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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.

Heat sensors form an important class of devices that are used across multiple fields and sectors. For applications such as electronic skin and health monitoring, it is particularly advantageous if the output electronic signals are not only high, stable, and reproducible, but also self-generated to minimize power consumption. Here, we present an ultrasensitive heat sensing concept that fulfills these criteria while also being compatible with scalable low-cost manufacturing on flexible substrates. The concept resembles a traditional thermocouple, but with separated electrodes bridged by a gel-like electrolyte and with orders of magnitudes higher signals (around 11mVK(-1)). The sensor pixels provide stable and reproducible signals upon heating, which, for example, could be used for heat mapping. Further modification to plasmonic nanohole metasurface electrodes made the sensors capable of also detecting light-induced heating. Finally, we present devices on flexible substrates and show that they can be used to detect human touch. Funding Agencies|Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research; Swedish Research CouncilSwedish Research CouncilEuropean Commission; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Vinnova Digital Cellulose Competence Center (DCC)Vinnova [2016-05193]; Linkoping University; Treesearch.se.; Essity

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms a promising alternative to conventional inorganic conductors, where deposition of thin films via vapour phase polymerization (VPP) has gained particular interest owing to high electrical conductivity within the plane of the film. The conductivity perpendicular to the film is typically much lower, which may be related not only to preferential alignment of PEDOT crystallites but also to vertical stratification across the film. In this study, we reveal non-linear vertical microstructural variations across VPP PEDOT:Tos thin films, as well as significant differences in doping level between the top and bottom surfaces. The results are consistent with a VPP mechanism based on diffusion-limited transport of polymerization precursors. Conducting polymer films with vertical inhomogeneity may find applications in gradient-index optics, functionally graded thermoelectrics, and optoelectronic devices requiring gradient doping. The fulltext is published under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.https://creativecommons.org/licenses/by-nc/3.0/

Electrically conducting polymers (ECPs) are becoming increasingly important in areas such as optoelectronics, biomedical devices, and energy systems. Still, their detailed charge transport properties produce an anomalous optical conductivity dispersion that is not yet fully understood in terms of physical model equations for the broad range optical response. Several modifications to the classical Drude model have been proposed to account for a strong non-Drude behavior from terahertz (THz) to infrared (IR) ranges, typically by implementing negative amplitude oscillator functions to the model dielectric function that effectively reduce the conductivity in those ranges. Here we present an alternative description that modifies the Drude model via addition of positive-amplitude Lorentz oscillator functions. We evaluate this so-called Drude-Lorentz (DL) model based on the first ultra-wide spectral range ellipsometry study of ECPs, spanning over four orders of magnitude: from 0.41 meV in the THz range to 5.90 eV in the ultraviolet range, using thin films of poly(3,4-ethylenedioxythiophene): tosylate (PEDOT: Tos) as a model system. The model could accurately fit the experimental data in the whole ultrawide spectral range and provide the complex anisotropic optical conductivity of the material. Examining the resonance frequencies and widths of the Lorentz oscillators reveals that both spectrally narrow vibrational resonances and broader resonances due to localization processes contribute significantly to the deviation from the Drude optical conductivity dispersion. As verified by independent electrical measurements, the DL model accurately determines the electrical properties of the thin film, including DC conductivity, charge density, and (anisotropic) mobility. The ellipsometric method combined with the DL model may thereby become an effective and reliable tool in determining both optical and electrical properties of ECPs, indicating its future potential as a contact-free alternative to traditional electrical characterization. Funding Agencies|Swedish Research Council; Swedish Foundation for Strategic Research; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

Strong light-matter coupling can form hybrid states at new energy levels that share properties of both light and matter. This principle offers new routes to control material functions without modifying the chemical structure of molecules. In this work, we coupled ambipolar semiconducting thin films to a Fabry-Perot cavity and investigated effects on charge transport. By constructing thin-film transistors inside optical cavities, we could simultaneously study coupling features and charge transport in the same samples. The cavity resonance was detuned by controlling the thickness of the top spacer layer in the cavity. We found no significant influence on charge transport for our systems, which may be related to insufficiently strong coupling. Possible additional origins and future directions are also discussed. Funding Agencies|Wenner-Gren Foundations; Swedish Research CouncilSwedish Research CouncilEuropean Commission [621-2014-5599]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research; AForsk foundation; National Research Foundation of Korea (NRF)National Research Foundation of Korea; Korea government (MSIT)Korean Government [2020R1A2C1102558]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Certain bird species have evolved spectacular colors that arise from organized nanostructures of melanin. Its high refractive index (similar to 1.8) and broadband absorptive properties enable vivid structural colors that are nonsusceptible to photo-bleaching. Mimicking natural melanin structural coloration could enable several important applications, in particular, for non-iridescent 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 cm(2)) 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. Funding Agencies|Wenner-Gren Foundation; Swedish Research CouncilSwedish Research Council; Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation; Swedish Foundation for Strategic researchSwedish Foundation for Strategic Research; Linkoping University; Wallenberg Wood Science Center the Wallenberg Wood Science Centre; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Materials that provide independent control of infrared thermal radiation and haze in the visible could benefit many areas and applications, including clothing, packaging and photovoltaics. Here, we study this possibility for a metamaterial composite paper based on cellulose nanofibrils (CNF) and silicon dioxide (SiO2) microparticles with infrared (IR) Frohlich phonon resonances. This CNF-SiO2 composite shows outstanding transparency in the visible wavelength range, with the option of controlling light diffusion and haze from almost zero to 90% by varying the SiO2 microparticle concentration. We further show that the transparent metamaterial paper could maintain high thermal emissivity in the atmospheric IR window, as attributed to strong IR absorption of both the nanocellulose and the resonant SiO2 microparticles. The high IR emissivity and low visible absorption make the paper suitable for passive radiative cooling and we demonstrate cooling of the paper to around 3 degrees C below ambient air temperature by exposing it to the sky. Funding Agencies|Knut and Allice Wallenberg Foundation via a Wallenberg Scholarship; Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation; Linkoping University; Wallenberg Wood Science Center; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research; Swedish Armed Forces Research and Technology programme

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. Funding agencies: Swedish Foundation for Strategic Research [RMA11-0037]; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Chalmers Nanoscience and Nanotechnology Area of

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. © 2017 American Chemical Society. Funding Agencies|VR, Vetenskapsrådet; SSF, Stiftelsen för Strategisk Forskning; 2009 00971; 248154, FP7, Seventh Framework Programme; 309127, FP7, Seventh Framework Programme; RMA08-0109, SSF, Sjögren’s Syndrome Foundation; KVA, Royal Swedish Academy of Sciences

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. Funding Agencies|Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research; AForsk Foundation; Knut and Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU No 2009 00971]

Being able to dynamically shape light at the nanoscale is one of the ultimate goals in nano-optics1. Resonant light-matter interaction can be achieved using conventional plasmonics based on metal nanostructures, but their tunability is highly limited due to a fixed permittivity2. Materials with switchable states and methods for dynamic control of light-matter interaction at the nanoscale are therefore desired. Here we show that nanodisks of a conductive polymer can support localized surface plasmon resonances in the near-infrared and function as dynamic nano-optical antennas, with their resonance behaviour tunable by chemical redox reactions. These plasmons originate from the mobile polaronic charge carriers of a poly(3,4-ethylenedioxythiophene:sulfate) (PEDOT:Sulf) polymer network. We demonstrate complete and reversible switching of the optical response of the nanoantennas by chemical tuning of their redox state, which modulates the material permittivity between plasmonic and dielectric regimes via non-volatile changes in the mobile charge carrier density. Further research may study different conductive polymers and nanostructures and explore their use in various applications, such as dynamic meta-optics and reflective displays.

The coupling between charge accumulation in a conjugated polymer and the ionic charge compensation, provided from an electrolyte, defines the mode of operation in a vast array of different organic electrochemical devices. The most explored mixed organic ion-electron conductor, serving as the active electrode in these devices, is poly(3,4-ethyelenedioxythiophene) doped with polystyrelensulfonate (PEDOT:PSS). In this progress report, scientists of the Laboratory of Organic Electronics at Linkoping University review some of the achievements derived over the last two decades in the field of organic electrochemical devices, in particular including PEDOT:PSS as the active material. The recently established understanding of the volumetric capacitance and the mixed ion-electron charge transport properties of PEDOT are described along with examples of various devices and phenomena utilizing this ion-electron coupling, such as the organic electrochemical transistor, ionic-electronic thermodiffusion, electrochromic devices, surface switches, and more. One of the pioneers in this exciting research field is Prof. Olle Inganas and the authors of this progress report wish to celebrate and acknowledge all the fantastic achievements and inspiration accomplished by Prof. Inganas all since 1981. Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Research Council; Onnesjo Foundation; Swedish Foundation for Strategic Research; European Commission; Wenner-Gren Foundations; AForsk Foundation; strategic research area of Advanced Functional Materials at Linkoping University; Vinnova

Structural color generation by plasmonic and other means has attracted significant interest as a solution to avoid inks based on dyes. Prominent advantages include better robustness compared with organic dyes while also providing high chromaticity and brightness in ultrathin films. However, lack of cheap and scalable fabrication techniques has so far limited structural coloration to only a few applications and functional devices. Here, we demonstrate reflective (plasmonic) structural coloration at high resolution by inkjet printing on non-patterned surfaces. The method is flexible, scalable to large areas, and avoids complicated or costly fabrication steps. Optical microcavities on flexible plastic substrates were made starting with an inkjet-printed silver film as a bottom mirror. Inkjet-printed organic dielectric micropixels then served as the spacer layer, resulting in optical microcavities with reflective structural colors after coating with a thin semi-transparent metallic top layer. Optimization of ink formulation allowed for uniform pixels with minimum coffee stain effects as well as control of spacer thickness (around 50-150 nm) and color by varying the solid content of the ink. We investigate the possibility to obtain red, green and blue (RGB) pixels and demonstrate the improvement of particularly the blue coloration using wavelength-dependent plasmon absorption of gold nanoislands as a top mirror. Inkjet printing of optical microcavities and plasmonic cavities may find use in various applications, such as reflective displays in color. Funding Agencies|Swedish Foundation for Strategic Research; AForsk Foundation; Wenner-Gren Foundations; Swedish Research Council; Royal Swedish Academy of Sciences; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Ag nanoparticles (NPs) are deposited on BiVO4 photoanodes to study their effect on the photoelectrochemical (PEC) water splitting performance of the semiconductor. 15 nm light-absorbing NPs and 65 ...

Electrochromic displays based on conducting polymers exhibit higher contrasts and are cheaper, faster, more durable, and easier to synthesize as well as to process than their non-polymeric counterparts. However, current devices are typically based on thin electrochromic layers on top of a reflecting surface, which limits the thickness of the polymer layer to a few hundred nanometers. Here, we embed a light-scattering material within the electrochromic material to achieve a freestanding electrochromic paper-like electrode (50 to 500 μm). The device is based on a cellulose composite combining PEDOT:PSS as the electrochromic material and TiO2 nanoparticles as the reflecting material. Owing to the excellent refractive properties of TiO2, this nanocomposite is white in the neutral state and, when reduced, turns blue resulting in a color contrast around 30. The composite has a granular morphology and, as shown by AFM, an intermingling of TiO2 and PEDOT:PSS at the surface. Variation of the amount of TiO2 within the composite material is shown to result in a trade-off in optical and electrical properties. A proof-of-concept freestanding electrochromic device was fabricated by casting all layers successively to maximize the interlayer conformation. This freestanding device was found to be stable for over 100 cycles when ramped between 3 and −3 V.

Photoelectrochemical (PEC) water splitting is a promising technology that uses light absorbing semiconductors to convert solar energy directly into a chemical fuel (i.e., hydrogen). PEC water splitting has the potential to become a key technology in achieving a sustainable society, if high solar to fuel energy conversion efficiencies are obtained with earth abundant materials. This review article discusses recent developments and discoveries in the mechanisms by which the localized surface plasmon resonance (LSPR) in metallic nanoparticles can increase or complement a neighbouring semiconductor in light absorption for catalytic water splitting applications. These mechanisms can mitigate the intrinsic optical limitations of semiconductors (e.g., metal oxides) for efficient solar water splitting. We identify four types of enhancement mechanisms in the recent literature: (i) light scattering, (ii) light concentration, (iii) hot electron injection (HEI), and (iv) plasmon-induced resonance energy transfer (PIRET). (i) Light scattering and (ii) light concentration are light trapping mechanisms that can increase the absorption of light with energies above the semiconductor optical band-edge. These two mechanisms are ideal to enhance the absorption of promising semiconductors with narrow bandgap energies that suffer from limited absorption coefficients and bulk charge recombination. On the other hand, (iii) HEI and the recently discovered (iv) PIRET are mechanisms that can enhance the absorption also below the semiconductor optical band-edge. Therefore, HEI and PIRET have the potential to extend the light utilization to visible and near-infrared wavelengths of semiconductors with excellent electrochemical properties, but with large bandgap energies. New techniques and theories that have been developed to elucidate the above mentioned plasmonic mechanisms are presented and discussed for their application in metal oxide photoelectrodes. Finally, other plasmonic and non-plasmonic effects that do not increase the device absorption, but affect the electrochemical properties of the semiconductor (e.g., charge carrier transport) are also discussed, since a complete understanding of these phenomena is fundamental for the design of an efficient plasmonic NP-semiconductor water splitting device. Funding Agencies|NWO (VENI project); Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research; Royal Swedish Academy of Sciences; AForsk Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

Plasmons and excitons can interact to form new hybridized light–matter states, with a multitude of potential applications including optical logic circuits and single-photon switches. Here, we report the first observation of strong coupling based on optically thin plasmonic nanohole films. The absorptive plasmon resonances of these nanohole films lead to suppressed transmission and Fano-shaped extinction peaks. We prepared silver nanohole films by colloidal lithography, which enables large-scale fabrication of nanoholes distributed in a short-range order. When coated with J-aggregate molecules, both extinction and absorption spectra show clear formation of two separated polariton resonances, with vacuum Rabi splitting on the order of 300 meV determined from anticrossing experiments. In accordance with strong coupling theory, the splitting magnitude increases linearly with the square root of molecular concentration. The extinction peak positions are blue-shifted from the absorption polariton positions, as explained by additional Fano interference between the hybridized states and the metal film. This highlights that absorption measurements are important not only to prove strong coupling but also to correctly determine hybridized polariton positions and splitting magnitudes in hybrid plasmonic nanohole systems. The polariton absorption peaks also show strong dependence on illumination direction, as found related to inherent directionality of the plasmonic nanohole metasurface and differences in light interaction with nonhybridized molecules. Importantly, optical simulations could successfully reproduce the experimental results and all coupling features. Furthermore, simulated spatial distribution of the absorption provides additional evidence of strong coupling in the hybrid nanohole system. The work paves the way toward strong coupling applications based on optically thin nanohole systems, as further promoted by the scalable fabrication. Funding agencies: Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research; AForsk Foundation; Royal Swedish Academy of Sciences; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping Univer

State-of-the-art solar energy harvesting systems based on photovoltaic technology require constant illumination for optimal operation. However, weather conditions and solar illumination tend to fluctuate. Here, a device is presented that extracts electrical energy from such light fluctuations. The concept combines light-induced heating of gold nanodisks (acting as plasmonic optical nanoantennas), and an organic pyroelectric copolymer film (poly(vinylidenefluoride-co-trifluoroethylene)), that converts temperature changes into electrical signals. This hybrid device can repeatedly generate current pulses, not only upon the onset of illumination, but also when illumination is blocked. Detailed characterization highlights the key role of the polarization state of the copolymer, while the copolymer thickness has minor influence on performance. The results are fully consistent with plasmon-assisted pyroelectric effects, as corroborated by combined optical and thermal simulations that match the experimental results. Owing to the tunability of plasmonic resonances, the presented concept is compatible with harvesting near infrared light while concurrently maintaining visible transparency. Funding agencies: Wenner-Gren Foundations; Swedish Research Council [2015-05070]; Swedish Foundation for Strategic Research; AForsk Foundation; Royal Swedish Academy of Sciences; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Lin

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.

The conversion of light to electrical and chemical energy has the potential to provide meaningful advances to many aspects of daily life, including the production of energy, water purification, and optical sensing. Recently, plasmonic nanoparticles (PNPs) have been increasingly used in artificial photosynthesis (e.g., water splitting) devices in order to extend the visible light utilization of semiconductors to light energies below their band gap. These nanoparticles absorb light and produce hot electrons and holes that can drive artificial photosynthesis reactions. For n-type semiconductor photoanodes decorated with PNPs, hot charge carriers are separated by a process called hot electron injection (HEI), where hot electrons with sufficient energy are transferred to the conduction band of the semiconductor. An important parameter that affects the HEI efficiency is the nanoparticle composition, since the hot electron energy is sensitive to the electronic band structure of the metal. Alloy PNPs are of particular importance for semiconductor/PNPs composites, because by changing the alloy composition their absorption spectra can be tuned to accurately extend the light absorption of the semiconductor. This work experimentally compares the HEI efficiency from Ag, Au, and Ag/Au alloy nanoparticles to TiO2 photoanodes for the photoproduction of hydrogen. Alloy PNPs not only exhibit tunable absorption but can also improve the stability and electronic and catalytic properties of the pure metal PNPs. In this work, we find that the Ag/Au alloy PNPs extend the stability of Ag in water to larger applied potentials while, at the same time, increasing the interband threshold energy of Au. This increasing of the interband energy of Au suppresses the visible-light-induced interband excitations, favoring intraband excitations that result in higher hot electron energies and HEI efficiencies.

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is well known for its electrochromic properties in the visible region. Less focus has been devoted to the infrared (IR) wavelength range, although tunable IR properties could enable a wide range of novel applications. As an example, modern day vehicles have thermal cameras to identify pedestrians and animals in total darkness, but road and speed signs cannot be easily visualized by these imaging systems. IR electrochromism could enable a new generation of dynamic road signs that are compatible with thermal imaging, while simultaneously providing contrast also in the visible region. Here, we present the first metal-free flexible IR electrochromic devices, based on PEDOT:Tosylate as both the electrochromic material and electrodes. Lateral electrochromic devices enabled a detailed investigation of the IR electrochromism of thin PEDOT:Tosylate films, revealing large changes in their thermal signature, with effective temperature changes up to 10 [degree]C between the oxidized (1.5 V) and reduced (-1.5 V) states of the polymer. Larger scale (7 [times] 7 cm) vertical electrochromic devices demonstrate practical suitability and showed effective temperature changes of approximately 7 [degree]C, with good optical memory and fast switching (1.9 s from the oxidized state to the reduced state and 3.3 s for the reversed switching). The results are highly encouraging for using PEDOT:Tosylate for IR electrochromic applications. Funding agencies: Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research; AForsk Foundation; Knut and Alice Wallenberg Foundation (Tail of the sun), Vinnova as part of the Swedish national innovation program SIO Graphene; Swedish Gover

We demonstrate scalable, low-cost and low-temperature (Funding agencies: Ministry of Higher Education and Scientific Research, Khartoum-Sudan [700]; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Material at Linkoping University [2009 00971]; Swedish Foundation for Strate

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) has shown promise as air electrode in renewable energy technologies like metal-air batteries and fuel cells. PEDOT is based on atomic elements of high abundance and is synthesized at low temperature from solution. The mechanism of oxygen reduction reaction (ORR) over chemically polymerized PEDOT: Cl still remains controversial with eventual role of transition metal impurities. However, regardless of the mechanistic route, we here demonstrate yet another key active role of PEDOT in the ORR mechanism. Our study demonstrates the decoupling of conductivity (intrinsic property) from electrocatalysis (as an extrinsic phenomenon) yielding the evidence of doping of the polymer by oxygen during ORR. Hence, the PEDOT electrode is electrochemically reduced (undoped) in the voltage range of ORR regime, but O-2 keeps it conducting; ensuring PEDOT to act as an electrode for the ORR. The interaction of oxygen with the polymer electrode is investigated with a battery of spectroscopic techniques. Funding Agencies|European Research Council (ERC) [307596]; Knut and Alice Wallenberg foundation; Wenner-Gren Foundations; Swedish Research Council; Swedish Foundation for Strategic Research [0-3D]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]

Sensors for monitoring temperature, heat flux, and thermal radiation are essential for applications such as electronic skin. While pyroelectric and thermoelectric effects are suitable candidates as functional elements in such devices, both concepts show individual drawbacks in terms of zero equilibrium signals for pyroelectric materials and small or slow response of thermoelectric materials. Here, these drawbacks are overcome by introducing the concept of thermodiffusion-assisted pyroelectrics, which combines and enhances the performance of pyroelectric and ionic thermoelectric materials. The presented integrated concept provides both rapid initial response upon heating and stable synergistically enhanced signals upon prolonged exposure to heat stimuli. Likewise, incorporation of plasmonic metasurfaces enables the concept to provide both rapid and stable signals for radiation-induced heating. The performance of the concept and its working mechanism can be explained by ion-electron interactions at the interface between the pyroelectric and ionic thermoelectric materials. Funding Agencies|Swedish Foundation for Strategic Research; Swedish Research Council; AForsk Foundation; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [200900971]

Long DNA molecules can self-entangle into knots. Experimental techniques for observing such DNA knots (primarily gel electrophoresis) are limited to bulk methods and circular molecules below 10 kilobase pairs in length. Here, we show that solid-state nanopores can be used to directly observe individual knots in both linear and circular single DNA molecules of arbitrary length. The DNA knots are observed as short spikes in the nanopore current traces of the traversing DNA molecules and their detection is dependent on a sufficiently high measurement resolution, which can be achieved using high-concentration LiCl buffers. We study the percentage of molecules with knots for DNA molecules of up to 166 kilobase pairs in length and find that the knotting occurrence rises with the length of the DNA molecule, consistent with a constant knotting probability per unit length. Our experimental data compare favourably with previous simulation-based predictions for long polymers. From the translocation time of the knot through the nanopore, we estimate that the majority of the DNA knots are tight, with remarkably small sizes below 100 nm. In the case of linear molecules, we also observe that knots are able to slide out on application of high driving forces (voltage).

Temperature gradients are generated by the sun and a vast array of technologies and can induce molecular concentration gradients in solutions via thermodiffusion (Soret effect). For ions, this leads to a thermovoltage that is determined by the thermal gradient Delta T across the electrolyte, together with the ionic Seebeck coefficient alpha(i). So far, redox-free electrolytes have been poorly explored in thermoelectric applications due to a lack of strategies to harvest the energy from the Soret effect. Here, we report the conversion of heat into stored charge via a remarkably strong ionic Soret effect in a polymeric electrolyte (Seebeck coefficients as high as alpha(i) = 10 mV K-1). The ionic thermoelectric supercapacitor (ITESC) is charged under a temperature gradient. After the temperature gradient is removed, the stored electrical energy can be delivered to an external circuit. This new means to harvest energy is particularly suitable for intermittent heat sources like the sun. We show that the stored electrical energy of the ITESC is proportional to (Delta T alpha(i))(2). The resulting ITESC can convert and store several thousand times more energy compared with a traditional thermoelectric generator connected in series with a supercapacitor. Funding Agencies|European Research Council (ERC) [307596]; Swedish foundation for strategic research (SSF); Knut and Alice Wallenberg foundation (KAW); Swedish Energy Agency; Wenner-Gren Foundations; Advanced Functional Materials Centre at Linkoping University.The previous status of this article was Manuscript.

Smart materials can be used for a wide variety of applications, including sensing and energy harvesting. Implementation of smart materials in large area devices requires scalable manufacturing. The use of paper-making techniques would offer an enormous production capacity, allowing for low-cost and large-scale manufacturing. In this work we present a successful pilot scale paper machine manufacturing of functional composite papers (100 m min−1 with a web width of 30 cm) based on cellulose fibres and commercial tetrapodal zinc oxide microwhiskers (ZnO-Ts). Carbon electrodes could successfully be printed on the paper to form complete electronic devices where the paper itself is the active material. This enabled development of a ZnO-composite paper photosensor, where we characterized its stability, sensitivity and speed. The devices show excellent photosensing properties over a wide range of light irradiances (0.01–1 Sun), including short response times (~10 s) and long-term stability. Under simulated sunlight and a bias voltage of 1 V, small (0.5 cm2) two-probe interdigitated photosensor devices provided 12 μA photocurrent. Under the same conditions, four-probe measurements of the composite paper showed a sheet resistance of 6.9 107 Ω/sq. Four-probe measurements also demonstrated that the paper conductivity varies linearly with light irradiance. To the best of our knowledge, this is the first example of pilot paper machine production of an optoelectronic paper, demonstrating the potential for large-scale paper manufacturing of active smart paper from low-cost industrial bulk materials.

Lignin is one of the most abundant biopolymers, constituting 25% of plants. The pulp and paper industries extract lignin in their process and today seek new applications for this by-product. Here, ...

Thermoelectric materials enable conversion of heat to electrical energy. The performance of electronic thermoelectric materials is typically evaluated using a figure of merit ZT = sigma alpha 2T/lambda, where sigma is the conductivity, alpha is the so-called Seebeck coefficient, and lambda is the thermal conductivity. However, it has been unclear how to best evaluate the performance of ionic thermoelectric materials, like ionic solids and electrolytes. These systems cannot be directly used in a traditional thermoelectric generator, because they are based on ions that cannot pass the interface between the thermoelectric material and external metal electrodes. Instead, energy can be harvested from the ionic thermoelectric effect by charging a supercapacitor. In this study, the authors investigate the ionic thermoelectric properties at varied relative humidity for the polyelectrolyte polystyrene sulfonate sodium and correlate these properties with the charging efficiency when used in an ionic thermoelectric supercapacitor (ITESC). In analogy with electronic thermoelectric generators, the results show that the charging efficiency of the ITESC can be quantitatively related to the figure of merit ZT(i) = sigma i alpha i2T/lambda. This means that the performance of ionic thermoelectric materials can also be compared and predicted based on the ZT, which will be highly valuable in the design of high-performance ITESCs. Funding Agencies|European Research Council (ERC-starting-grant) [307596]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

The revelation of protein-protein interactions is one of the main preoccupations in the field of proteomics. Nanoplasmonics has emerged as an attractive surface-based technique because of its ability to sense protein binding under physiological conditions in a label-free manner. Here, we use short-range ordered holes with a diameter of approximately 150 nm and a depth of approximately 50 nm as a nanoplasmonic template. A approximately 40 nm high cylindrical region of Au is exposed on the walls of the holes only, while the rest of the surface consists of TiO2. Since the sensitivity is confined to the nanometric holes, the use of two different materials for the sensor substrate offers the opportunity to selectively bind proteins to the most sensitive Au regions on the sensor surface. This was realized by applying material-selective poly(ethylene glycol)-based surface chemistry, restricting NeutrAvidin binding to surface-immobilized biotin on the Au areas only. We show that under mass-transport limited conditions (low nM bulk concentrations), the initial time-resolved response of uptake could be increased by a factor of almost 20 compared with the case where proteins were allowed to bind on the entire sensor surface and stress the generic relevance of this concept for nanoscale sensors. In the scope of further optimizing the limit of detection (LOD) of the sensor structure, we present finite-element (FE) simulations to unravel spatially resolved binding rates. These revealed that the binding rates in the holes occur in a highly inhomogeneous manner with highest binding rates observed at the upper rim of the holes and the lowest rates observed at the bottom of the holes. By assuming a plasmonic field distribution with enhanced sensitivity at the Au-TiO2 interface, the FE simulations reproduced the experimental findings qualitatively.

We have developed a multilayer flux-transformer-based high-TC SQUID (flip-chip) magnetometer that improves signal-to-noise-ratios (SNR) in ultra-low field magnetic resonance (ulf-MR) recordings of protons in water. Direct ulf-MR-based benchmarking of the flip-chip versus a standard planar high-TC SQUID magnetometer resulted in improvement of the SNR by a factor of 2. This gain is attributable to the improved transformation coefficient (1.9 vs 5.3 nT/Φ0) that increased the signal available to the flip-chip sensor and to the lower noise at the measurement frequency (15 vs 25 fT/Hz1/2 at 4 kHz). The improved SNR can lead to better spectroscopic resolution, lower imaging times, and higher resolution in ulf-MR imaging systems based on high- TC SQUID technology. The experimental details of the sensors, calibration, and ulf-MR benchmarking are presented in this report.

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.