The Origin of Thermal Gradient-Induced Voltage in Polyelectrolytes.

Ionic thermoelectric materials can generate large thermal voltages under temperature gradients while also being low-cost and environmentally friendly. Many electrolytes with large Seebeck coefficients are reported in recent years, however, the mechanism of the thermal voltage is remained elusive. In this work, three types of polyelectrolytes are studied with different cations and identified a significant contribution to their thermal voltage originating from a concentration gradient. This conclusion is based on studies of the loss and gain of water upon temperature changes, variations in conductivity with water content and temperature, and the voltages induced by changes in water content. The results are analyzed by the "hopping mode" dynamics of charge transport in electrolytes. The hydration of different cations influences the water concentration gradient, which affects the barrier height and ion-induced potential in the electrodes. This work shows that the hydro-voltage in ionic thermoelectric devices can be one order of magnitude larger than the contribution from thermodiffusion-induced potentials, and becomes the main contributor to energy harvesting when implemented into ionic thermoelectric supercapacitors. Together with the rationalized theoretical discussion, this work clarifies the mechanism of thermal voltages in electrolytes and provides a new path for the development of ionic thermoelectric materials.

Electrochromic Inorganic Nanostructures with High Chromaticity and Superior Brightness.

The possibility of actively controlling structural colors has recently attracted a lot of attention, in particular for new types of reflective displays (electronic paper). However, it has proven challenging to achieve good image quality in such devices, mainly because many subpixels are necessary and the semitransparent counter electrodes lower the total reflectance. Here we present an inorganic electrochromic nanostructure based on tungsten trioxide, gold, and a thin platinum mirror. The platinum reflector provides a wide color range and makes it possible to "reverse" the device design so that electrolyte and counter electrode can be placed behind the nanostructures with respect to the viewer. Importantly, this makes it possible to maintain high reflectance regardless of how the electrochemical cell is constructed. We show that our nanostructures clearly outperform the latest commercial color e-reader in terms of both color range and brightness.

Noniridescent Biomimetic Photonic Microdomes by Inkjet Printing.

Certain bird species have evolved spectacular colors that arise from organized nanostructures of melanin. Its high refractive index (∼1.8) and broadband absorptive properties enable vivid structural colors that are nonsusceptible to photobleaching. Mimicking natural melanin structural coloration could enable several important applications, in particular, for noniridescent systems with colors that are independent of incidence angle. Here, we address this by forming melanin photonic crystal microdomes by inkjet printing. Owing to their curved nature, the microdomes exhibit noniridescent vivid structural coloration, tunable throughout the visible range via the size of the nanoparticles. Large-area arrays (>1 cm2) of high-quality photonic microdomes could be printed on both rigid and flexible substrates. Combined with scalable fabrication and the nontoxicity of melanin, the presented photonic microdomes with noniridescent structural coloration may find use in a variety of applications, including sensing, displays, and anticounterfeit holograms.

In vivo polymerization and manufacturing of wires and supercapacitors in plants.

Electronic plants, e-Plants, are an organic bioelectronic platform that allows electronic interfacing with plants. Recently we have demonstrated plants with augmented electronic functionality. Using the vascular system and organs of a plant, we manufactured organic electronic devices and circuits in vivo, leveraging the internal structure and physiology of the plant as the template, and an integral part of the devices. However, this electronic functionality was only achieved in localized regions, whereas new electronic materials that could be distributed to every part of the plant would provide versatility in device and circuit fabrication and create possibilities for new device concepts. Here we report the synthesis of such a conjugated oligomer that can be distributed and form longer oligomers and polymer in every part of the xylem vascular tissue of a Rosa floribunda cutting, forming long-range conducting wires. The plant's structure acts as a physical template, whereas the plant's biochemical response mechanism acts as the catalyst for polymerization. In addition, the oligomer can cross through the veins and enter the apoplastic space in the leaves. Finally, using the plant's natural architecture we manufacture supercapacitors along the stem. Our results are preludes to autonomous energy systems integrated within plants and distribute interconnected sensor-actuator systems for plant control and optimization.

Active control of plasmonic colors: emerging display technologies.

In recent years there has been a growing interest in the use of plasmonic nanostructures for color generation, a technology that dates back to ancient times. Plasmonic structural colors have several attractive features but once the structures are prepared the colors are normally fixed. Lately, several concepts have emerged for actively tuning the colors, which opens up for many new potential applications, the most obvious being novel color displays. In this review we summarize recent progress in active control of plasmonic colors and evaluate them with respect to performance criteria for color displays. It is suggested that actively controlled plasmonic colors are generally less interesting for emissive displays but could be useful for new types of electrochromic devices relying on ambient light (electronic paper). Furthermore, there are several other potential applications such as images to be revealed on demand and colorimetric sensors.

Thermoplasmonic Semitransparent Nanohole Electrodes.

Nonradiative decay of plasmons in metallic nanostructures offers unique means for light-to-heat conversion at the nanoscale. Typical thermoplasmonic systems utilize discrete particles, while metal nanohole arrays were instead considered suitable as heat sinks to reduce heating effects. By contrast, we show for the first time that under uniform broadband illumination (e.g., the sun) ultrathin plasmonic nanohole arrays can be highly competitive plasmonic heaters and provide significantly higher temperatures than analogous nanodisk arrays. Our plasmonic nanohole arrays also heat significantly more than nonstructured metal films, while simultaneously providing superior light transmission. Besides being efficient light-driven heat sources, these thin perforated gold films can simultaneously be used as electrodes. We used this feature to develop "plasmonic thermistors" for electrical monitoring of plasmon-induced temperature changes. The nanohole arrays provided temperature changes up to 7.5 K by simulated sunlight, which is very high compared to previously reported plasmonic systems under similar conditions (solar illumination and ambient conditions). Both temperatures and heating profiles quantitatively agree with combined optical and thermal simulations. Finally, we demonstrate the use of a thermoplasmonic nanohole electrode to power the first hybrid plasmonic ionic thermoelectric device, resulting in strong solar-induced heat gradients and corresponding thermoelectric voltages.

Switchable Plasmonic Metasurfaces with High Chromaticity Containing Only Abundant Metals.

Plasmonic color generation offers several advantages but is also limited by the cost and availability of noble metals like gold. In this work, we present color-tunable metasurfaces with high chromaticity and reflectivity consisting of an aluminum mirror, a dielectric spacer, and a plasmonic nanohole array in copper. Copper is shown to be an excellent alternative to gold when properly protected from oxidation and makes it possible to generate a wide RGB gamut covering 27% of the standard RGB. By patterning the metasurfaces into microscale pixel triplets, color photos can be well reproduced with high resolution over wafer-sized areas. Further, we demonstrate active modulation of the reflected intensity using an electrochromic conductive polymer deposited on top of the nanostructures by screen printing. This technology opens up for ultrathin and flexible reflective displays in full color, that is, plasmonic electronic paper, compatible with large-scale sustainable production.

Solar Transparent Radiators by Optical Nanoantennas.

Architectural windows are a major cause of thermal discomfort as the inner glazing during cold days can be several degrees colder than the indoor air. Mitigating this, the indoor temperature has to be increased, leading to unavoidable thermal losses. Here we present solar thermal surfaces based on complex nanoplasmonic antennas that can raise the temperature of window glazing by up to 8 K upon solar irradiation while transmitting light with a color rendering index of 98.76. The nanoantennas are directional, can be tuned to absorb in different spectral ranges, and possess a structural integrity that is not substrate-dependent, and thus they open up for application on a broad range of surfaces.

Self-Aligned Plasmonic Nanopores by Optically Controlled Dielectric Breakdown.

We present a novel cost-efficient method for the fabrication of high-quality self-aligned plasmonic nanopores by means of an optically controlled dielectric breakdown. Excitation of a plasmonic bowtie nanoantenna on a dielectric membrane localizes the high-voltage-driven breakdown of the membrane to the hotspot of the enhanced optical field, creating a nanopore that is automatically self-aligned to the plasmonic hotspot of the bowtie. We show that the approach provides precise control over the nanopore size and that these plasmonic nanopores can be used as single molecule DNA sensors with a performance matching that of TEM-drilled nanopores. The principle of optically controlled breakdown can also be used to fabricate nonplasmonic nanopores at a controlled position. Our novel fabrication process guarantees alignment of the nanopore with the optical hotspot of the nanoantenna, thus ensuring that pore-translocating biomolecules interact with the concentrated optical field that can be used for detection and manipulation of analytes.

Photoresistance switching of plasmonic nanopores.

Fast and reversible modulation of ion flow through nanosized apertures is important for many nanofluidic applications, including sensing and separation systems. Here, we present the first demonstration of a reversible plasmon-controlled nanofluidic valve. We show that plasmonic nanopores (solid-state nanopores integrated with metal nanocavities) can be used as a fluidic switch upon optical excitation. We systematically investigate the effects of laser illumination of single plasmonic nanopores and experimentally demonstrate photoresistance switching where fluidic transport and ion flow are switched on or off. This is manifested as a large (∼ 1-2 orders of magnitude) increase in the ionic nanopore resistance and an accompanying current rectification upon illumination at high laser powers (tens of milliwatts). At lower laser powers, the resistance decreases monotonically with increasing power, followed by an abrupt transition to high resistances at a certain threshold power. A similar rapid transition, although at a lower threshold power, is observed when the power is instead swept from high to low power. This hysteretic behavior is found to be dependent on the rate of the power sweep. The photoresistance switching effect is attributed to plasmon-induced formation and growth of nanobubbles that reversibly block the ionic current through the nanopore from one side of the membrane. This explanation is corroborated by finite-element simulations of a nanobubble in the nanopore that show the switching and the rectification.

Temperature dependence of DNA translocations through solid-state nanopores.

In order to gain a better physical understanding of DNA translocations through solid-state nanopores, we study the temperature dependence of λ-DNA translocations through 10 nm diameter silicon nitride nanopores, both experimentally and theoretically. The measured ionic conductance G, the DNA-induced ionic-conductance blockades [Formula: see text] and the event frequency Γ all increase with increasing temperature while the DNA translocation time τ decreases. G and [Formula: see text] are accurately described when bulk and surface conductances of the nanopore are considered and access resistance is incorporated appropriately. Viscous drag on the untranslocated part of the DNA coil is found to dominate the temperature dependence of the translocation times and the event rate is well described by a balance between diffusion and electrophoretic motion. The good fit between modeled and measured properties of DNA translocations through solid-state nanopores in this first comprehensive temperature study, suggest that our model captures the relevant physics of the process.

DNA translocations through solid-state plasmonic nanopores.

Nanopores enable label-free detection and analysis of single biomolecules. Here, we investigate DNA translocations through a novel type of plasmonic nanopore based on a gold bowtie nanoantenna with a solid-state nanopore at the plasmonic hot spot. Plasmonic excitation of the nanopore is found to influence both the sensor signal (nanopore ionic conductance blockade during DNA translocation) and the process that captures DNA into the nanopore, without affecting the duration time of the translocations. Most striking is a strong plasmon-induced enhancement of the rate of DNA translocation events in lithium chloride (LiCl, already 10-fold enhancement at a few mW of laser power). This provides a means to utilize the excellent spatiotemporal resolution of DNA interrogations with nanopores in LiCl buffers, which is known to suffer from low event rates. We propose a mechanism based on plasmon-induced local heating and thermophoresis as explanation of our observations.

Plasmon-enhanced four-wave mixing by nanoholes in thin gold films.

Nonlinear plasmonics opens up for wavelength conversion, reduced interaction/emission volumes, and nonlinear enhancement effects at the nanoscale with many compelling nanophotonic applications foreseen. We investigate nonlinear plasmonic responses of nanoholes in thin gold films by exciting the holes individually with tightly focused laser beams, employing a degenerated pump/probe and Stokes excitation scheme. Excitation of the holes results in efficient generation of both narrowband four-wave mixing (FWM) and broadband multiphoton excited luminescence, blueshifted relative to the excitation beams. Clear enhancements were observed when matching the pump/probe wavelength with the hole plasmon resonance. These observations show that the FWM generation is locally excited by nanoholes and has a resonant behavior primarily governed by the dimensions of the individual holes.

Plasmonic nanopore for electrical profiling of optical intensity landscapes.

We present a novel method for sensitive mapping of optical intensity distributions at subdiffraction-limited resolution. This is achieved with a novel device, a plasmonic nanopore, which combines a plasmonic bowtie nanoantenna with a 10 nm-in-diameter solid-state nanopore. Variations in the local optical intensity modulate the plasmonic heating, which we measure electrically through changes in the ionic conductance of the nanopore. We demonstrate the method by profiling the focal volume of a 10 mW laser beam that is tightly focused by a high-numerical-aperture microscope objective. The results show a complex three-dimensional intensity distribution that closely matches predictions obtained by theoretical calculations of the optical system. In addition to laser profiling, the ionic conductance of a nanopore is also shown to provide quantitative estimates of the temperature in the proximity of single plasmonic nanostructures.

Switchable Broadband Terahertz Absorbers Based on Conducting Polymer-Cellulose Aerogels.

Terahertz (THz) technologies provide opportunities ranging from calibration targets for satellites and telescopes to communication devices and biomedical imaging systems. A main component will be broadband THz absorbers with switchability. However, optically switchable materials in THz are scarce and their modulation is mostly available at narrow bandwidths. Realizing materials with large and broadband modulation in absorption or transmission forms a critical challenge. This study demonstrates that conducting polymer-cellulose aerogels can provide modulation of broadband THz light with large modulation range from ≈ 13% to 91% absolute transmission, while maintaining specular reflection loss < -30 dB. The exceptional THz modulation is associated with the anomalous optical conductivity peak of conducting polymers, which enhances the absorption in its oxidized state. The study also demonstrates the possibility to reduce the surface hydrophilicity by simple chemical modifications, and shows that broadband absorption of the aerogels at optical frequencies enables de-frosting by solar-induced heating. These low-cost, aqueous solution-processable, sustainable, and bio-friendly aerogels may find use in next-generation intelligent THz devices.

Periodic modulations of optical tweezers near solid-state membranes.

Optical tweezers operated near solid-state membranes show unexplained periodic modulations in the optical trap position. An experimental study of the oscillations is presented, as well as optical simulations based on the finite-difference time-domain method, providing insight into the underlying interference phenomenon. This work provides a complete description as well as a solution to the enduring problem of modulations in optical traps near solid-state membranes.

Material-selective surface chemistry for nanoplasmonic sensors: optimizing sensitivity and controlling binding to local hot spots.

Optical sensors utilizing the principle of localized surface plasmon resonance (LSPR) offer the advantage of a simple label-free mode of operation, but the sensitivity is typically limited to a very thin region close to the surface. In bioanalytical sensing applications, this can be a significant drawback, in particular since the surface needs to be coated with a recognition layer in order to ensure specific detection of target molecules. We show that the signal upon protein binding decreases dramatically with increasing thickness of the recognition layer, highlighting the need for thin high quality recognition layers compatible with LSPR sensors. The effect is particularly strong for structures that provide local hot spots with highly confined fields, such as in the gap between pairs of gold disks. While our results show a significant improvement in sensor response for pairs over single gold disks upon binding directly to the gold surface, disk pairs did not provide larger signal upon binding of proteins to a recognition layer (already for around 3 nm thin layers) located on the gold. Local plasmonic hot spots are however shown advantageous in combination with directed binding to the hot spots. This was demonstrated using a structure consisting of three surface materials (gold, titanium dioxide, and silicon dioxide) and a new protocol for material-selective surface chemistry of these three materials, which allows for controlled binding only in the gap between pairs of disks. Such a design increased the signal obtained per bound molecule by a factor of around four compared to binding to single disks.

Tuneable Anisotropic Plasmonics with Shape-Symmetric Conducting Polymer Nanoantennas.

A wide range of nanophotonic applications rely on polarization-dependent plasmonic resonances, which usually requires metallic nanostructures that have anisotropic shape. This work demonstrates polarization-dependent plasmonic resonances instead by breaking symmetry via material permittivity. The study shows that molecular alignment of a conducting polymer can lead to a material with polarization-dependent plasma frequency and corresponding in-plane hyperbolic permittivity region. This result is not expected based only on anisotropic charge mobility but implies that also the effective mass of the charge carriers becomes anisotropic upon polymer alignment. This unique feature is used to demonstrate circularly symmetric nanoantennas that provide different plasmonic resonances parallel and perpendicular to the alignment direction. The nanoantennas are further tuneable via the redox state of the polymer. Importantly, polymer alignment could blueshift the plasma wavelength and resonances by several hundreds of nanometers, forming a novel approach toward reaching the ultimate goal of redox-tunable conducting polymer nanoantennas for visible light.

Video-Rate Switching of High-Reflectivity Hybrid Cavities Spanning All Primary Colors.

Dynamically tunable reflective structural colors are attractive for reflective displays (electronic paper). However, it is challenging to tune a thin layer of structural color across the full red-green-blue (RGB) basis set of colors at video rates and with long-term stability. In this work, this is achieved through a hybrid cavity built from metal-insulator-metal (MIM) "nanocaves" and an electrochromic polymer (PProDOTMe2 ). The reflective colors are modulated by electrochemically doping/dedoping the polymer. Compared with traditional subpixel-based systems, this hybrid structure provides high reflectivity (>40%) due to its "monopixel" nature and switches at video rates. The polymer bistability helps deliver ultralow power consumption (≈2.5 mW cm-2 ) for video display applications and negligible consumption (≈3 µW cm-2 ) for static images, compatible with fully photovoltaic powering. In addition, the color uniformity of the hybrid material is excellent (over cm-2 ) and the scalable fabrication enables large-area production.

Cellulose-Based Radiative Cooling and Solar Heating Powers Ionic Thermoelectrics.

Cellulose opens for sustainable materials suitable for radiative cooling thanks to inherent high thermal emissivity combined with low solar absorptance. When desired, solar absorptance can be introduced by additives such as carbon black. However, such materials still shows high thermal emissivity and therefore performs radiative cooling that counteracts the heating process if exposed to the sky. Here, this is addressed by a cellulose-carbon black composite with low mid-infrared (MIR) emissivity and corresponding suppressed radiative cooling thanks to a transparent IR-reflecting indium tin oxide coating. The resulting solar heater provides opposite optical properties in both the solar and thermal ranges compared to the cooler material in the form of solar-reflecting electrospun cellulose. Owing to these differences, exposing the two materials to the sky generated spontaneous temperature differences, as used to power an ionic thermoelectric device in both daytime and nighttime. The study characterizes these effects in detail using solar and sky simulators and through outdoor measurements. Using the concept to power ionic thermoelectric devices shows thermovoltages of >60 mV and 10 °C temperature differences already at moderate solar irradiance of ≈400 W m-2 .