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ß-NaYF4 nanocrystals are a popular class of optical materials. They can be doped with optically active lanthanide ions and shaped into core-multi-shell geometries with controlled dopant distributions. Here, we follow the synthesis of ß-NaYF4 nanocrystals from α-NaYF4 precursor particles using in situ small-angle and wide-angle X-ray scattering and ex situ electron microscopy. We observe an evolution from a unimodal particle size distribution to bimodal, and eventually back to unimodal. The final size distribution is narrower in absolute numbers than the initial distribution. These peculiar growth dynamics happen in large part before the α-to-ß phase transformation. We propose that the splitting of the size distribution is caused by variations in the reactivity of α-NaYF4 precursor particles, potentially due to inter-particle differences in stoichiometry. Rate equation modeling confirms that a continuous distribution of reactivities can result in the observed particle growth dynamics.
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The growth of two-dimensional platelets of the CdX family (X = S, Se, or Te) in an organic solvent requires the presence of both long- and short-chain ligands. This results in nanoplatelets of atomically precise thickness and long-chain ligand-stabilized Cd top and bottom surfaces. The platelets show a bright and spectrally pure luminescence. Despite the enormous interest in CdX platelets for optoelectronics, the growth mechanism is not fully understood. Riedinger et al. studied the reaction without a solvent and showed the favorable role for short-chain carboxylates for growth in two dimensions. Their model, based on the total energy of island nucleation, shows favored side facet growth versus growth on the top and bottom surfaces. However, several aspects of the synthesis under realistic conditions are not yet understood: Why are both short- and long-chain ligands required to obtain platelets? Why does the synthesis result in both isotropic nanocrystals and platelets? At which stage of the reaction is there bifurcation between isotropic and 2D growth? Here, we report an in situ study of the CdSe nanoplatelet reaction under practical synthesis conditions. We show that without short-chain ligands, both isotropic and mini-nanoplatelets form in the early stage of the process. However, most remaining precursors are consumed in isotropic growth. Addition of acetate induces a dramatic shift toward nearly exclusive 2D growth of already existing mini-nanoplatelets. Hence, although myristate stabilizes mini-nanoplatelets, mature nanoplatelets only grow by a subtle interplay between myristate and acetate, the latter catalyzes fast lateral growth of the side facets of the mini-nanoplatelets.
Assuntos
Compostos de Cádmio , Compostos de Selênio , Acetatos , Compostos de Cádmio/química , Ligantes , Miristatos , Ácido Mirístico , Compostos de Selênio/química , Solventes , Análise Espectral , Raios XRESUMO
We study the crystallization of colloidal dispersions under capillary-action-induced shear as the dispersion is drawn into flat walled capillaries. Using confocal microscopy and small angle x-ray scattering, we find that the shear near the capillary walls influences the crystallization to result in large random hexagonal close-packed (RHCP) crystals with long-range orientational order over tens of thousands of colloidal particles. We investigate the crystallization mechanism and find partial crystallization under shear, initiating with hexagonal planes at the capillary walls, where shear is highest, followed by epitaxial crystal growth from these hexagonal layers after the shear is stopped. We then characterize the three-dimensional crystal structure finding that the shear-induced crystallization leads to larger particle separations parallel to the shear and vorticity directions as compared to the equilibrium RHCP structure. Confocal microscopy reveals that competing shear directions, where the capillary walls meet at a corner, create differently oriented hexagonal planes of particles. The single-orientation RHCP colloidal crystals remain stable after formation and are produced without the need of complex shear cell arrangements.
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Hot-injection synthesis is renowned for producing semiconductor nanocolloids with superb size dispersions. Burst nucleation and diffusion-controlled size focusing during growth have been invoked to rationalize this characteristic yet experimental evidence supporting the pertinence of these concepts is scant. By monitoring a CdSe synthesis in-situ with X-ray scattering, we find that nucleation is an extended event that coincides with growth during 15-20% of the reaction time. Moreover, we show that size focusing outpaces predictions of diffusion-limited growth. This observation indicates that nanocrystal growth is dictated by the surface reactivity, which drops sharply for larger nanocrystals. Kinetic reaction simulations confirm that this so-called superfocusing can lengthen the nucleation period and promote size focusing. The finding that narrow size dispersions can emerge from the counteracting effects of extended nucleation and reaction-limited size focusing ushers in an evidence-based perspective that turns hot injection into a rational scheme to produce monodisperse semiconductor nanocolloids.
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We employ a system of cubic colloids with rounded corners to study the close-packed monolayers that form via convective assembly. We show that by controlled solvent evaporation large densely packed monolayers of colloidal cubes are obtained. Using scanning electron microscopy and particle-tracking algorithms, we investigate the local order in detail and show that the obtained monolayers possess their predicted close-packed optimal packings, the Λ0-lattice and the Λ1-lattice, as well as the simple square-lattice and disordered packings. We further show that shape details of the cube corners are important for the final packing symmetry, where the frequency of the Λ1-lattice increases with decreasing roundness of the corners, whereas the frequency of the Λ0-lattice is unaffected. The formation of both optimal packings is found to be a consequence of the out-of-equilibrium formation process, which leads to small shifts in rows of cubes, thereby transforming the Λ1-lattice into the Λ0-lattice.
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We studied the formation of supraparticles from nanocrystals confined in slowly evaporating oil droplets in an oil-in-water emulsion. The nanocrystals consist of an FeO core, a CoFe2O4 shell, and oleate capping ligands, with an overall diameter of 12.5 nm. We performed in situ small- and wide-angle X-ray scattering experiments during the entire period of solvent evaporation and colloidal crystallization. We observed a slow increase in the volume fraction of nanocrystals inside the oil droplets up to 20%, at which a sudden crystallization occurs. Our computer simulations show that crystallization at such a low volume fraction is only possible if attractive interactions between colloidal nanocrystals are taken into account in the model as well. The spherical supraparticles have a diameter of about 700 nm and consist of a few crystalline face-centered cubic domains. Nanocrystal supraparticles bear importance for magnetic and optoelectronic applications, such as color tunable biolabels, color tunable phosphors in LEDs, and miniaturized lasers.
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Ptychographic coherent X-ray imaging is applied to obtain a projection of the electron density of colloidal crystals, which are promising nanoscale materials for optoelectronic applications and important model systems. Using the incident X-ray wavefield reconstructed by mixed states approach, a high resolution and high contrast image of the colloidal crystal structure is obtained by ptychography. The reconstructed colloidal crystal reveals domain structure with an average domain size of about 2 µm. Comparison of the domains formed by the basic close-packed structures, allows us to conclude on the absence of pure hexagonal close-packed domains and confirms the presence of random hexagonal close-packed layers with predominantly face-centered cubic structure within the analyzed part of the colloidal crystal film. The ptychography reconstruction shows that the final structure is complicated and may contain partial dislocations leading to a variation of the stacking sequence in the lateral direction. As such in this work, X-ray ptychography is extended to high resolution imaging of crystalline samples.
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The structural rearrangement of polystyrene colloidal crystals under dry sintering conditions has been revealed by in situ grazing incidence X-ray scattering. The measured diffraction patterns were analysed using distorted wave Born approximation (DWBA) theory and the structural parameters of the as-grown colloidal crystals of three different particle sizes were determined for the in-plane and out-of-plane directions in a film. By analysing the temperature evolution of the diffraction peak positions, integrated intensities, and widths, the detailed scenario of the structural rearrangement of crystalline domains at the nanoscale has been revealed, including thermal expansion, particle shape transformation and crystal amorphisation. Based on DWBA analysis, we demonstrate that in the process of dry sintering, the shape of colloidal particles in a crystal transforms from a sphere to a polyhedron. Our results deepen the understanding of the thermal annealing of polymer colloidal crystals as an efficient route for the design of new nano-materials.
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For magnetite spherical nanoparticles, the orientation of the dipole moment in the crystal does not affect the morphology of either zero field or field induced structures. For non-spherical particles however, an interplay between particle shape and direction of the magnetic moment can give rise to unusual behaviors, in particular when the moment is not aligned along a particle symmetry axis. Here we disclose for the first time the unique magnetic properties of hematite cubic particles and show the exact orientation of the cubes' dipole moment. Using a combination of experiments and computer simulations, we show that dipolar hematite cubes self-organize into dipolar chains with morphologies remarkably different from those of spheres, and demonstrate that the emergence of these structures is driven by competing anisotropic interactions caused by the particles' shape anisotropy and their fixed dipole moment. Furthermore, we have analytically identified a specific interplay between energy, and entropy at the microscopic level and found that an unorthodox entropic contribution mediates the organization of particles into the kinked nature of the dipolar chains.
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Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.
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The hierarchical self-assembly of sugar and surfactant molecules into hollow tubular microstructures was characterized in situ with high resolution small-angle X-ray scattering spanning more than three orders of magnitude of spatial scales. Scattering profiles reveal that aqueous host-guest inclusion complexes self-assemble into multiple equally spaced curved bilayers forming a collection of concentric hollow cylinders. Scattering data can be described by a simple theoretical model of the microtubes. The interlamellar distance was found to be surprisingly large. Moreover, we report that the multi-walled structure of the microtubes swells as the concentration or the temperature is varied.
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Ordered two-dimensional (2D) superstructures of colloidal nanocrystals (NCs) can be tailored by the size, shape, composition, and surface chemistry of the NC building blocks, which can give directionality to the resulting superstructure geometry. The exact formation mechanism of 2D NC superstructures is however not yet fully understood. Here, we show that oleic acid (OA) ligands induce atomic alignment of wurtzite ZnS bifrustum-shaped NCs. We find that in the presence of OA ligands the {002} facets of the ZnS bifrustums preferentially adhere to the liquid-air interface. Furthermore, OA ligands induce inter-NC interactions that also orient the NCs in the plane of the liquid-air interface, resulting in atomically aligned 2D superstructures. We follow the self-assembly process in real-time with in situ grazing incidence small-angle X-ray scattering and find that the NCs form a hexagonal superstructure at early stages after which they come closer over time, resulting in a close-packed NC superstructure. Our results demonstrate the profound influence that surface ligands have on the directionality of 2D NC superstructures and highlight the importance of detailed in situ studies in order to understand the self-assembly of NCs into 2D superstructures.
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Nanopartículas/química , Ácido Oleico/química , Sulfetos/química , Compostos de Zinco/química , Nanopartículas/ultraestrutura , Difração de Raios XRESUMO
In situ X-ray diffraction studies of structural evolution of colloidal crystal films formed by polystyrene spherical particles upon incremental heating are reported. The Bragg peak parameters, such as peak position, integrated intensity, and radial and azimuthal widths were analyzed as a function of temperature. A quantitative study of colloidal crystal lattice distortions and mosaic spread as a function of temperature was carried out using Williamson-Hall plots based on mosaic block model. The temperature dependence of the diameter of polystyrene particles was obtained from the analysis of Bragg peaks, and the form factor contribution extracted from the diffraction patterns. Four stages of structural evolution in a colloidal crystal upon heating were identified. Based on this analysis, a model of the heating and melting process in the colloidal crystal film is suggested.
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Structural transformations of superparamagnetic colloids confined within self-assembled microtubes are studied by systematically varying tube-colloid size ratios and external magnetic field directions. A magnetic field parallel to microtubes may stretch non-linear chains like zigzag chains into linear chains. Non-parallel fields induce new structures including repulsive chains of single colloids, kinked chains and repulsive dimers, which are not observed for unconfined magnetic colloids in the bulk. The formed colloidal structures are confirmed via model calculations which account for tube-colloid size ratio effects and their reconfigurability with the field direction. Furthermore, structures are formed that allow controllable switching between a helical and a non-helical state. All observed field-induced transformations in microtubes are reversible provided the microtubes are not completely filled with colloids. In addition, we demonstrate magnetic field-responsive 2D crystallization by extending control over colloidal configurations in single microtubes to multiple well-aligned microtubes.
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Manipulation of the self-assembly of magnetic colloidal particles by an externally applied magnetic field paves a way toward developing novel stimuli responsive photonic structures. Using microradian X-ray scattering technique we have investigated the different crystal structures exhibited by self-assembly of core-shell magnetite/silica nanoparticles. An external magnetic field was employed to tune the colloidal crystallization. We find that the equilibrium structure in absence of the field is random hexagonal close-packed (RHCP) one. External field drives the self-assembly toward a body-centered tetragonal (BCT) structure. Our findings are in good agreement with simulation results on the assembly of these particles.
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We study the influence of a magnetic field on the biaxial nematic phase of board-like goethite colloids both experimentally and theoretically. Using synchrotron small angle X-ray scattering techniques we find that applying a magnetic field along the main director of the biaxial nematic phase leads to a clear decrease in biaxiality with increasing magnetic field strength. Above a certain magnetic field strength the biaxiality is completely suppressed and the biaxial nematic phase transforms into an ordinary prolate uniaxial nematic phase. In order to interpret the physical mechanism behind this phenomenon, we develop a mean-field theory for the liquid crystal phase behaviour of the suspension. Within this theory the magnetic properties of the particles are modelled by taking into account the effect of both the permanent and the induced magnetic dipoles. The resulting phase diagrams support our experimental findings of the field-induced biaxial nematic to prolate uniaxial nematic transition. They additionally predict that for more plate-like particles, which initially would only display oblate nematic ordering of the shortest axis, the rare biaxial phase can be induced by applying a magnetic field with a carefully chosen field strength, a parameter which can be easily tuned.
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HYPOTHESIS: Multi-walled tubular aggregates formed by hierarchical self-assembly of beta-cyclodextrin (ß-CD) and sodium dodecylsulfate (SDS) hold a great potential as microcarriers. However, the underlying mechanism for this self-assembly is not well understood. To advance the application of these structures, it is essential to fine-tune the cavity size and comprehensively elucidate the energetic balance driving their formation: the bending modulus versus the microscopic line tension. EXPERIMENTS: We investigated temperature-induced changes in the hierarchical tubular aggregates using synchrotron small-angle X-ray scattering across a broad concentration range. Detailed analysis of the scattering patterns enabled us to determine the structural parameters of the microtubes and to construct a phase diagram of the system. FINDINGS: The microtubes grow from the outside in and melt from the inside out. We relate derived structural parameters to enthalpic changes driving the self-assembly process on the molecular level in terms of their bending modulus and microscopic line tension. We find that the conformation of the crystalline bilayer affects the saturation concentration, providing an example of a phenomenon we call conformational freezing point depression. Inspired by the colligative phenomenon of freezing point depression, well known from undergraduate physics, we model this system by including the membrane conformation, which can describe the energetics of this hierarchical system and give access to microscopic properties without free parameters.
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In this paper, lithographic methods are successfully employed to create growth templates for colloidal self-assembly, enabling the inclusion of crystallographic defects at predetermined positions. It is shown that through smart template design stacking faults can be grown predictably into face centered cubic structures. More interestingly, by precise guiding of the stacking faults hollow intergrowth channels can be grown at predetermined lateral and vertical positions. The mechanisms involved in defect growth are promising for extension of this technique to more complex crystal structures, such as the diamond structure, as well as to more complex faults, including corners and t-junctions.
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Coloides/síntese química , Prótons , Coloides/química , Cristalografia , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
We study the self-assembly of colloidal CdSe/CdS nanorods (NRs) at the liquid/air interface combining time-resolved in situ grazing-incidence small angle X-ray scattering (GISAXS) and ex situ transmission electron microscopy (TEM). Our study shows that NR superstructure formation occurs at the liquid/air interface. Short NRs self-assemble into micrometers long tracks of NRs lying side by side flat on the surface. In contrast, longer NRs align vertically into ordered superstructures. Systematic variation of the NR length and initial concentration of the NR dispersion allowed us to tune the orientation of the NRs in the final superstructure. With GISAXS, we were able to follow the dynamics of the self-assembly. We propose a model of hierarchical self-organization that provides a basis for the understanding of the length-dependent self-organization of NRs at the liquid/air interface. This opens the way to new materials based on NR membranes and anisotropic thin films.