A detailed study of the number of nearest neighbors in Janus rod systems reflect a deep connection between this local measure of structure, and the structure factor which represents the most global measure of order.

Lipid-Based Liquid Crystals As Carriers for Antimicrobial Peptides: Phase Behavior and Antimicrobial Effect

International audience

Mastering heterostructured colloidal nanocrystal properties for light-emitting diodes and solar cells

Solution-grown colloidal nanocrystal (NC) materials represent ideal candidates for optoelectronic devices, due to the flexibility with which they can be synthesized, the ease with which they can be processed for devicefabrication purposes and, foremost, for their excellent and size-dependent tunable optical properties, such as high photoluminescence (PL) quantum yield, color purity, and broad absorption spectra up to the near infrared. The advent of surfactant-assisted synthesis of thermodynamically stable colloidal solutions of NCs has led to peerless results in terms of uniform size distribution, composition, rational shape-design and the possibility of building heterostructured NCs (HNCs) comprising two or more different materials joined together. By tailoring the composition, shape and size of each component, HNCs with gradually higher levels of complexity have been conceived and realized, which are endowed with outstanding characteristics and optoelectronic properties. In this review, we discuss recent advances in the design of HNCs for efficient light-emitting diodes (LEDs) and photovoltaic (PV) solar cell devices. In particular, we will focus on the materials required to obtain superior optoelectronic quality and efficient devices, as well as their preparation and processing potential and limitations

Diketonylpyridinium cations as a support of new ionic liquid crystals and ion-conductive materials: analysis of counter-ion effects

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO^(R(n)pyH)] + and BF_(4)^(-) , ReO_(4)^(-), NO_(3)^(-), CF_(3)SO_(3)^(-), CuCl_(4)^(2-) counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO^(R(12)pyH)][ReO_(4)] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl_(4)^(2-) salts exhibit the best LC properties followed by the ReO_(4)^(-) ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO_(4)^(-) , and CuCl_(4)^(2-) families, and for the solid phase in one of the non-mesomorphic Cl^(-) salts. The highest ionic conductivity was found for the smectic mesophase of the ReO_(4)^(-) containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.

Anisotropic Assembly of Colloidal Nanoparticles: Exploiting Substrate Crystallinity

We show that the crystal structure of a substrate can be exploited to drive the anisotropic assembly of colloidal nanoparticles. Pentanethiol-passivated Au particles of approximately 2 nm diameter deposited from toluene onto hydrogen-passivated Si(111) surfaces form linear assemblies (rods) with a narrow width distribution. The rod orientations mirror the substrate symmetry, with a high degree of alignment along principal crystallographic axes of the Si(111) surface. There is a strong preference for anisotropic growth with rod widths substantially more tightly distributed than lengths. Entropic trapping of nanoparticles provides a plausible explanation for the formation of the anisotropic assemblies we observe.