Structural Coloration with Nonclose‐Packed Array of Bidisperse Colloidal Particles

Colloidal crystals and glasses have their own photonic effects. Colloidal crystals show high reflectivity at narrowband, whereas colloidal glasses show low reflectivity at broadband. To compromise the opposite optical properties, a simple means is suggested to control the colloidal arrangement between crystal and glass by employing two different sizes of silica particles with repulsive interparticle potential. Monodisperse silica particles with repulsive potential spontaneously form crystalline structure at volume fraction far below 0.74. When two different sizes of silica particles coexist, the arrangement of silica particles is significantly influenced by two parameters: size contrast and mixing ratio. When the size contrast is small, a long‐range order is partially conserved in the entire mixing ratio, resulting in a pronounced reflectance peak and brilliant structural color. When the size contrast is large, the long‐range order is rapidly reduced along with mixing ratio. Nevertheless, a short‐range order survives, which causes low reflectivity at a broad wavelength, developing faint structural colors. These findings offer an insight into controlling the colloidal arrangements and provide a simple way to tune the optical property of colloidal arrays for structural coloration.     

Ptychographic X‐Ray Imaging of Colloidal Crystals

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.     

Real‐Time Label‐Free Monitoring of Nanoparticle Cell Uptake

The surface plasmon resonance technique in combination with whole cell sensing is used for the first time for real‐time label‐free monitoring of nanoparticle cell uptake. The uptake kinetics of several types of nanoparticles relevant to drug delivery applications into HeLa cells is determined. The cell uptake of the nanoparticles is confirmed by confocal microscopy. The cell uptake of silica nanoparticles and polyethylenimine–plasmid DNA polyplexes is studied as a function of temperature, and the uptake energies are determined by Arrhenius plots. The phase transition temperature of the HeLa cell membrane is detected when monitoring cell uptake of silica nanoparticles at different temperatures. The HeLa cell uptake of the mesoporous silica nanoparticles is energy‐independent at temperatures slightly higher than the phase transition temperature of the HeLa cell membrane, while the uptake of polyethylenimine–DNA polyplexes is energy‐dependent and linear as a function of temperature with an activation energy of Ea = 62 ± 7 kJ mol^?1 = 15 ± 2 kcal mol^?1. The HeLa cell uptake of red blood cell derived extracellular vesicles is also studied as a function of the extracellular vesicle concentration. The results show a concentration dependent behavior reaching a saturation level of the extracellular vesicle uptake by HeLa cells.     

Bio‐Inspired Bright Structurally Colored Colloidal Amorphous Array Enhanced by Controlling Thickness and Black Background

Inspired by Steller's jay, which displays angle‐independent structural colors, angle‐independent structurally colored materials are created, which are composed of amorphous arrays of submicrometer‐sized fine spherical silica colloidal particles. When the colloidal amorphous arrays are thick, they do not appear colorful but almost white. However, the saturation of the structural color can be increased by (i) appropriately controlling the thickness of the array and (ii) placing the black background substrate. This is similar in the case of the blue feather of Steller's jay. Based on the knowledge gained through the biomimicry of structural colored materials, colloidal amorphous arrays on the surface of a black particle as the core particle are also prepared as colorful photonic pigments. Moreover, a structural color on–off system is successfully built by controlling the background brightness of the colloidal amorphous arrays.     

Large‐Scale Noniridescent Structural Color Printing Enabled by Infiltration‐Driven Nonequilibrium Colloidal Assembly

Structural colors originating from interaction of light with intricately arranged micro‐/nanostructures have stimulated considerable interest because of their inherent photostability and energy efficiency. In particular, noniridescent structural color with wide viewing angle has been receiving increasing attention recently. However, no method is yet available for rapid and large‐scale fabrication of full‐spectrum structural color patterns with wide viewing angles. Here, infiltration‐driven nonequilibrium assembly of colloidal particles on liquid‐permeable and particle‐excluding substrates is demonstrated to direct the particles to form amorphous colloidal arrays (ACAs) within milliseconds. The infiltration‐assisted (IFAST) colloidal assembly opens new possibilities for rapid manufacture of noniridescent structural colors of ACAs and straightforward structural color mixing. Full‐spectrum noniridescent structural colors are successfully produced by mixing primary structural colors of red, blue, and yellow using a commercial office inkjet printer. Rapid fabrication of large‐scale structural color patterns with sophisticated color combination/layout by IFAST printing is realized. The IFAST technology is versatile for developing structural color patterns with wide viewing angles, as colloidal particles, inks, and substrates are flexibly designable for diverse applications.     

Self‐Powered Real‐Time Arterial Pulse Monitoring Using Ultrathin Epidermal Piezoelectric Sensors

Continuous monitoring of an arterial pulse using a pressure sensor attached on the epidermis is an important technology for detecting the early onset of cardiovascular disease and assessing personal health status. Conventional pulse sensors have the capability of detecting human biosignals, but have significant drawbacks of power consumption issues that limit sustainable operation of wearable medical devices. Here, a self‐powered piezoelectric pulse sensor is demonstrated to enable in vivo measurement of radial/carotid pulse signals in near‐surface arteries. The inorganic piezoelectric sensor on an ultrathin plastic achieves conformal contact with the complex texture of the rugged skin, which allows to respond to the tiny pulse changes arising on the surface of epidermis. Experimental studies provide characteristics of the sensor with a sensitivity (≈0.018 kPa^?1), response time (≈60 ms), and good mechanical stability. Wireless transmission of detected arterial pressure signals to a smart phone demonstrates the possibility of self‐powered and real‐time pulse monitoring system.     

Sub‐Micron Polymeric Stomatocytes as Promising Templates for Confined Crystallization and Diffraction Experiments

The possibility of using sub‐micrometer polymeric stomatocytes is investigated to effectuate confined crystallization of inorganic compounds. These bowl‐shaped polymeric compartments facilitate confined crystallization while their glassy surfaces provide their crystalline cargos with convenient shielding from the electron beam's harsh effects during transmission electron microscopy experiments. Stomatocytes host the growth of a single nanocrystal per nanocavity, and the electron diffraction experiments reveal that their glassy membranes do not interfere with the diffraction patterns obtained from their crystalline cargos. Therefore, it is expected that the encapsulation and crystallization within these compartments can be considered as a promising template (nanovials) that hold and protect nanocrystals and protein clusters from the direct radiation damage before data acquisition, while they are examined by modern crystallography methodologies such as serial femtosecond crystallography.     

Interfacial Capillary‐Force‐Driven Self‐Assembly of Monolayer Colloidal Crystals for Supersensitive Plasmonic Sensors

Colloidal lithography technology based on monolayer colloidal crystals (MCCs) is considered as an outstanding candidate for fabricating large‐area patterned functional nanostructures and devices. Although many efforts have been devoted to achieve various novel applicatons, the quality of MCCs, a key factor for the controllability and reproducibility of the patterned nanostructures, is often overlooked. In this work, an interfacial capillary‐force‐driven self‐assembly strategy (ICFDS) is designed to realize a high‐quality and highly‐ordered hexagonal monolayer MCCs array by resorting the capillary effect of the interfacial water film at substrate surface as well as controlling the zeta potential of the polystyrene particles. Compared with the conventional self‐assembly method, this approach can realize the reself‐assembly process on the substrate surface with few colloidal aggregates, vacancy, and crystal boundary defects. Furthermore, various typical large‐scale nanostructure arrays are achieved by combining reactive ion etching, metal‐assisted chemical etching, and so forth. Specifically, benefiting from the as‐fabricated high‐quality 2D hexagonal colloidal crystals, the surface plasmon resonance (SPR) sensors achieve an excellent refractive index sensitivity value of 3497 nm RIU^?1, which is competent for detecting bovine serum albumin with an ultralow concentration of 10^?8 m . This work opens a window to prepare high‐quality MCCs for more potential applications.     

Crystallization Kinetics and Morphology Control of Formamidinium–Cesium Mixed‐Cation Lead Mixed‐Halide Perovskite via Tunability of the Colloidal Precursor Solution

The meteoric rise of the field of perovskite solar cells has been fueled by the ease with which a wide range of high‐quality materials can be fabricated via simple solution processing methods. However, to date, little effort has been devoted to understanding the precursor solutions, and the role of additives such as hydrohalic acids upon film crystallization and final optoelectronic quality. Here, a direct link between the colloids concentration present in the [HC(NH₂)₂]_0.83Cs_0.17Pb(Br_0.2I_0.8)₃ precursor solution and the nucleation and growth stages of the thin film formation is established. Using dynamic light scattering analysis, the dissolution of colloids over a time span triggered by the addition of hydrohalic acids is monitored. These colloids appear to provide nucleation sites for the perovskite crystallization, which critically impacts morphology, crystal quality, and optoelectronic properties. Via 2D X‐ray diffraction, highly ordered and textured crystals for films prepared from solutions with lower colloidal concentrations are observed. This increase in material quality allows for a reduction in microstrain along with a twofold increase in charge‐carrier mobilities leading to values exceeding 20 cm² V^?1 s^?1. Using a solution with an optimized colloidal concentration, devices that reach current–voltage measured power conversion efficiency of 18.8% and stabilized efficiency of 17.9% are fabricated.     

Real‐Time Observation of Order‐Disorder Transformation of Organic Cations Induced Phase Transition and Anomalous Photoluminescence in Hybrid Perovskites

A fundamental understanding of the interplay between the microscopic structure and macroscopic optoelectronic properties of organic‐inorganic hybrid perovskite materials is essential to design new materials and improve device performance. However, how exactly the organic cations affect the structural phase transition and optoelectronic properties of the materials is not well understood. Here, real‐time, in situ temperature‐dependent neutron/X‐ray diffraction and photoluminescence (PL) measurements reveal a transformation of the organic cation CH₃NH₃ ⁺ from order to disorder with increasing temperature in CH₃NH₃PbBr₃ perovskites. The molecular‐level order‐to‐disorder transformation of CH₃NH₃ ⁺ not only leads to an anomalous increase in PL intensity, but also results in a multidomain to single‐domain structural transition. This discovery establishes the important role that organic cation ordering has in dictating structural order and anomalous optoelectronic phenomenon in hybrid perovskites.     

Real‐Time Tracking of Superparamagnetic Nanoparticle Self‐Assembly

The spontaneous self‐assembly process of superparamagnetic nanoparticles in a fast‐drying colloidal drop is observed in real time. The grazing‐incidence small‐angle X‐ray scattering (GISAXS) technique is employed for an in situ tracking of the reciprocal space, with a 3 ms delay time between subsequent frames delivered by a new generation of X‐ray cameras. A focused synchrotron beam and sophisticated sample oscillations make it possible to relate the dynamic reciprocal to direct space features and to localize the self‐assembly. In particular, no nanoparticle ordering is found inside the evaporating drop and near‐surface region down to a drop thickness of 90 µm. Scanning through the shrinking drop‐contact line indicates the start of self‐assembly near the drop three‐phase interface, in accord with theoretical predictions. The results obtained have direct implications for establishing the self‐assembly process as a routine technological step in the preparation of new nanostructures.