Combining UV radiation with vapor phase polymerization (VPP) enables the fabrication of conducting polymer films with tunable electrical, optical, and electrochemical properties. However, traditional mask-based UV exposure typically requires separation between a photomask and the sample, which limits resolution. This study circumvents this by using a maskless UV exposure system that directly projects high-resolution patterns onto the substrate. Using poly(3,4-ethylenedioxythiophene):toluenesulfonate (PEDOT:Tos) as a model material, the resulting minimum feature sizes are approximately 8 mu m-nearly half of what has been achieved using mask-based systems. We find that the obtained resolution is not limited by the optics but is related to material aspects such as molecular diffusion, providing guidelines for further optimizations. Our findings also show that the total delivered dose, rather than exposure time or irradiance, controls the film properties. The resulting PEDOT:Tos patterns exhibit distinct, stable color variations during electrochemical switching, highlighting the potential of maskless UV-VPP for high-resolution electrochromic displays.

Solar heating is important for many applications but less attractive for concepts requiring intermittent heating, such as ionic thermoelectric supercapacitors (ITESCs). However, the heating process even at constant solar illumination can be converted to temperature oscillations through water infiltration and evaporation. Here, this process is demonstrated for a carbon nanotube-cellulose membrane and used to induce temporally varying temperature gradients across an ITESC, which enables continuous operation through repeated charge and discharge cycles. A temperature variation of 10 K can be generated on the top electrode, which leads to a variation in the temperature difference across the ITESC of 7.5 K. Precise control over charge and discharge durations can be achieved by adjusting the volume and interval of the added water. The concept of temporarily adjusting temperatures by evaporative cooling may be extended to create intermittent heating also for other heat sources that are typically constant. A vertical ionic thermoelectric supercapacitor (ITESC) is driven by intermittent temperature gradients as induced by constant solar heating and periodic evaporative cooling. As shown, a solar absorber provides temperature oscillations on the top electrodes through water infiltration and evaporation. This concept enables continuous operation of ITESCs through repeated charge and discharge cycles. image

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. The thermal voltage of polyelectrolyte films largely depends on the water concentration gradient under a temperature difference, which can be optimized to promote the generated total voltage up to over 30 mV K-1.image

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 degrees C temperature differences already at moderate solar irradiance of approximate to 400 W m(-2).

Metals have been the dominant plasmonic materials for decades, but they suffer from limited tunability. By contrast, conducting polymers offer exceptional tunability and were recently introduced as a new category of dynamic plasmonic materials. Their charge carrier density can be drastically modulated via their redox state, offering reversible and gradual transitions between optically metallic and dielectric behavior. Nanoantennas made from conducting polymers can therefore be reversibly turned off and on again. This enables phase gradient metasurfaces with tunable functionalities, holding promise for applications such as video holograms. In this Perspective, we discuss the emergence of dynamic conducting polymer plasmonics as a new research direction, including recent developments, remaining challenges, and opportunities for future research. We hope that this Perspective will encourage more researchers to join the journey and contribute toward a rapid development of this interdisciplinary field.

Electrically tunable metasurfaces and interrelated nanofabrication techniques are essential for metasurface-based optoelectronic applications. We present a nanofabrication method suitable for various types of plasmonic polymer metasurfaces including inverted arrays of nanoantennas. Inverted metasurfaces are of particular interest since the metasurface itself can work as an electrode due to its interconnected nature, which enables electrical control without adopting an additional electrode. In comparison with inverted nanodisk arrays that support relatively weak resonance features, we show that inverted nanorod arrays can possess stronger resonances, even comparable with those of nanorod arrays. The origin of plasmon resonances in inverted arrays is systematically investigated using finite-difference time-domain (FDTD) simulations. Further, we demonstrate electrically tunable electrode-free metasurface devices using polymer inverted nanorod arrays, which can operate in the full spectral range of the material including the mid-infrared region. Electrically tunable and electrode-free metasurfaces using plasmonic polymer inverted nanoantenna arrays can operate across the entire spectral range of the material, including the mid-infrared region.

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. Traditional anisotropic nanoantennas have asymmetric shape. In this work, symmetry is instead broken by straining of a conducting polymer, leading to an in-plane anisotropic plasma frequency. This enables circularly symmetric nanoantennas with polarization-dependent localized surface plasmon resonances. The polarization dependence is consistent with inverse changes of the effective mass and mobility of thecharge carriers along different in-plane directions.image

Nanostructures of conventional metals offer manipulation of light at the nanoscale but are largely limited to static behavior due to fixed material properties. To develop the next frontier of dynamic nano-optics and metasurfaces, this study utilizes the redox-tunable optical properties of conducting polymers, as recently shown to be capable of sustaining plasmons in their most conducting oxidized state. Electrically tunable conducting polymer nano-optical antennas are presented, using nanodisks of poly(3,4-ethylenedioxythiophene:sulfate) (PEDOT:Sulf) as a model system. In addition to repeated on/off switching of the polymeric nanoantennas, the concept enables gradual electrical tuning of the nano-optical response, which was found to be related to the modulation of both density and mobility of the mobile polaronic charge carriers in the polymer. The resonance position of the PEDOT:Sulf nanoantennas can be conveniently controlled by disk size, here reported down to a wavelength of around 1270 nm. The presented concept may be used for electrically tunable metasurfaces, with tunable farfield as well as nearfield. The work thereby opens for applications ranging from tunable flat meta-optics to adaptable smart windows.

Optical nanoantennas provide control of light at the nanoscale, which makes them important for diverse areas ranging from photocatalysis and flat metaoptics to sensors and biomolecular tweezing. They have traditionally been limited to metallic and dielectric nanostructures that sustain plasmonic and Mie resonances, respectively. More recently, nanostructures of organic J-aggregate excitonic materials have been proposed capable of also supporting nanooptical resonances, although their advance has been hampered from difficulty in nanostructuring. Here, the authors present the realization of organic J-aggregate excitonic nanostructures, using nanocylinder arrays as model system. Extinction spectra show that they can sustain both plasmon-like resonances and dielectric resonances, owing to the material providing negative and large positive permittivity regions at the different sides of its exciton resonance. Furthermore, it is found that the material is highly anisotropic, leading to hyperbolic and elliptic permittivity regions. Nearfield analysis using optical simulation reveals that the nanostructures therefore support hyperbolic localized surface exciton resonances and elliptic Mie resonances, neither of which has been previously demonstrated for this type of material. The anisotropic nanostructures form a new type of optical nanoantennas, which combined with the presented fabrication process opens up for applications such as fully organic excitonic metasurfaces.

Plasmonic metasurfaces for color generation are emerging as important components for next generation display devices. Fabricating bright plasmonic colors economically and via easily scalable methods, however, remains difficult. Here, the authors demonstrate an efficient and scalable strategy based on colloidal lithography to fabricate silver-based reflective metal-insulator-nanodisk plasmonic cavities that provide a cyan-magenta-yellow (CMY) color palette with high relative luminance. With the same basic structure, they exploit different mechanisms to efficiently produce a complete subtractive color palette. Finite-difference time-domain simulations reveal that these mechanisms include gap surface plasmon modes for thin insulators and hybridized modes between disk plasmons and Fabry-Perot modes for thicker systems. To produce yellow hues, they take advantage of higher-energy gap surface plasmon modes to allow resonance dips in the blue spectral region for comparably large nanodisks, thereby circumventing difficult fabrication of nanodisks less than 80 nm. It is anticipated that incorporation of these strategies can reduce fabrication constraints, produce bright saturated colors, and expedite large-scale production.