Colloidal Grains Research Articles

Influence of liquid properties of colloidal crystals to thermal stability of colloidal crystals on different substrate surfaces through heterogeneous nucleation

The effects of liquid properties, such as pH and conductivity, on the thermal stability of electrostatically interacting colloidal silica crystals generated from heterogeneous nuclei were investigated mainly by measuring relative reflection spectra. The melting behavior of the colloidal crystals was also investigated. The melting points of both negatively and positively charged 3-aminopropyltriethoxysilane (APS)-treated substrates with different surface charges increased or decreased with increasing or decreasing pH. For both substrates, pH 5.5 was the modulation point of the crystal melting, and the melting point increased with increasing pH. For the negatively charged substrate, the melting point increased slowly as the pH decreased from pH 5.5. Meanwhile, the melting point of the APS-treated substrate increased more with decreasing pH from 5.5 than that of the negatively charged substrate. The cationisation of the substrate increased with decreasing pH, resulting in stronger electrostatic interactions with the negatively charged colloidal crystals and enhanced thermal stability. Next, we investigated the size of colloidal crystal grains in sample bottles for different liquid properties, and the results show that at the higher pH, the smaller crystal grains, indicating that pH affects both the substrates and crystals. Moreover, the binding effect of the APS-treated substrate on the crystals became stronger at lower pH, thereby enhancing the thermal stability of the crystals.Graphical

Defect Passivation in Lead‐Halide Perovskite Nanocrystals and Thin Films: Toward Efficient LEDs and Solar Cells

AbstractLead‐halide perovskites (LHPs), in the form of both colloidal nanocrystals (NCs) and thin films, have emerged over the past decade as leading candidates for next‐generation, efficient light‐emitting diodes (LEDs) and solar cells. Owing to their high photoluminescence quantum yields (PLQYs), LHPs efficiently convert injected charge carriers into light and vice versa. However, despite the defect‐tolerance of LHPs, defects at the surface of colloidal NCs and grain boundaries in thin films play a critical role in charge‐carrier transport and nonradiative recombination, which lowers the PLQYs, device efficiency, and stability. Therefore, understanding the defects that play a key role in limiting performance, and developing effective passivation routes are critical for achieving advances in performance. This Review presents the current understanding of defects in halide perovskites and their influence on the optical and charge‐carrier transport properties. Passivation strategies toward improving the efficiencies of perovskite‐based LEDs and solar cells are also discussed.

Defect Passivation in Lead-Halide Perovskite Nanocrystals and Thin Films: Toward Efficient LEDs and Solar Cells.

Lead‐halide perovskites (LHPs), in the form of both colloidal nanocrystals (NCs) and thin films, have emerged over the past decade as leading candidates for next‐generation, efficient light‐emitting diodes (LEDs) and solar cells. Owing to their high photoluminescence quantum yields (PLQYs), LHPs efficiently convert injected charge carriers into light and vice versa. However, despite the defect‐tolerance of LHPs, defects at the surface of colloidal NCs and grain boundaries in thin films play a critical role in charge‐carrier transport and nonradiative recombination, which lowers the PLQYs, device efficiency, and stability. Therefore, understanding the defects that play a key role in limiting performance, and developing effective passivation routes are critical for achieving advances in performance. This Review presents the current understanding of defects in halide perovskites and their influence on the optical and charge‐carrier transport properties. Passivation strategies toward improving the efficiencies of perovskite‐based LEDs and solar cells are also discussed.

Jumping Sundogs, Cat’s Eye and Ferrofluids

We have explored some features of the complex fluids present in Earth’s atmosphere by the observation of some optical phenomena and compared them to the optical phenomena observed in gems and magnetic materials. The main feature of a complex fluid is that it contains polyatomic structures such as polymer molecules or colloidal grains. This paper includes some setups using tabletop experiments, which are intended to show concretely the principles discussed, giving a sense of how well the idealizations treated apply to the atmospheric systems. We have explored sundogs, light pillars, and the halo formation, which involve the existence of a certain structure in the atmospheric medium, resembling the structures observed in some types of gems and ferrofluids.

Convenient and Efficient Fabrication of Colloidal Crystals Based on Solidification-Induced Colloidal Assembly.

The simple yet efficient and versatile fabrication of colloidal crystals was investigated based on the solidification-induced colloidal crystallization process with particle/water suspension as precursor. The resulting colloidal crystals were constituted by crystal grains with sizes ranging from several tens of micrometers to a few millimeters. Each of the grains had a close-hexagonal array of colloids, which endowed the bulk colloidal crystal powders with some specific optical properties. The freezing of water was shown as the major driving force to form colloidal crystal grains, which supersaturated the solution with nanoparticles and thus induced the formation and growth of colloidal crystal seeds. This process is intrinsically different from those conventional methods based on shearing force, surface tension, columbic interaction or magnetic interaction, revealing a new strategy to fabricate colloidal crystals in a convenient and efficient way.

Self‐Assembly: The Control of Colloidal Grain Boundaries through Evaporative Vertical Self‐Assembly (Small 12/2019)

Self‐Assembly: The Control of Colloidal Grain Boundaries through Evaporative Vertical Self‐Assembly (Small 12/2019)

The Control of Colloidal Grain Boundaries through Evaporative Vertical Self-Assembly.

Self-assembly continuously gains attention as an excellent method to create novel nanoscale structures with a wide range of applications in photonics, optoelectronics, biomedical engineering, and heat transfer applications. However, self-assembly is governed by a diversity of complex interparticle forces that cause fabricating defectless large scale (>1 cm) colloidal crystals, or opals, to be a daunting challenge. Despite numerous efforts to find an optimal method that offers the perfect colloidal crystal by minimizing defects, it has been difficult to provide physical interpretations that govern the development of defects such as grain boundaries. This study reports the control over grain domains and intentional defect characteristics that develop during evaporative vertical deposition. The degree of particle crystallinity and evaporation conditions is shown to govern the grain domain characteristics, such as shapes and sizes. In particular, the grains fabricated with 300 and 600 nm sphere diameters can be tuned into single-column structures exceeding ≈1 mm by elevating heating temperature up to 93 °C. The understanding of self-assembly physics presented in this work will enable the fabrication of novel self-assembled structures with high periodicity and offer fundamental groundworks for developing large-scale crack-free structures.

Self-Driven Fractional Rotational Diffusion of the Harmonic Three-Mass System

In flat space, changing a system's velocity requires the presence of an external force. However, an isolated nonrigid system can freely change its orientation due to the nonholonomic nature of the angular momentum conservation law. Such nonrigid isolated systems may thus manifest their internal dynamics as rotations. In this work, we show that for such systems chaotic internal dynamics may lead to macroscopic rotational random walk resembling thermally induced motion. We do so by studying the classical harmonic three-mass system in the strongly nonlinear regime, the simplest physical model capable of zero angular momentum rotation as well as chaotic dynamics. At low energies, the dynamics are regular and the system rotates at a constant rate with zero angular momentum. For sufficiently high energies a rotational random walk is observed. For intermediate energies the system performs ballistic bouts of constant rotation rates interrupted by unpredictable orientation reversal events, and the system constitutes a simple physical model for Lévy walks. The orientation reversal statistics in this regime lead to a fractional rotational diffusion that interpolates smoothly between the ballistic and regular diffusive regimes.

Acousto-optic modulation in ion implanted semiconductor plasmas having SDDC

Abstract The present paper is aimed to the exploration of acousto-optic (AO) modulational amplification in ion implanted semiconductors. The AO modulational process has been treated as a four wave parametric mixing process and the effective third-order acousto-optic susceptibility characterizing the instability process has been deduced. By considering that the origin of modulational interaction lies in the third order AO susceptibility arising from the nonlinear induced current density and using the coupled mode theory, an analytical investigation of an intense laser beam in a strain dependent dielectric constant (SDDC) semiconductor crystal is presented. We found a significant change in threshold and gain characteristics with changes in charge imbalance parameter. The presence of colloidal grains (CGs) plays an effective role in changing the threshold intensity and effective gain constant.

Colloidal crystal order and structure revealed by tabletop extreme ultraviolet scattering and coherent diffractive imaging.

Colloidal crystals with specific electronic, optical, magnetic, vibrational properties, can be rationally designed by controlling fundamental parameters such as chemical composition, scale, periodicity and lattice symmetry. In particular, silica nanospheres -which assemble to form colloidal crystals- are ideal for this purpose, because of the ability to infiltrate their templates with semiconductors or metals. However characterization of these crystals is often limited to techniques such as grazing incidence small-angle scattering that provide only global structural information and also often require synchrotron sources. Here we demonstrate small-angle Bragg scattering from nanostructured materials using a tabletop-scale setup based on high-harmonic generation, to reveal important information about the local order of nanosphere grains, separated by grain boundaries and discontinuities. We also apply full-field quantitative ptychographic imaging to visualize the extended structure of a silica close-packed nanosphere multilayer, with thickness information encoded in the phase. These combined techniques allow us to simultaneously characterize the silica nanospheres size, their symmetry and distribution within single colloidal crystal grains, the local arrangement of nearest-neighbor grains, as well as to quantitatively determine the number of layers within the sample. Key to this advance is the good match between the high harmonic wavelength used (13.5nm) and the high transmission, high scattering efficiency, and low sample damage of the silica colloidal crystal at this wavelength. As a result, the relevant distances in the sample - namely, the interparticle distance (≈124nm) and the colloidal grains local arrangement (≈1μm) - can be investigated with Bragg coherent EUV scatterometry and ptychographic imaging within the same experiment simply by tuning the EUV spot size at the sample plane (5μm and 15μm respectively). In addition, the high spatial coherence of high harmonics light, combined with advances in imaging techniques, makes it possible to image near-periodic structures quantitatively and nondestructively, and enables the observation of the extended order of quasi-periodic colloidal crystals, with a spatial resolution better than 20nm. In the future, by harnessing the high time-resolution of tabletop high harmonics, this technique can be extended to dynamically image the three-dimensional electronic, magnetic, and transport properties of functional nanosystems.

Formation of Liquid Marbles Using pH-Responsive Particles: Rolling vs Electrostatic Methods.

Aqueous dispersions of micrometer-sized, monodisperse polystyrene (PS) particles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate] (PDEA) colloidal stabilizer on their surfaces were dried under ambient conditions at pH 3.0 and 10.0. The resulting dried cake-like particulate materials were ground into powders and used as a stabilizer to fabricate liquid marbles (LMs) by rolling and electrostatic methods. The powder obtained from pH 3.0 aqueous dispersion consisted of polydisperse irregular-shaped colloidal crystal grains of densely packed colloids which had hydrophilic character. On the other hand, the powder obtained from pH 10.0 aqueous dispersion consisted of amorphous and disordered colloidal aggregate grains with random sizes and shapes, which had hydrophobic character. Reflecting the hydrophilic-hydrophobic balance of the dried PDEA-PS particle powders, stable LMs were fabricated with distilled water droplets by rolling on the powders prepared from pH 10.0, but the water droplets were adsorbed into the powders prepared from pH 3.0. In the electrostatic method, where an electric field assists transport of powders to a droplet surface, the PDEA-PS powders prepared from pH 3.0 jumped to an earthed pendant distilled water droplet to form a droplet of aqueous dispersion. Conversely the larger powder aggregates prepared from pH 10.0 did not jump due to cohesion between the hydrophobic PDEA chains on the PS particles, resulting in no LM formation.

Local Melting Attracts Grain Boundaries in Colloidal Polycrystals.

We find that laser-induced local melting attracts and deforms grain boundaries in 2D colloidal crystals. When a melted region in contact with the edge of a crystal grain recrystallizes, it deforms the grain boundary-this attraction is driven by the multiplicity of deformed grain boundary configurations. Furthermore, the attraction provides a method to fabricate artificial colloidal crystal grains of arbitrary shape, enabling new experimental studies of grain boundary dynamics and ultimately hinting at a novel approach for fabricating materials with designer microstructures.

Revealing Three-Dimensional Structure of an Individual Colloidal Crystal Grain by Coherent X-Ray Diffractive Imaging.

We present results of a coherent x-ray diffractive imaging experiment performed on a single colloidal crystal grain. The full three-dimensional (3D) reciprocal space map measured by an azimuthal rotational scan contained several orders of Bragg reflections together with the coherent interference signal between them. Applying the iterative phase retrieval approach, the 3D structure of the crystal grain was reconstructed and positions of individual colloidal particles were resolved. As a result, an exact stacking sequence of hexagonal close-packed layers including planar and linear defects were identified.

Effect of cooling rate on crystallization process of thermo-sensitive poly-N-isopropylacrylamide colloid

Grain size has a significant influence on the performances of materials. Cooling rate is a key process parameter for controlling the size of crystal grain. Real-time observations of crystallization process on an atomic scale under different cooling rates are helpful for an in-depth understanding of this scientific issue. However, it is very difficult to observe directly the crystallization process on an atomic scale because it is small in size and fast in motion. Over last decades, colloidal suspension has attracted many researches attention as a model system of condensed matter to investigate phase transition kinetics at a particle scale level because colloidal particles are micrometer-sized and their thermal motions can be directly visualized and measured with an optical microscope. Thermo-sensitive poly-N-isopropylacrylamide (PNIPAM) colloidal suspension is one of the model systems and its phase transition can be easily controlled by temperature. In this paper, the PNIPAM colloidal system is used to make the real-time observation of the influence of the cooling rate on crystal grain size. Firstly, the crystal nucleation and growth process of PNIPAM colloidal suspension at a cooling rate of 30.0 ℃/h is observed with a high-resolution transmission microscope. It is found that liquid-solid phase transition of the PNIPAM colloidal suspension begins from a sudden transient nucleation, followed by a rapid grain growth as temperature decreases. The variation of crystal phase fraction with temperature undergoes three stages: slow, rapid and slow. In the initial stage, nuclei are limited and the growth driving force is low, therefore the crystal phase fraction changes slowly. In the middle stage, as temperature decreases, the growth driving force further increases and the crystal phase fraction increases rapidly. In the final stage, the crystal grains begin to adjoin with each other and the left liquid volume becomes less and less, so the crystal phase fraction increases in a slow mode again. Secondly, the PNIPAM colloidal crystal under different cooling rates from 0.5 ℃/h to 30.0 ℃/h is observed with Bragg diffraction technique. The grain size of PNIPAM crystal is also measured. It is found that the size of PNIPAM colloidal crystal grain decreases with the increase of cooling rate and the relationship between the grain size and the cooling rate obeys a power-law formula, which is also used to well describe the effect of cooling rate on grain size in metallic system. This suggests that the crystallization behavior of PNIPAM colloidal system under continuous cooling is similar to those of metallic systems. However, the fitted power-law pre-factor of PNIPAM colloidal system is very different from those of the metallic systems because the sizes and motions of PNIPAM particles are much larger and slower than those of atoms, respectively.

Colloidal crystal grain boundary formation and motion

The ability to assemble nano- and micro- sized colloidal components into highly ordered configurations is often cited as the basis for developing advanced materials. However, the dynamics of stochastic grain boundary formation and motion have not been quantified, which limits the ability to control and anneal polycrystallinity in colloidal based materials. Here we use optical microscopy, Brownian Dynamic simulations, and a new dynamic analysis to study grain boundary motion in quasi-2D colloidal bicrystals formed within inhomogeneous AC electric fields. We introduce “low-dimensional” models using reaction coordinates for condensation and global order that capture first passage times between critical configurations at each applied voltage. The resulting models reveal that equal sized domains at a maximum misorientation angle show relaxation dominated by friction limited grain boundary diffusion; and in contrast, asymmetrically sized domains with less misorientation display much faster grain boundary migration due to significant thermodynamic driving forces. By quantifying such dynamics vs. compression (voltage), kinetic bottlenecks associated with slow grain boundary relaxation are understood, which can be used to guide the temporal assembly of defect-free single domain colloidal crystals.

Double hexagonal close-packed structure revealed in a single colloidal crystal grain by Bragg rod analysis

A coherent X-ray diffraction study of a single colloidal crystal grain composed of silica spheres is reported. The diffraction data contain Bragg peaks and additional features in the form of Bragg rods, which are related to the stacking of the hexagonally close-packed layers. The profile of the Bragg rod shows distinct intensity modulations which, under the specific experimental conditions used here, are directly related to the stacking sequence of the layers. Using a model for the scattered intensity along the Bragg rod for an exact stacking sequence of a finite number of hexagonally close-packed layers, it is found that a double hexagonal close-packed stacking sequence is present in the colloidal crystal grain. This analysis method opens up ways to obtain crucial structural information from finite-sized crystalline samples by employing advanced third-generation X-ray sources.

Three-dimensional structure of a single colloidal crystal grain studied by coherent x-ray diffraction

A coherent x-ray diffraction experiment was performed on an isolated colloidal crystal grain at the coherence beamline P10 at PETRA III. Using azimuthal rotation scans the three-dimensional (3D) scattered intensity from the sample in the far-field was measured. It includes several Bragg peaks as well as the coherent interference around these peaks. The analysis of the scattered intensity reveals the presence of plane defects in a single grain of the colloidal sample. We confirm these findings by model simulations. In these simulations we also analyze the experimental conditions required to phase the 3D diffraction pattern from a single colloidal grain. This approach has the potential to produce a high resolution image of the sample revealing its inner structure, with possible structural defects.

Direct Observation of Grain Rotation-Induced Grain Coalescence in Two-Dimensional Colloidal Crystals

A spatially modulated laser is used to produce multiple localized thermal gradients in a colloidal sample placed above a gold surface. We use an optical microscope to observe real time dynamics of the resulting two-dimensional colloidal crystal grains and find that grain rotation-induced grain coalescence (GRIGC) occurs with the rotation of both grains before coalescence. Control over the grain size shows that the time scale for grain boundary annealing in our system is in good agreement with theoretical expressions formulated for nanocrystal growth.

Buckling-driven morphological transformation of droplets of a mixed colloidal suspension during evaporation-induced self-assembly by spray drying

Morphological transformation during evaporation-induced self-assembly of a mixed colloidal suspension in micrometric droplets has been investigated. It has been demonstrated that a buckling-driven shape transition of drying droplets of mixed colloidal suspension takes place during evaporation-induced self-assembly. Further, it is also shown that the distortion modulations get significantly amplified with enhancement in volume fraction of anisotropic soft colloidal component of the mixed colloids. It has been argued that the reduction in elastic modulus of formed shell, at the boundary of a drying droplet, and the anisotropic nature of one of the colloidal components facilitate the deformation process. Hierarchical structures of these assembled colloidal grains have been probed using electron microscopy and scattering techniques.

Crystallization of charged paramagnetic colloidal grains

Two-dimensional crystallization of charged paramagnetic colloidal particles by adjusting the coupling parameter was investigated using digital video microscopy. A phase transition from a dispersed distribution to a highly ordered colloidal crystal was achieved when we adjusted the electro and magnetostatic interparticle interactions. The crystallization process of the colloidal monolayer was characterized quantitatively in terms of the radial pair distribution function. The subtle competition between the repulsive interparticle potential energy and thermal excitations of the particles determines the crystallization of the colloidal system. The results can help us understand the underlying mechanisms of electromagnetic colloidal systems' phase transitions and to fabricate colloidal crystals.