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.

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.

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.

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.

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.

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.

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.

Microstructural and Thermal Transport Properties of Regioregular Poly(3-hexylthiophene-2,5-diyl) Thin Films.

Polymeric thin films offer a wide range of exciting properties and applications, with several advantages compared to inorganic counterparts. The thermal conductivity of such thin films ranges typically between 0.1-1 W m-1 K-1. This low thermal conductivity can cause problems with heat dissipation in various applications. Detailed knowledge about thermal transport in polymeric thin films is desired to overcome these shortcomings, especially in light of the multitude of possible microstructures for semi-crystalline thin films. Therefore, poly(3-hexylthiophene-2,5-diyl) (P3HT) is chosen as a model system to analyze the microstructure and optoelectronic properties using X-ray scattering and absorption spectra along with the thermal transport properties using the photoacoustic technique. This combination of analysis methods allows for determining the optoelectronic and thermal transport properties on the same specimen, supplemented by structural information. The effect of different molecular weights and solvents during film preparation is systematically examined. A variation of the optoelectronic properties, mainly regarding molecular weight, is apparent, while no direct influence of the solvent during preparation is discernible. In contrast, the thermal conductivities of all films examined fall within a similar range. Therefore, the microstructural properties in the ordered regions do not significantly affect the resulting thermal properties in the sample space investigated in this work. We conclude that it is mainly the amorphous regions that determine the thermal transport properties, as these represent a bottleneck for thermal transport.

A tailored indoor setup for reproducible passive daytime cooling characterization.

Passive daytime cooling materials can lower global energy consumption owing to their autonomous cooling capability. Although a significant number of passive cooling materials have been developed recently, their performance characterization is still challenging. Field tests experience high variability due to uncontrollable changes in environmental conditions. Here, we design an indoor setup to characterize the performance of passive cooling materials reproducibly and independently of weather and season. Outdoor measurement conditions are approximated using a liquid-nitrogen-cooled aluminum dome, a solar simulator, and a wavelength-selective inverse sky-window filter. In contrast to outdoor measurements, the results of various reference materials show remarkable precision and repeatability. Additionally, the impact of solar light intensity and temperature on the passive cooling performance can be experimentally investigated. Our setup is a first step in the development of a standardized test method to bring accuracy, reproducibility, and comparability to the emerging field of passive cooling materials.

Reflection Mechanism of Dielectric Corner Reflectors: The Role of the Diffraction of Evanescent Waves and the Goos-Hänchen Shift.

Nano- and microstructures have been developed for asymmetric light transmission (ALT) filters operating in a wide wavelength range. One of the most straightforward structures with ALT properties is a dielectric corner reflector (DCR) comprising a one-dimensional grating of a triangular shape on one surface. The DCR possesses strong reflection only for one-way light illumination due to multiple total internal reflections (TIRs) inside the triangular grating. For triangular structures being much larger than the wavelength of light, the reflection properties are expected to be fully described by geometrical optics. However, geometrical optics do not account for the Goos-Hänchen (GH) shift, which is caused by the evanescent wave of the TIR. In this work, the reflection mechanism of DCRs is elucidated using the finite element method and a quantitative model built by considering the GH shift. The reduction in reflection of the DCR is dominated by diffraction of the evanescent wave at the corner of the triangular structure. Our model is based on simple mathematics and can optimize the DCR geometry for applications addressing a wide wavelength range such as radiative cooling.

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.

Ultralight Heat-Insulating, Electrically Conductive Carbon Fibrous Sponges for Wearable Mechanosensing Devices with Advanced Warming Function.

Ultralight highly porous sponges are attractive for electronic devices due to superelasticity, outstanding resilience, and thermal insulation. However, fabricating an ultralight conductive sponge with low thermal conductivity, mechanical flexibility, and piezoresistivity, as well as adjustable heating behavior, is still a challenge. Here, an ultralight carbon nanofibrous sponge fabricated by pyrolyzing a graphene oxide coated polyimide sponge is reported. The resulting carbon sponge demonstrates a high electrical conductivity of 0.03-4.72 S m-1 and a low thermal conductivity of 0.027-0.038 W m-1 K-1 (20 °C, in ambient air), as well as a low density to ∼6 mg cm-3. Additionally, the sponge exhibits mechanical flexibility, stability, excellent piezoresistivity, and an adjustable heating behavior. Hence, it could be utilized as a sensing device, including thermal management, making them promising for use in smart sportswear, human-machine interfaces, and wearable healthcare devices.

Nanoscale-Structured Hybrid Bragg Stacks with Orientation- and Composition-Dependent Mechanical and Thermal Transport Properties: Implications for Nacre Mimetics and Heat Management Applications.

Layered nanomaterials fascinate researchers for their mechanical, barrier, optical, and transport properties. Nacre is a biological example thereof, combining excellent mechanical properties by aligned submicron inorganic platelets and nanoscale proteinic interlayers. Mimicking nacre with advanced nanosheets requires ultraconfined organic layers aimed at nacre-like high reinforcement fractions. We describe inorganic/polymer hybrid Bragg stacks with one or two fluorohectorite clay layers alternating with one or two poly(ethylene glycol) layers. As indicated by X-ray diffraction, perfect one-dimensional crystallinity allows for homogeneous single-phase materials with up to a 84% clay volume fraction. Brillouin light spectroscopy allows the exploration of ultimate mechanical moduli without disturbance by flaws, suggesting an unprecedentedly high Young's modulus of 162 GPa along the aligned clays, indicating almost ideal reinforcement under these conditions. Importantly, low heat conductivity is observed across films, κ⊥ = 0.11-0.15 W m-1 K-1, with a high anisotropy of κ∥/κ⊥ = 28-33. The macroscopic mechanical properties show ductile-to-brittle change with an increase in the clay volume fraction from 54% to 70%. Conceptually, this work reveals the ultimate elastic and thermal properties of aligned layered clay nanocomposites in flaw-tolerant conditions.

Ultrafast imaging of terahertz electric waveforms using quantum dots.

Microscopic electric fields govern the majority of elementary excitations in condensed matter and drive electronics at frequencies approaching the Terahertz (THz) regime. However, only few imaging schemes are able to resolve sub-wavelength fields in the THz range, such as scanning-probe techniques, electro-optic sampling, and ultrafast electron microscopy. Still, intrinsic constraints on sample geometry, acquisition speed and field strength limit their applicability. Here, we harness the quantum-confined Stark-effect to encode ultrafast electric near-fields into colloidal quantum dot luminescence. Our approach, termed Quantum-probe Field Microscopy (QFIM), combines far-field imaging of visible photons with phase-resolved sampling of electric waveforms. By capturing ultrafast movies, we spatio-temporally resolve a Terahertz resonance inside a bowtie antenna and unveil the propagation of a Terahertz waveguide excitation deeply in the sub-wavelength regime. The demonstrated QFIM approach is compatible with strong-field excitation and sub-micrometer resolution-introducing a direct route towards ultrafast field imaging of complex nanodevices in-operando.

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.

Time-Temperature Integrating Optical Sensors Based on Gradient Colloidal Crystals.

Manipulation-free and autonomous recording of temperature states for extended periods of time is of increasing importance for food spoilage and battery safety assessment. An optical readout is preferred for low-tech visual inspection. Here, a concept for time-temperature integrators based on colloidal crystals is introduced. Two unique features in this class of advanced materials are combined: 1) the film-formation kinetics can be controlled by orders of magnitude based on mixtures of particles with distinct glass transition temperatures. 2) A gradual variation of the particle mixture along a linear gradient of the colloidal crystal enables local readout. Tailor-made latex particles of identical size but different glass transition temperatures provide a homogenous photonic stopband. The disappearance of this opalescence is directly related to the local particle ratio and the exposure to a time and temperature combination. This sensing material can be adjusted to report extended intermediate and short excessive temperature events, which makes it specifically suitable for long-term tracing and threshold applications.

Design of Multimodal Absorption in the Mid-IR: A Metal Dielectric Metal Approach.

Specific control on the mid-infrared (mid-IR) emission properties is attracting increasing attention for thermal camouflage and passive cooling applications. Metal-dielectric-metal (MDM) structures are well known to support strong magnetic polariton resonances in the optical and near-infrared range. We extend the current understanding of such an MDM structure by specifically designing Au disc arrays on top of ZnS-Au-Si substrates and pushing their resonances to the mid-IR regime. Therefore, we combine fabrication via lift-off photolithography with the finite element method and an inductance-capacitance model. With this combination of techniques, we demonstrate that the magnetic polariton resonance of the first order strongly depends on the individual disc diameter. Furthermore, the fabrication of multiple discs within one unit cell allows a linear combination of the fundamental resonances to conceive broadband absorptance. Quite importantly, even in mixed resonator cases, the absorptance spectra can be fully described by a superposition of the individual disc properties. Our contribution provides rational guidance to deterministically design mid-IR emitting materials with specific narrow- or broadband properties.

Multiplexed lock-in thermography.

Many modern measurement methods for heat transfer work in the frequency domain. A certain average temperature rise in the sample is unavoidable if the sample can only be heated, e.g., by an intensity modulated light source. This average temperature rise influences the measured thermal properties because they are, in general, temperature dependent. Here, we explore square waves and multiplexed sine waves with the goal of reducing the average temperature rise. We apply these signals to lock-in thermography and show the feasibility of a simultaneous measurement at multiple frequencies. In addition, we propose the use of the Goertzel algorithm to efficiently extract individual spectral components from the temperature signal.

Anisotropic Thermal Transport in Spray-Coated Single-Phase Two-Dimensional Materials: Synthetic Clay Versus Graphene Oxide.

Directional control on material properties such as mechanical moduli or thermal conductivity are of paramount importance for the development of nanostructured next-generation devices. Two-dimensional materials are particularly interesting in this context owing to their inherent structural anisotropy. Here, we compare graphene oxide (GO) and synthetic clay sodium fluorohectorite (Hec) with respect to their thermal transport properties. The unique sheet structure of both allows preparation of highly ordered Bragg stacks of these pure materials. The thermal conductivity parallel to the platelets strongly exceeds that perpendicular to them. We find a significant difference in the performance between GO and synthetic clay. Our analysis of the textured structure, size of the platelets, and chemical composition shows that Hec is a superior two-dimensional component to GO. Consequently, synthetic clay is a promising material for thermal management applications in electronic devices where electrically insulating materials are prerequisites.