Prolate spheroidal polystyrene nanoparticles: matrix assisted synthesis, interface properties, and scattering analysis.

Shape-anisotropic colloids are increasingly attracting attention for the fabrication of nano- and mesostructured materials. Polymer-based prolate spheroids are typically accessible through a two-step fabrication procedure comprising the synthesis of monodisperse particles of initially spherical shape and their stretching into elongated, ellipsoidal-like objects. The particle stretching is conducted within a matrix polymer, most commonly polyvinylalcohol, which allows heating beyond the glass transition temperature of the polymer particles, e.g. polystyrene. Here, we investigate various aspects of the synthesis and their consequences for the resulting colloids. Loading the stretching matrix with a high amount of polymer particles results in small particle clusters, which are separated during the mechanical stretching step. At the same time, the matrix polymer physisorbs at the particle surface which can be removed via a rigorous work-up procedure. Overall, this process allows for a precise adjustment of the aspect ratio of the prolate spheroids with a small size distribution and retained electrostatic stabilization. We analyse these particles with a range of microscopic and scattering techniques, including depolarized dynamic light scattering that gives access to the rotational diffusion coefficients.

An Integrated, Exchangeable Three-Electrode Electrochemical Setup for AFM-Based Scanning Electrochemical Microscopy.

Scanning electrochemical microscopy (SECM) is a versatile scanning probe technique that allows monitoring of a plethora of electrochemical reactions on a highly resolved local scale. SECM in combination with atomic force microscopy (AFM) is particularly well suited to acquire electrochemical data correlated to sample topography, elasticity, and adhesion, respectively. The resolution achievable in SECM depends critically on the properties of the probe acting as an electrochemical sensor, i.e., the working electrode, which is scanned over the sample. Hence, the development of SECM probes received much attention in recent years. However, for the operation and performance of SECM, the fluid cell and the three-electrode setup are also of paramount importance. These two aspects received much less attention so far. Here, we present a novel approach to the universal implementation of a three-electrode setup for SECM in practically any fluid cell. The integration of all three electrodes (working, counter, and reference) near the cantilever provides many advantages, such as the usage of conventional AFM fluid cells also for SECM or enables the measurement in liquid drops. Moreover, the other electrodes become easily exchangeable as they are combined with the cantilever substrate. Thereby, the handling is improved significantly. We demonstrated that high-resolution SECM, i.e., resolving features smaller than 250 nm in the electrochemical signal, could be achieved with the new setup and that the electrochemical performance was equivalent to the one obtained with macroscopic electrodes.

Selective broadband absorption by mode splitting for radiative cooling.

A plasmonic-photonic structure based on colloidal lithography was designed for a scalable radiative cooling system and its absorption properties were theoretically investigated. The structure comprises a SiO2 core, which is on top of an Au reflector and partially covered by an indium tin oxide (ITO) shell. This simple and scalable structure possesses a strong selective absorption in the primary atmospheric transparency window (8-13 µm). The strong selective absorption is attributed to a mode splitting of the localized surface plasmon (LSP) of the ITO shell. To understand the mechanisms of the mode splitting, a quantitative analysis was conducted using a coupled-oscillator model and a coupled-dipole method. The analysis revealed that the mode splitting is induced by a strong coupling between the LSP of the ITO shell and a magnetic dipole Mie resonance of the SiO2 core.

The effect of morphology and particle-wall interaction on colloidal near-wall dynamics.

We investigated the near-wall Brownian dynamics of different types of colloidal particles with a typical size in the 100 nm range using evanescent wave dynamic light scattering (EWDLS). In detail we studied dilute suspensions of silica spheres and shells with a smooth surface and silica particles with controlled surface roughness. While the near wall dynamics of the particle with a smooth surface differ only slightly from the theoretical prediction for hard sphere colloids, the rough particles diffuse significantly slower. We analysed the experimental data by comparison with model calculations and suggest that the deviating dynamics of the rough particles are not due to increased hydrodynamic interaction with the wall. Rather, the particle roughness significantly changes their DLVO interaction with the wall, which in turn affects their diffusion.

Tunable Thermoelastic Anisotropy in Hybrid Bragg Stacks with Extreme Polymer Confinement.

Controlling thermomechanical anisotropy is important for emerging heat management applications such as thermal interface and electronic packaging materials. Whereas many studies report on thermal transport in anisotropic nanocomposite materials, a fundamental understanding of the interplay between mechanical and thermal properties is missing, due to the lack of measurements of direction-dependent mechanical properties. In this work, exceptionally coherent and transparent hybrid Bragg stacks made of strictly alternating mica-type nanosheets (synthetic hectorite) and polymer layers (polyvinylpyrrolidone) were fabricated at large scale. Distinct from ordinary nanocomposites, these stacks display long-range periodicity, which is tunable down to angstrom precision. A large thermal transport anisotropy (up to 38) is consequently observed, with the high in-plane thermal conductivity (up to 5.7 W m-1 K-1 ) exhibiting an effective medium behavior. The unique hybrid material combined with advanced characterization techniques allows correlating the full elastic tensors to the direction-dependent thermal conductivities. We, therefore, provide a first analysis on how the direction-dependent Young's and shear moduli influence the flow of heat.

Direct Measurement of the In-Plane Thermal Diffusivity of Semitransparent Thin Films by Lock-In Thermography: An Extension of the Slopes Method.

We present an extension of the well-known slopes method for characterization of the in-plane thermal diffusivity of semitransparent polymer films. We introduce a theoretical model which considers heat losses due to convection and radiation mechanisms, as well as semitransparency of the material to the exciting laser heat source (visible range) and multiple reflections at the film surfaces. Most importantly, a potential semitransparency of the material in the IR detection range is also considered. We prove by numerical simulations and by an asymptotic expansion of the surface temperature that the slopes method is also valid for any semitransparent film in the thermally thin regime. Measurements of the in-plane thermal diffusivity performed on semitransparent polymer films covering a wide range of absorption coefficients (to the exciting wavelength and in the IR detection range of our IR camera) validate our theoretical findings.

Ordered Particle Arrays via a Langmuir Transfer Process: Access to Any Two-Dimensional Bravais Lattice.

We demonstrate how to directly transform a close-packed hexagonal colloidal monolayer into nonclose-packed particle arrays of any two-dimensional symmetry at the air/water interface. This major advancement in the field of nanoparticle self-assembly is based on a simple one-dimensional stretching step in combination with the particle array orientation. Our method goes far beyond existing strategies and allows access to all possible two-dimensional Bravais lattices. A key element of our work is the possibility to macroscopically stretch a particle array in a truly one-dimensional manner, which has not been possible up to now. We achieve this by stretching the nanoparticle array at an air/water interface during the transfer process. The degree of stretching is simply controlled by the wettability of the transfer substrate. To retain the symmetry of the transferred structure, the capillary forces upon drying have to be circumvented. We demonstrate two concepts based on thermal fixation for this. It allows for the first time to fabricate nonclose-packed, nonhexagonal colloidal monolayers on a macroscopic length scale.

Computing the 3D Radial Distribution Function from Particle Positions: An Advanced Analytic Approach.

The radial distribution function, g( r), is ubiquitously used to analyze the internal structure of particulate systems. However, experimentally derived particle coordinates are always confined to a finite sample volume. This poses a particular challenge on computing g( r): Once the radial distance, r, extends beyond the sample boundaries in at least one dimension, substantial deviations from the true g( r) function can occur. State of the art algorithms for g( r) mitigate this issue for instance by using artificial periodic boundary conditions. However, ignoring the finite nature of the sample volume distorts g( r) significantly. Here, we present a simple, analytic algorithm for the computation of g( r) in finite samples. No additional assumptions about the sample are required. The key idea is to use an analytic solution for the intersection volume between a spherical shell and the sample volume. In addition, we discovered a natural upper bound for the radial distance that only depends on sample size and shape. This analytic approach will prove to be invaluable for the quantitative analysis of the increasing amount of experimentally derived tomography data.

Atomic force microscopy with nanoelectrode tips for high resolution electrochemical, nanoadhesion and nanoelectrical imaging.

Multimodal nano-imaging in electrochemical environments is important across many areas of science and technology. Here, scanning electrochemical microscopy (SECM) using an atomic force microscope (AFM) platform with a nanoelectrode probe is reported. In combination with PeakForce tapping AFM mode, the simultaneous characterization of surface topography, quantitative nanomechanics, nanoelectronic properties, and electrochemical activity is demonstrated. The nanoelectrode probe is coated with dielectric materials and has an exposed conical Pt tip apex of ∼200 nm in height and of ∼25 nm in end-tip radius. These characteristic dimensions permit sub-100 nm spatial resolution for electrochemical imaging. With this nanoelectrode probe we have extended AFM-based nanoelectrical measurements to liquid environments. Experimental data and numerical simulations are used to understand the response of the nanoelectrode probe. With PeakForce SECM, we successfully characterized a surface defect on a highly-oriented pyrolytic graphite electrode showing correlated topographical, electrochemical and nanomechanical information at the highest AFM-SECM resolution. The SECM nanoelectrode also enabled the measurement of heterogeneous electrical conductivity of electrode surfaces in liquid. These studies extend the basic understanding of heterogeneity on graphite/graphene surfaces for electrochemical applications.

Interfacial and volumetric sensitivity of the dry sintering process of polymer colloidal crystals: a thermal transport and photonic bandgap study.

We introduce the in situ characterization of the dry sintering process of face-centred cubic colloidal crystals by two complementary techniques: thermal transport and photonic stopband characterization. Therefore, we employed time-dependent, isothermal laser flash analysis and specular reflectivity experiments close to the glass transition temperature of the colloidal crystal. Both methods yield distinctly different time constants of the film formation process. This discrepancy can be attributed to a volume- (photonic stopband) and interface-driven (thermal transport) sensitivity of the respective characterization method. Nevertheless, both methods yield comparable apparent activation energies. Finally, we extended the sintering process characterization to further polymer compositions, with vastly different glass transition temperatures. We could show that the film formation rate is governed by the viscoelastic properties of the polymers at the respective annealing temperature.

Multi-scale structural characterization of ceramic-based photonic glasses for structural colors.

Structural colors arise from selective light interaction with (nano)structures, which give them advantages over pigmented colors such as resistance to fading and possibility to be fabricated out of traditional low-cost and non-toxic materials. Since the color arises from the photonic (nano)structures, different structural features can impact their photonic response and thus, their color. Therefore, the detailed characterization of their structural features is crucial for further improvement of structural colors. In this work, we present a detailed multi-scale structural characterization of ceramic-based photonic glasses by using a combination of high-resolution ptychographic X-ray computed tomography and small angle X-ray scattering. Our results uncover the structure-processing-properties' relationships of such nanoparticles-based photonic glasses and point out to the need of a review of the structural features used in simulation models concomitantly with the need for further investigations by experimentalists, where we point out exactly which structural features need to be improved.

Passive Daytime Cooling Foils for Everyone: A Scalable Lamination Process Based on Upcycling Aluminum-Coated Chips Bags.

The increasing energy demand for space cooling and environmental pollution caused by post-consumer plastic waste are two of the most challenging issues today. Passive daytime cooling, which dissipates heat to outer space without external energy input, has emerged recently as a sustainable technique for space cooling. In this work, a plastic waste-based passive daytime cooling foil is reported to alleviate both issues simultaneously. The mirror-like aluminum-plastic laminate (APL) waste exhibits a satisfactory solar reflectance of 85.7%. Combining the APL waste with a laminated pouch foil reveals a remarkably simple but effective plastic waste-based cooling foil with a high emissivity of 0.87 in the atmospheric window, resulting in a compelling daytime cooling performance. The sustainable aluminum-plastic laminate waste-based cooling foil is flexible, easily scalable, low-cost, and fabricated with a common laminator. This makes the fabrication of passive cooling materials possible even for nonexperts, which will help to provide advanced sun shelters and comfortable temperatures to a wider community.

Electromagnetically Induced Absorption Overcomes the Upper Limit of Light Absorption: Dipole-Dipole Coupling with Phase Retardation in Plasmonic-Dielectric Dimers.

Electromagnetically induced absorption (EIA) by a phase-retarded coupling is theoretically investigated using a dimer composed of a plasmonic and dielectric particle. This phase-retarded coupling originates from the particles interacting with each other through their scattered intermediate fields (in between near and far fields). Our analysis based on the coupled-dipole method and an extended coupled-oscillator model indicates that EIA by the phase-retarded coupling occurs due to constructive interference in the scattered fields of the particles. By employing the finite element method, we demonstrate that the absorption of the plasmonic particle is dramatically enhanced by tuning the interparticle distance and achieving constructive interference. In contrast to EIA by near-field coupling, which has been intensively researched using coupled plasmonic systems, EIA by a phase-retarded coupling enables us to strengthen the absorption of plasmonic systems more significantly. This significant absorption enhancement is expected to be beneficial to advancing various applications, such as energy harvesting and radiative cooling.

Machine Learning Enabled Image Analysis of Time-Temperature Sensing Colloidal Arrays.

Smart, responsive materials are required in various advanced applications ranging from anti-counterfeiting to autonomous sensing. Colloidal crystals are a versatile material class for optically based sensing applications owing to their photonic stopband. A careful combination of materials synthesis and colloidal mesostructure rendered such systems helpful in responding to stimuli such as gases, humidity, or temperature. Here, an approach is demonstrated to simultaneously and independently measure the time and temperature solely based on the inherent material properties of complex colloidal crystal mixtures. An array of colloidal crystals, each featuring unique film formation kinetics, is fabricated. Combined with machine learning-enabled image analysis, the colloidal crystal arrays can autonomously record isothermal heating events - readout proceeds by acquiring photographs of the applied sensor using a standard smartphone camera. The concept shows how the progressing use of machine learning in materials science has the potential to allow non-classical forms of data acquisition and evaluation. This can provide novel insights into multiparameter systems and simplify applications of novel materials.

A Continuous Gradient Colloidal Glass.

Colloidal crystals and glasses manipulate light propagation depending on their chemical composition, particle morphology, and mesoscopic structure. This light-matter interaction has been intensely investigated, but a knowledge gap remains for mesostructures comprising a continuous property gradient of the constituting particles. Here, a general synthetic approach to bottom-up fabrication of continuous size gradient colloidal ensembles is introduced. First, the technique synthesizes a dispersion with a specifically designed gradual particle size distribution. Second, self-assembly of this dispersion yields a photonic colloidal glass with a continuous size gradient from top to bottom. Local and bulk characterization methods are used to highlight the significant potential of this mesostructure, resulting in vivid structural colors along, and in superior light scattering across the gradient. The process describes a general pathway to mesoscopic gradients. It can expectedly be transferred to a variety of other particle-based systems where continuous gradients will provide novel physical insights and functionalities.

From Chitosan to Chitin: Bio-Inspired Thin Films for Passive Daytime Radiative Cooling.

Passive radiative daytime cooling is an emerging technology contributing to carbon-neutral heat management. Optically engineered materials with distinct absorption and emission properties in the solar and mid-infrared range are at the heart of this technology. Owing to their low emissive power of about 100 W m-2 during daytime, substantial areas need to be covered with passive cooling materials or coatings to achieve a sizeable effect on global warming. Consequently, biocompatible materials are urgently needed to develop suitable coatings with no adverse environmental impact. It is shown how chitosan films with different thicknesses can be produced from slightly acidic aqueous solutions. The conversion to their insoluble form chitin in the solid state is demonstrated and the conversion is monitored with infrared (IR) and NMR spectroscopy. In combination with a reflective backing material, the films show below-ambient temperature cooling capabilities with a suitable emissivity in the mid-IR region and low solar absorption of 3.1-6.9%, depending on the film thickness. This work highlights the potential of chitosan and chitin as widely available biocompatible polymers for passive radiative cooling applications.

Extremely low thermal conductivity and high electrical conductivity of sustainable carbon-ceramic electrospun nonwoven materials.

Materials with an extremely low thermal and high electrical conductivity that are easy to process, foldable, and nonflammable are required for sustainable applications, notably in energy converters, miniaturized electronics, and high-temperature fuel cells. Given the inherent correlation between high thermal and high electrical conductivity, innovative design concepts that decouple phonon and electron transport are necessary. We achieved this unique combination of thermal conductivity 19.8 ± 7.8 mW/m/K (cross-plane) and 31.8 ± 11.8 mW/m/K (in-plane); electrical conductivity 4.2 S/cm in-plane in electrospun nonwovens comprising carbon as the matrix and silicon-based ceramics as nano-sized inclusions with a sea-island nanostructure. The carbon phase modulates electronic transport for high electrical conductivity, and the ceramic phase induces phonon scattering for low thermal conductivity by excessive boundary scattering. Our strategy can be used to fabricate the unique nonwoven materials for real-world applications and will inspire the design of materials made from carbon and ceramic.

Collective mechanical behavior of multilayer colloidal arrays of hollow nanoparticles.

The collective mechanical behavior of multilayer colloidal arrays of hollow silica nanoparticles (HSNP) is explored under spherical nanoindentation through a combination of experimental, numerical, and theoretical approaches. The effective indentation modulus E(ind) is found to decrease with an increasing number of layers in a nonlinear manner. The indentation force versus penetration depth behavior for multilayer hollow particle arrays is predicted by an approximate analytical model based on the spring stiffness of the individual particles and the multipoint, multiparticle interactions as well as force transmission between the layers. The model is in good agreement with experiments and with detailed finite element simulations. The ability to tune the effective indentation modulus, E(ind), of the multilayer arrays by manipulating particle geometry and layering is revealed through the model, where E(ind) = (0.725m(-3/2) + 0.275)E(mon) and E(mon) is the monolayer modulus and m is number of layers. E(ind) is seen to plateau with increasing m to E(ind_plateau) = 0.275E(mon) and E(mon) scales with (t/R)(2), t being the particle shell thickness and R being the particle radius. The scaling law governing the nonlinear decrease in indentation modulus with an increase in layer number (E(ind) scaling with m(-3/2)) is found to be similar to that governing the indentation modulus of thin solid films E(ind_solid) on a stiff substrate (where E(ind_solid) scales with h(-1.4) and also decreases until reaching a plateau value) which also decreases with an increase in film thickness h. However, the mechanisms underlying this trend for the colloidal array are clearly different, where discrete particle-to-particle interactions govern the colloidal array behavior in contrast to the substrate constraint on deformation, which governs the thickness dependence of the continuous thin film indentation modulus.

Visible mie scattering in nonabsorbing hollow sphere powders.

Hollow silica nanoparticles (HSNP) with diameters comparable to visible wavelengths and with thin shells (<15 nm) feature an unexpected color effect. Single particle and powder spectroscopy, as well as calculations based on Mie theory were used to investigate this phenomenon. The use of HSNPs increases the transport mean free path of light significantly, which reduces multiple scattering, and thus the Mie resonances become visible to the bare eye.