Diffusion Decoupling in Binary Colloidal Systems Observed with Contrast Variation Multispeckle Diffusing Wave Spectroscopy.

In the study of colloidal glasses, crystallization is often suppressed by leveraging size polydispersity, ranging from systems where particle sizes exhibit a continuous distribution to systems composed of particles of two or more distinct sizes. The effects of the disparities in size of the particles on the colloidal glass transition are not yet completely understood. Especially, the question of the existence of a decoupled glass transition between the large and small population remains. In order to measure colloidal dynamics on very long time scales and to disentangle the dynamics of the two populations, we employ contrast variation multispeckle diffusing wave spectroscopy. With this method, we aim to analyze the effect of size ratio, a = rPS/ rpNIPAM, on particle dynamics near the glass transition of a binary colloidal system. We find that both for long-time (α-) and short-time (ß-) relaxation, the dynamics of the small particles either completely decouple from the large ones ( a = 0.2), moving freely through a glassy matrix, or are identical to the dynamics of the larger-sized population ( a = 0.37 and 1.44). For a size ratio of 0.37, we find a single-glass transition for both particle populations. The postulated double-glass transition in simulations and theory is not observed.

Anomalous dynamics of interstitial dopants in soft crystals.

The dynamics of interstitial dopants govern the properties of a wide variety of doped crystalline materials. To describe the hopping dynamics of such interstitial impurities, classical approaches often assume that dopant particles do not interact and travel through a static potential energy landscape. Here we show, using computer simulations, how these assumptions and the resulting predictions from classical Eyring-type theories break down in entropically stabilized body-centered cubic (BCC) crystals due to the thermal excitations of the crystalline matrix. Deviations are particularly severe close to melting where the lattice becomes weak and dopant dynamics exhibit strongly localized and heterogeneous dynamics. We attribute these anomalies to the failure of both assumptions underlying the classical description: (i) The instantaneous potential field experienced by dopants becomes largely disordered due to thermal fluctuations and (ii) elastic interactions cause strong dopant-dopant interactions even at low doping fractions. These results illustrate how describing nonclassical dopant dynamics requires taking the effective disordered potential energy landscape of strongly excited crystals and dopant-dopant interactions into account.

Linking slow dynamics and microscopic connectivity in dense suspensions of charged colloids.

The quest to unravel the nature of the glass transition, where the viscosity of a liquid increases by many orders of magnitude, while its static structure remains largely unaffected, remains unresolved. While various structural and dynamical precursors to vitrification have been identified, a predictive and quantitative description of how subtle changes at the microscopic scale give rise to the steep growth in macroscopic viscosity is missing. It was recently proposed that the presence of long-lived bonded structures within the liquid may provide the long-sought connection between local structure and global dynamics. Here we directly observe and quantify the connectivity dynamics in liquids of charged colloids en route to vitrification using three-dimensional confocal microscopy. We determine the dynamic structure from the real-space van Hove correlation function and from the particle trajectories, providing upper and lower bounds on connectivity dynamics. Based on these data, we extend Dyre's model for the glass transition to account for particle-level structural dynamics; this results in a microscopic expression for the slowing down of relaxations in the liquid that is in quantitative agreement with our experiments. These results indicate how vitrification may be understood as a dynamical connectivity transition with features that are strongly reminiscent of rigidity percolation scenarios.

Linking Particle Dynamics to Local Connectivity in Colloidal Gels.

Colloidal gels are a prototypical example of a heterogeneous network solid whose complex properties are governed by thermally activated dynamics. In this Letter we experimentally establish the connection between the intermittent dynamics of individual particles and their local connectivity. We interpret our experiments with a model that describes single-particle dynamics based on highly cooperative thermal debonding. The model, in quantitative agreement with experiments, provides a microscopic picture for the structural origin of dynamical heterogeneity in colloidal gels and sheds new light on the link between structure and the complex mechanics of these heterogeneous solids.

Particle Dynamics in Colloid-Polymer Mixtures with Different Polymer Architectures.

Nonadsorbing polymers are widely used as thickening agents for colloids. A quantitative description of the structure and dynamics of such colloid-polymer mixtures is crucial to reveal the mechanisms accounting for the desired mechanical properties. We use confocal microscopy to study colloids with three types of commonly used polymers with different architectures: linear, subgranular cross-linked, and branched microgels. All three thickeners give rise to heterogeneous colloidal dynamics, characterized by non-Gaussian displacement distributions. However, while the ensemble-averaged particle dynamics in these materials are very similar, the underlying individual particle dynamics are not. Linear polymers give rise to depletion attraction and the formation of colloidal gels, in which the majority of particles are immobilized, while a few weakly bound particles have much higher mobility. By contrast, the branched and cross-linked polymers thicken the continuous phase of the colloid, squeezing the particles into dense pockets, where the mobility is reduced and requires more cooperative rearrangements.

Propagation and attenuation of mechanical signals in ultrasoft 2D solids.

The propagation of elastic waves in soft materials plays a crucial role in the spatiotemporal transmission of mechanical signals, e.g., in biological mechanotransduction or in the failure of marginal solids. At high Reynolds numbers Re ≫ 1, inertia dominates and wave propagation is readily observed. However, mechanical cues in soft and biological materials often occur at low Re, where waves are overdamped. Overdamped waves are not only difficult to observe experimentally, also theoretically their description remains incomplete. Here, we present direct measurements of the propagation and attenuation of mechanical signals in colloidal soft solids, induced by an optical trap. We derive an analytical theory for low Re wave propagation and damping, which is in excellent agreement with the experiments. Our results present both a previously unexplored method to characterize damped waves in soft solids and a theoretical framework showing how localized mechanical signals can provoke a remote and delayed response.

Allosteric pathway selection in templated assembly.

Assembling large numbers of molecular building blocks into functional nanostructures is no trivial task. It relies on guiding building blocks through complex energy landscapes shaped by synergistic and antagonistic supramolecular interactions. In nature, the use of molecular templates is a potent strategy to navigate the process to the desired structure with high fidelity. Yet, nature's templating strategy remains to be fully exploited in man-made nanomaterials. Designing effective template-guided self-assembling systems can only be realized through precise insight into how the chemical design of building blocks and the resulting balance of repulsive and attractive forces give rise to pathway selection and suppression of trapped states. We develop a minimal model to unravel the kinetic pathways and pathway selection of the templated assembly of molecular building blocks on a template. We show how allosteric activation of the associative interactions can suppress undesired solution-aggregation pathways and gives rise to a true template-assembly path.

Gel Trapping Enables Optical Spectroscopy of Single Solvated Conjugated Polymers in Equilibrium.

Single-molecule studies have provided a wealth of insight into the photophysics of conjugated polymers in the solid and desolvated state. Desolvating conjugated chains, e.g., by their embedding in inert solid matrices, invariably leads to chain collapse and the formation of intermolecular aggregates, which have a pronounced effect on their properties. By contrast, the luminescent properties of individual semiconducting polymers in their solvated and thermodynamic state remain largely unexplored. In this paper, we demonstrate a versatile gel trapping technique that enables the chemistry-free immobilization and interrogation of individual conjugated macromolecules, which retain a fully equilibrated conformation by contrast to conventional solid-state immobilization methods. We show how the technique can be used to record full luminescence spectra of single chains, to evaluate their time-resolved fluorescence, and to probe their photodynamics. Finally, we explore how the photophysics of different conjugated polymers is strongly affected by desolvation and chain collapse.

Apparent strength versus universality in glasses of soft compressible colloids.

Microgel colloids, solvent swollen hydrogel particles of microscopic size, are in osmotic equilibrium with their surroundings. This has a profound effect on the behaviour of dense solutions of these polymeric colloids, most notably their ability to swell and deswell depending on the osmotic pressure of the system as a whole. Here we develop a minimal simulation model to treat this intrinsic volume regulation in order to explore the effects this has on the properties of dense solutions close to a liquid-solid transition. We demonstrate how the softness dependent volume regulation of particles gives rise to an apparent change in the fragility of the colloidal glass transition, which can be scaled out through the use of an adjusted volume fraction that accounts for changes in particle size. Moreover, we show how the same model can be used to explain the selective deswelling of soft microgels in a crystalline matrix of harder particles leading to robust crystals free of defects. Our results not only highlight the non-trivial effects of osmotic regulation in governing the apparent physics of microgel suspensions, but also provides a platform to efficiently account for particle deswelling in simulations.

Doping colloidal bcc crystals - interstitial solids and meta-stable clusters.

The addition of a small amount of dopant impurities to crystals is a common method to tune the properties of materials. Usually the doping grade is restricted by the low solubility of the dopants; increasing the doping concentration beyond this solubility limit leads to supersaturated solutions in which dopant clusters dominate the material properties, often leading to deterioration of strength and performance. Descriptions of doped solids often assume that thermal excitations of the on average perfect matrix are small. However, especially for bcc crystals close to their melting point it has recently become clear that the effects of thermal disorder are strong. Here we study the doping of weak bcc crystals of charged colloids via Brownian dynamics simulations. We find a complex phase diagram upon varying the dopant concentration. At low dopant concentrations we find an interstitial solid solution. As we increase the amount of dopants a complex meta-stable liquid-in-solid cluster phase emerges. Ultimately this phase becomes meta-stable with respect to macroscopic crystal-crystal coexistence. These results illustrate the complex behaviour that emerges when thermal excitations of the matrix drive impure crystals to a weak state.

High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors.

The study of the photophysical properties of organic-metallic lead halide perovskites, which demonstrate excellent photovoltaic performance in devices with electron- and hole-accepting layers, helps to understand their charge photogeneration and recombination mechanism and unravels their potential for other optoelectronic applications. We report surprisingly high photoluminescence (PL) quantum efficiencies, up to 70%, in these solution-processed crystalline films. We find that photoexcitation in the pristine CH3NH3PbI3-xClx perovskite results in free charge carrier formation within 1 ps and that these free charge carriers undergo bimolecular recombination on time scales of 10s to 100s of ns. To exemplify the high luminescence yield of the CH3NH3PbI3-xClx perovskite, we construct and demonstrate the operation of an optically pumped vertical cavity laser comprising a layer of perovskite between a dielectric mirror and evaporated gold top mirrors. These long carrier lifetimes together with exceptionally high luminescence yield are unprecedented in such simply prepared inorganic semiconductors, and we note that these properties are ideally suited for photovoltaic diode operation.

Bright light-emitting diodes based on organometal halide perovskite.

Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI(3-x)Cl(x) perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9'-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr(-1) m(-2) at a current density of 363 mA cm(-2), with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m(-2) at a current density of 123 mA cm(-2), giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.