Since the early discovery of the antireflection properties of insect compound eyes, new examples of natural antireflective coatings have been rare. Here, we report the fabrication and optical characterization of a biologically inspired antireflective surface that emulates the intricate surface architectures of leafhopper-produced brochosomes-soccer ball-like microscale granules with nanoscale indentations. Our method utilizes double-layer colloidal crystal templates in conjunction with site-specific electrochemical growth to create these structures, and is compatible with various materials including metals, metal oxides, and conductive polymers. These brochosome coatings (BCs) can be designed to exhibit strong omnidirectional antireflective performance of wavelengths from 250 to 2000 nm, comparable to the state-of-the-art antireflective coatings. Our results provide evidence for the use of brochosomes as a camouflage coating against predators of leafhoppers or their eggs. The discovery of the antireflective function of BCs may find applications in solar energy harvesting, imaging, and sensing devices.
Phase-change materials, such as meta-stable undercooled (supercooled) liquids, have been widely recognized as a suitable route for complex fabrication and engineering. Despite comprehensive studies on the undercooling phenomenon, little progress has been made in the use of undercooled metals, primarily due to low yields and poor stability. This paper reports the use of an extension of droplet emulsion technique (SLICE) to produce undercooled core-shell particles of structure; metal/oxide shell-acetate (‘/' = physisorbed, ’-‘ = chemisorbed), from molten Field’s metal (Bi-In-Sn) and Bi-Sn alloys. These particles exhibit stability against solidification at ambient conditions. Besides synthesis, we report the use of these undercooled metal, liquid core-shell, particles for heat free joining and manufacturing at ambient conditions. Our approach incorporates gentle etching and/or fracturing of outer oxide-acetate layers through mechanical stressing or shearing, thus initiating a cascade entailing fluid flow with concomitant deformation, combination/alloying, shaping, and solidification. This simple and low cost technique for soldering and fabrication enables formation of complex shapes and joining at the meso- and micro-scale at ambient conditions without heat or electricity.
Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). While most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous mixed-metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to hematite, while those of a-Fe100-y-zCoyNizOx are comparable to noble metal oxide catalysts currently used in commercial electrolyzers.
Determining the structures of nanoparticles at atomic resolution is vital to understand their structure-property correlations. Large metal nanoparticles with core diameter beyond 2 nm have, to date, eluded characterization by single-crystal X-ray analysis. Here we report the chemical syntheses and structures of two giant thiolated Ag nanoparticles containing 136 and 374 Ag atoms (that is, up to 3 nm core diameter). As the largest thiolated metal nanoparticles crystallographically determined so far, these Ag nanoparticles enter the truly metallic regime with the emergence of surface plasmon resonance. As miniatures of fivefold twinned nanostructures, these structures demonstrate a subtle distortion within fivefold twinned nanostructures of face-centred cubic metals. The Ag nanoparticles reported in this work serve as excellent models to understand the detailed structure distortion within twinned metal nanostructures and also how silver nanoparticles can span from the molecular to the metallic regime.
Understanding the links between chemical composition, nano-structure and the dynamic properties of silicate melts and glasses is fundamental to both Earth and Materials Sciences. Central to this is whether the distribution of mobile metallic ions is random or not. In silicate systems, such as window glass, it is well-established that the short-range structure is not random but metal ions cluster, forming percolation channels through a partly broken network of corner-sharing SiO4 tetrahedra. In alumino-silicate glasses and melts, extensively used in industry and representing most of the Earth magmas, metal ions compensate the electrical charge deficit of AlO4- tetrahedra, but until now clustering has not been confirmed. Here we report how major changes in melt viscosity, together with glass Raman and Nuclear Magnetic Resonance measurements and Molecular Dynamics simulations, demonstrate that metal ions nano-segregate into percolation channels, making this a universal phenomenon of oxide glasses and melts. Furthermore, we can explain how, in both single and mixed alkali compositions, metal ion clustering and percolation radically affect melt mobility, central to understanding industrial and geological processes.
Conductive metal films are patterned into transparent metal nanowire networks by using electrospun fibers as a mask. Both the transmittance and sheet resistance (6 Ω/□ at 83% transmittance and 24 Ω/□ at 92% transmittance) of the metal nanowires based electrode out-perform commercial indium doped tin oxide (ITO) electrodes. The metal nanowire based transparent electrodes were fabricated on both rigid glass and flexible polyethylene terephthalate (PET) substrates. In addition to state of art performance, the transparent electrodes also exhibit outstanding toughness. They can withstand repeated scotch tape peeling and various bending tests. The method for making the metal nanowire is scalable and a touch screen on flexible substrate is demonstrated.
Lithium-ion conducting solid electrolytes hold the promise for enabling high-energy battery chemistries and circumventing safety issues of conventional lithium batteries. Achieving the combination of high ionic conductivity and broad electrochemical window in solid electrolytes is a grand challenge for the synthesis of battery materials. Herein we show an enhancement of room-temperature lithium-ion conductivity of 3 orders of magnitude by creating nanostructured Li3PS4. This material has a wide (5 V) electrochemical window and superior chemical stability against lithium metal. The nanoporous structure of Li3PS4 reconciles two vital effects that enhance ionic conductivity: (1) The reduced dimension to nanometer-sized framework stabilizes the high conduction beta phase that occurs at elevated temperatures; and (2) The high surface-to-bulk ratio of nanoporous β-Li3PS4 promotes surface conduction. Manipulating the ionic conductivity of solid electrolytes has far-reaching implications for materials design and synthesis in a broad range of applications such as batteries, fuel-cells, sensors, photovoltaic systems, and so forth.
We propose a hypothesis that a very thin layer can be made more transparent by adding a thin coating with susceptibility of opposing sign. Two experimental tests backed by a theoretical model support this hypothesis. First, we show that the visible and near-infrared transmission through a semi-transparent silver film can be enhanced by up to ~70% and spectrally tailored depending on the type and thickness of the dielectric coating. Material types explored as dielectric coating layers include conventional metal oxides (titanium dioxide) and lesser-explored elemental semiconductors (undoped silicon, p-type silicon, and germanium). Second, and more surprisingly, we show that coating a 50-nm-thick silicon nitride membrane with a 10-nm-thick silver layer can modestly enhance the transmission by up to 6 ± 1% in the blue part of the spectrum. Transmission enhancements are observed for three silver-coated membranes in different configurations. Thinner silver coatings are theoretically capable of enhancement factors greater than 10%, but implementation is restricted by challenges in making smooth and continuous silver films below 10 nm in thickness. This study is important because it is the first demonstration of reciprocity with respect to the transmission enhancements achieved by combining thin metallic and dielectric layers.
The microscopic kinetics of ubiquitous solid-solid phase transitions remain poorly understood. Here, by using single-particle-resolution video microscopy of colloidal films of diameter-tunable microspheres, we show that transitions between square and triangular lattices occur via a two-step diffusive nucleation pathway involving liquid nuclei. The nucleation pathway is favoured over the direct one-step nucleation because the energy of the solid/liquid interface is lower than that between solid phases. We also observed that nucleation precursors are particle-swapping loops rather than newly generated structural defects, and that coherent and incoherent facets of the evolving nuclei exhibit different energies and growth rates that can markedly alter the nucleation kinetics. Our findings suggest that an intermediate liquid should exist in the nucleation processes of solid-solid transitions of most metals and alloys, and provide guidance for better control of the kinetics of the transition and for future refinements of solid-solid transition theory.
Globally, billions of individuals wash their hair in water, which acts as an exogenous metal source. Many studies which measure the metal levels found on human hair specifically aim to remove exogenous materials prior to analysis. While this is needed when using hair analysis to probe the impact of the local environment on endogenous metal levels, it’s not relevant for understanding exactly what is on hair as a result of contact with its daily environment. Understanding these levels are important, as the presence of redox active metals, such as copper and iron, can impact fibre health, either due to UV irradiation, or during the hair colouring process. A global hair sampling study of over 300 individuals from nine countries has been performed, and the combined endogenous and exogenous metals analysed. The levels measured vary widely, even within the narrow geography of each hair sampling location. The levels of calcium, magnesium, copper and iron were not correlated, and within each location there are expected to be individuals with high metal levels. Levels increased from hair root to tip for calcium, magnesium and copper, attributed to hair’s contact with the environment showing the impact of exogenous metals in the overall levels on hair. Levels of redox metals were comparable between individuals who coloured or did not colour their hair, although water hardness ions were statistically significantly higher for hair colouring individuals. Individuals who perceived their hair health as poor had higher metal levels on their hair. Controlling metals on hair, either by preventing their binding during environmental contact, or through controlling their ability to cause hair damage, should lead to improved consumer perceived hair health. © 2013 Society of Cosmetic Scientists and the Société Française de Cosmétologie.