Synthesis of Linear Black Gold Nanostructures Processable as Sunlight and Low-Energy Light Collecting Films for Photo-Thermoelectricity.

As one of the effort to cope with the energy crisis and carbon neutrality, utilization of low-grade energy generated indoors (e.g., light) is imperative because this saves building and house energy, which accounts for ≈40% of total energy consumption. Although photovoltaic devices could contribute to energy savings, it is also necessary to harvest heat from indoor lights to generate electricity because the light absorbed by materials is mostly transformed into heat. For daily life uses, materials should not only have high absorptance and low emittance but also be easily processed into various forms. To this end, this work synthesizes black aqueous suspensions containing winding and bent linear gold nanostructures with diameters of 3-5 nm and length-to-diameter ratios of ≈4-10. Their optical and photo-thermal characteristics are understood through experimental and theoretical investigations. Black gold nanostructures are conveniently processed into metal-dielectric films on metal, glass, and flexible substrates. The film on copper has an absorptance of 0.97 and an emittance of 0.08. Under simulated sunlight and indoor LED light illumination, the film has equivalent photo-thermal and photo-thermoelectric performances to a top-tier sunlight-collecting film. This work attempts to modify the film structure to generate more usable electricity from low-energy indoor light.

Reaction-Based Scalable Inorganic Patterning on Rigid and Soft Substrates for Photovoltaic Roofs with Minimal Optical Loss and Sustainable Sunlight-Driven-Cleaning Windows.

Recently developed fabrication methods for inorganic patterns (such as laser printing and optical lithography) can avoid some patterning processes conducted by conventional etching and lithography (such as substrate etching and modulation) and are thereby useful for applications in which the substrates and materials must not be damaged during patterning. Simultaneously, it is also necessary to develop facile and economical methods producing inorganic patterns on various substrates without requiring a special apparatus while attaining the above-mentioned advantages. The present study proposes a reaction-based method for fabricating inorganic patterns by immersing substrates coated with a colloidal nanosheet into an aqueous solution containing inorganic precursors. Silica and TiO2 patterns spontaneously developed during the conversion of each inorganic precursor. These patterns were successful on rigid and flexible substrates. We fabricated these patterns on a wafer-sized silicon and large flexible poly(ethylene terephthalate) film, suggesting the scalability. We fabricated a biomimetic pattern on both sides of a glass window, as a photovoltaic roof, for minimal optical losses to maximally present photovoltaic effects of a solar cell. The TiO2 pattern on glass window exhibits sustainable sunlight-driven-cleaning activity for contaminants. The method could provide a platform for economical high-performance inorganic patterns for energy, environmental, electronics, and other areas.

Optically Left-Handed Nanopearl Beads with Inductance-Capacitance Circuits at Visible-Near-Infrared Frequencies Based on Scalable Methods.

Optically left-handed materials refract the propagating light in the opposite direction. Most research has focused on the design of various structures, including split-ring resonators, either on planes or in particle cluster forms to resonate with specific light frequencies. However, for particle-based materials, the circuital structures for optical left-handedness have not been fully understood and the effect of interior structure on the optical handedness have not been investigated. Additionally, scalable methods to deploy the unique characteristics of the materials have not been reported so far and are still urgent. Here, optically left-handed nanopearl beads are synthesized in up to 1.25 L solutions. Nanopearl beads contain assembled Au nanocolloids, a dielectric sphere, and a thin silica layer that fixes the assembled structures to sustainably yield unique inductance-capacitance circuits at specific visible-near-infrared frequencies. The frequencies are tunable by modulating the interior structures. Investigation of the circuit structures and Poynting vectors generated within the nanopearl beads suggest the likelihood of their left-handedness. Moreover, the effects of interior structures on the optical handedness of the nanopearl beads are extensively investigated. The results could help commercialize optically left-handed materials and pioneer fields that have not been realized so far.

Hydrochromic Smart Windows to Remove Harmful Substances by Mimicking Medieval European Stained Glasses.

Medieval European stained glass windows are known to display various splendid colors and remove harmful airborne substances. At present, the functions of medieval stained glass windows are imperative, from the environment, health, and energy perspectives, to develop multi-functional windows that report/control environmental conditions and remove harmful substances by utilizing visible-near-infrared light sources. Here, we suggest a strategy to mimic medieval European stained glasses for devising plasmonic-based multi-functional smart stained glass windows. The stained glass windows are prepared from the deposition of gold nanoparticles on a glass that is preliminarily coated with a responsive colloidal nanosheet. The temperature responsiveness of the nanosheet enables the effective control the gold nanoparticle density of the stained glasses. Therefore, the windows can display blue, violet, and cranberry colors. The colors become iridescent by introducing a photonic crystal monolayer. The stained glass windows are hydrochromic: they switch the colors (blue ↔ cranberry) and modulate light transmittance depending on humidity conditions. Moreover, they can remove formaldehyde under the illumination of a low-power indoor light. These functions provide a new platform for the futuristic smart windows that clean indoor air for the human health and save energy.

Flow Behaviors of Polymer Colloids and Curing Resins Affect Pore Diameters and Heights of Periodic Porous Polymer Films to Direct Their Surface and Optical Characteristics.

Manipulation of both pore diameters and heights of two-dimensional periodic porous polymer films is important to extensively control their characteristics. However, except for using different sized colloid templates in replication methods, an effective method that tunes these factors has rarely been reported. We found that both parameters are controllable by adjusting the flow behaviors of polystyrene colloids and curing resin precursors during the preparation of phenolic resin and poly(dimethylsiloxane) periodic porous films by embedding their precursors into colloidal crystal monolayers. We adjust the flow behaviors by either varying film preparation temperatures (≥glass transition temperature of polystyrene) or using the precursors mixed with different amounts of solvents that renders the colloids viscous. Consequently, the pore diameters and film heights change by 36-56 and 56-84%, respectively. Such modulation results in the change in height to diameter ratios and the areal fractions of resins at air-film interfaces, thereby significantly changing the water contact angles on these surfaces and their photonic characteristics. This straightforward method does not require additional steps, differently sized colloids, or different amounts of precursors for these parameter controls.

Solution-Processed Plasmonic-Dielectric Sunlight-Collecting Nanofilms for Solar Thermoelectric Application.

It is important but remains a challenge to develop solution-processed plasmonic solar thermoelectricity films on various substrates, without strictly considering hierarchical plasmonic-dielectric-metal structures, to harvest a wide range of visible to near-infrared sunlight. We simply fabricate plasmonic silica metastructure sunlight-collecting nanofilms on highly reflective Cu and Si surfaces by introducing spin coating (with an Ag and silica colloidal mixture, a spin coater, and a heating plate) and low-temperature annealing (in an oven at 200 °C for 1 h) processes. The approximately 250 nm thick metastructure consists of a top 60 nm thick silica layer as an antireflective film and a bottom 190 nm thick Ag nanoparticle-silica hybrid film as a sunlight harvester. The metastructure film reduces the reflectivity of Cu (>90%) and Si (25-35%) to less than 5% at visible to near-infrared frequencies. The metastructure film on the Cu sheet has an absorptance of 0.95 and a thermal emittance of 0.06, ideal for high-performance sunlight absorbers. The solar thermoelectric powers of the film-coated Cu and Si are 15.4 and 4.7 times those of the uncoated Cu and Si substrates, respectively. The metastructure film on Cu exhibited a similar or slightly higher performance than that of a top-class vapor-deposited commercialized absorber film on Cu, demonstrating the robustness of the present method.