In 2017, a new family of in-plane, chemically-ordered quaternary MAX phases, coined i-MAX, has been reported since 2017. The first i-MAX phase, (Mo2/3Sc1/3)(2)AlC, garnered significant research attention due to the presence of chemically ordered Sc within the Mo-dominated M layer, and the facilitated removal of both Al and Sc upon etching, resulting in 2D i-MXene, Mo1.33C, with ordered divacancies. The i-MXene renders an exceptionally low resistivity of 33.2 mu omega m(-1) and a high volumetric capacitance of approximate to 1150 F cm(-3). This discovery has been followed by the synthesis of, to date, 32 i-MAX phases and 5 i-MXenes, where the latter have shown potential for applications including, but not limited to, energy storage and catalysis. Herein, fundamental investigations of i-MAX phases and i-MXenes, along with their applicability in supercapacitive and catalytic applications, are reviewed. Moreover, recent results on ion intercalation and post-etching treatment of Mo1.33C are presented. The charge storage performance can also be tuned by forming MXene hydrogel and through inert atmosphere annealing, where the latter renders a superior volumetric capacitance of approximate to 1635 F cm(-3). This report demonstrates the potential of the i-MXene family for catalytic and energy storage applications, and highlights novel research directions for further development and successful employment in practical applications.

The thermoelectric (TE) phenomena are intensively explored by the scientific community due to the rather inefficient way energy resources are used with a large fraction of energy wasted in the form of heat. Among various materials, mixed ion-electron conductors (MIEC) are recently being explored as potential thermoelectrics, primarily due to their low thermal conductivity. The combination of electronic and ionic charge carriers in those inorganic or organic materials leads to complex evolution of the thermovoltage (V_oc) with time, temperature, and/or humidity. One of the most promising organic thermoelectric materials, poly(3,4-ethyelenedioxythiophene)-polystyrene sulfonate (PEDOT-PSS), is an MIEC. A previous study reveals that at high humidity, PEDOT-PSS undergoes an ionic Seebeck effect due to mobile protons. Yet, this phenomenon is not well understood. In this work, the time dependence of the V_oc is studied and its behavior from the contribution of both charge carriers (holes and protons) is explained. The presence of a complex reorganization of the charge carriers promoting an internal electrochemical reaction within the polymer film is identified. Interestingly, it is demonstrated that the time dependence behavior of V_oc is a way to distinguish between three classes of polymeric materials: electronic conductor, ionic conductor, and mixed ionic–electronic conductor

All-organic active matrix addressed displays based on electrochemical smart pixels made on flexible substrates are reported. Each individual smart pixel device combines an electrochemical transistor with an electrochromic display cell, thus resulting in a low-voltage operating and robust display technology. Poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS) served as the active material in the electrochemical smart pixels, as well as the conducting lines, of the monolithically integrated active-matrix display. Different active-matrix display addressing schemes have been investigated and a matrix display fill factor of 65 % was reached. This is achieved by combining a three-terminal electrochemical transistor with an electrochromic display cell architecture, in which an additional layer of PEDOT:PSS was placed on top of the display cell counter electrode. In addition, we have evaluated different kinds of electrochromic polymer materials aiming at reaching a high color switch contrast. This work has been carried out in the light of achieving a robust display technology that is easily manufactured using a standard label printing press, which forced us to use the fewest different materials as well as avoiding exotic and complex device architectures. Together, this yields a manufacturing process of only five discrete patterning steps, which in turn promise for that the active matrix addressed displays can be manufactured on paper or plastic substrates in a roll-to-roll production procedure.

Commercially available yarns are promising precursor for artificial muscles for smart fabric-based textile wearables. Electrochemically driven conductive polymer (CP) coated yarns have already shown their potential to be used in smart fabrics. Unfortunately, the practical application of these yarns is still hindered due to their slow ion exchange properties and low strain. Here, a method is demonstrated to morph poly-3,4-ethylenedioxythiophene:poly-styrenesulfonate (PEDOT:PSS) coated multifilament textile yarns in highly twisted and coiled structures, providing >1% linear actuation in <1 s at a potential of +0.6 V. A potential window of +0.6 V and -1.2 V triggers the fully reversible actuation of a coiled yarn providing >1.62% strain. Compared to the untwisted, regular yarns, the twisted and coiled yarns produce >9x and >20x higher strain, respectively. The strain and speed are significantly higher than the maximum reported results from other electrochemically operated CP yarns. The yarns actuation is explained by reversible oxidation/reduction reactions occurring at CPs. However, the helical opening/closing of the twisted or coiled yarns due to the torsional yarn untwisting/retwisting assists the rapid and large linear actuation. These PEDOT:PSS coated yarn actuators are of great interest to drive smart textile exoskeletons.

The semiconductor-electrode interface impacts the function and the performance of (opto) electronic devices. For printed organic electronics the electrode surface is not atomically clean leading to weakly interacting interfaces. As a result, solution-processed organic ultrathin films on electrodes typically form islands due to dewetting. It has therefore been utterly difficult to achieve homogenous ultrathin conjugated polymer films. This has made the investigation of the correct energetics of the conjugated polymer-electrode interface impossible. Also, this has hampered the development of devices including ultrathin conjugated polymer layers. Here, LangmuirShafer-manufactured homogenous mono-and multilayers of semiconducting polymers on metal electrodes are reported and the energy level bending using photoelectron spectroscopy is tracked. The amorphous films display an abrupt energy level bending that does not extend beyond the first monolayer. These findings provide new insights of the energetics of the polymer-electrode interface and opens up for new high-performing devices based on ultrathin semiconducting polymers.

Organic photovoltaics are under intense development and significant focus has been placed on tuning the donor ionization potential and acceptor electron affinity to optimize open circuit voltage. Here, it is shown that for a series of regioregular-poly(3-hexylthiophene): fullerene bulk heterojunction (BHJ) organic photovoltaic devices with pinned electrodes, integer charge transfer states present in the dark and created as a consequence of Fermi level equilibrium at BHJ have a profound effect on open circuit voltage. The integer charge transfer state formation causes vacuum level misalignment that yields a roughly constant effective donor ionization potential to acceptor electron affinity energy difference at the donor-acceptor interface, even though there is a large variation in electron affinity for the fullerene series. The large variation in open circuit voltage for the corresponding device series instead is found to be a consequence of trap-assisted recombination via integer charge transfer states. Based on the results, novel design rules for optimizing open circuit voltage and performance of organic bulk heterojunction solar cells are proposed.

A hybrid manufacturing approach for organic electrochemical transistors (OECTs) on flexible substrates is reported. The technology is based on conventional and digital printing (screen and inkjet printing), laser processing, and post-press technologies. A careful selection of the conductive, dielectric, and semiconductor materials with respect to their optical properties enables a self-aligning pattern formation which results in a significant reduction of the usual registration problems during manufacturing. For the prototype OECTs, based on this technology, on/off ratios up to 600 and switching times of 100 milliseconds at gate voltages in the range of 1 V were obtained.

In this work, the first example of a hierarchically structured hollow silica system is reported without any chemical modification to the enzyme involved in the process. The leaching of the physically adsorbed enzyme is substantially restrained in comparison to pure hollow silica supports. The hierarchical architecture is composed of the ordered hollow silica spheres with a shell-in-shell structure. This rationally integrated architecture, which serves as the host for glucose oxidase immobilization, displays many significant advantages, including increases in mechanical stability, enzyme loading, and bioactivity, and a decrease in enzyme leaching compared to existing pure hollow silica matrices. This facilitates further multifarious applications for enhanced enzyme immobilization, biosensors, and biocatalysis.

Monolithic sol-gel silica composites incorporating platinum-based chromophores and various types of gold nanoparticles (AuNPs) are prepared and polished to high optical quality. Their photophysical properties are investigated. The glass materials show well-defined localized surface plasmon resonance (SPR) absorbance from the visible to NIR. No redshifts of the AuNP plasmon absorption peaks due to the increase in nanoparticle doping concentration are observed in the glasses, proving that no or very small SPR coupling effects occur between the AuNPs. At 600 nm excitation, but not at 532 nm, the AuNPs improve the nonlinear absorption performance of glasses codoped with 50 × 10−3 m of a Pt-acetylide chromophore. The glasses doped with lower concentrations of AuNPs (2-5 μm average distance) and 50 × 10−3 m in chromophore, show a marked improvement in nonlinear absorption, with no or only small improvement for the more highly AuNP doped glasses. This study shows the importance of excitation wavelength and nanoparticle concentration for composite systems employing AuNPs to improve two-photon absorption of chromophores. [ABSTRACT FROM AUTHOR]

Light emission from ambipolar organic field-effect transistors (OFETs) is often observed when they are operated in the unipolar regime. This is unexpected, the light emission should be completely suppressed, because in the unipolar regime only one type of charge carrier is accumulated. Here, an electroluminescent diketopyrrolopyrrole copolymer is investigated. Local potential measurements by scanning Kelvin probe microscopy reveal a recombination position that is unstable in time due to the presence of injection barriers. The electroluminescence and electrical transport have been numerically analyzed. It is shown that the counterintuitive unipolar light emission is quantitatively explained by injection of minority carriers into deep tail states of the semiconductor. The density of the injected minority carriers is small. Hence they are relatively immobile and they recombine close the contact with accumulated majority carriers. The unipolar light output is characterized by a constant efficiency independent of gate bias. It is argued that light emission from OFETs predominantly originates from the unipolar regime when the charge transport is injection limited.

Methylglyoxal (MG) is a highly reactive dicarbonyl and the main precursor of advanced glycation end-products (AGEs). After myocardial infarction (MI), MG-derived AGEs accumulate in the heart and contribute to adverse remodeling and loss of cardiac function. In this study, the flavonoid fisetin, a dicarbonyl scavenger, is used to reduce the negative effects of MG in the post-MI heart. A fisetin-loaded collagen type I hydrogel (fisetin-HG) is injected intramyocardially in mice at 3 h post-MI, and compared to fisetin-alone, hydrogel-alone, or saline treatment. Fisetin-HG treatment increases the level of glyoxalase-1 (the main MG-metabolizing enzyme), reduces MG-AGE accumulation, and decreases oxidative stress in the MI heart, which is associated with smaller scar size and improved cardiac function. Treatment with fisetin-HG also promotes neovascularization and increases the number of pro-healing macrophages in the infarct area, while reducing the number of pro-inflammatory macrophages. Taken together, the results demonstrate that the fisetin-collagen hydrogel therapy can reduce the accumulation and negative effects of MG post-MI. This therapy may be a promising approach to limit adverse cardiac remodeling, prevent damage, and preserve function of the infarcted heart.

In electronics, the field-effect transistor (FET) is a crucial cornerstone and successful integration of this semiconductor device into circuit applications requires stable and ideal electrical characteristics over a wide range of temperatures and environments. Solution processing, using printing or coating techniques, has been explored to manufacture organic field-effect transistors (OFET) on flexible carriers, enabling radically novel electronics applications. Ideal electrical characteristics, in organic materials, are typically only found in single crystals. Tiresome growth and manipulation of these hamper practical production of flexible OFETs circuits. To date, neither devices nor any circuits, based on solution-processed OFETs, has exhibited an ideal set of characteristics similar or better than todays FET technology based on amorphous silicon. Here, bar-assisted meniscus shearing of dibenzo-tetrathiafulvalene to coat-process self-organized crystalline organic semiconducting domains with high reproducibility is reported. Including these coatings as the channel in OFETs, electric field and temperature-independent charge carrier mobility and no bias stress effects are observed. Furthermore, record-high gain in OFET inverters and exceptional operational stability in both air and water are measured.

The synthesis and experimental/theoretical characterization of a new series of electron-transporting copolymers based on the naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block are reported. Comonomers are designed to test the emergent effects of manipulating backbone torsional characteristics, and density functional theory (DFT) analysis reveals the key role of backbone conformation in optimizing electronic delocalization and transport. The NBA copolymer conformational and electronic properties are characterized using a broad array of molecular/macromolecular, thermal, optical, electrochemical, and charge transport techniques. All NBA copolymers exhibit strongly aggregated morphologies with significant nanoscale order. Copolymer charge transport properties are investigated in thin-film transistors and exhibit excellent electron mobilities ranging from 0.4 to 4.5 cm(2) V-1 s(-1). Importantly, the electron transport efficiency correlates with the film mesoscale order, which emerges from comonomer-dependent backbone planarity and extension. These results illuminate the key NBA building block structure-morphology-bulk property design relationships essential for processable, electronics-applicable high-performance polymeric semiconductors.

A novel patterning technique of conductive polymers produced by vapor phase polymerization is demonstrated. The method involves exposing an oxidant film to UV light which changes the local chemical environment of the oxidant and subsequently the polymerization kinetics. This procedure is used to control the conductivity in the conjugated polymer poly(3,4-ethylenedioxythiophene): tosylate by more than six orders of magnitude in addition to producing high-resolution patterns and optical gradients. The mechanism behind the modulation in the polymerization kinetics by UV light irradiation as well as the properties of the resulting polymer are investigated.

This work describes the preparation and properties of hydrogel surface chemistries enabling controlled and well-defined cell adhesion. The hydrogels may be prepared directly on plastic substrates, such as polystyrene slides or dishes, using a quick and experimentally simple photopolymerization process, compatible with photolithographic and microfluidic patterning methods. The intended application for these materials is as substrates for diagnostic cell adhesion assays, particularly for the analysis of human platelet function. The adsorption of fibrinogen and other platelet promoting molecules is shown to be completely inhibited by the hydrogel, provided that the film thickness is sufficient (>5 nm). This allows the hydrogel to be used as a matrix for presenting selected bioactive ligands without risking interference from nonspecifically adsorbed platelet adhesion factors, even in undiluted whole blood and blood plasma. This concept is demonstrated by preparing patterns of proteins on hydrogel surfaces, resulting in highly controlled platelet adhesion. Further insights into the protein immobilization and platelet adhesion processes are provided by studies using imaging surface plasmon resonance. The hydrogel surfaces used in this work appear to provide an ideal platform for cell adhesion studies of platelets, and potentially also for other cell types.

A method to decorate cellulose-based helices retrieved from the plant celery with a conductive polymer is proposed. Using a layer-by-layer method, the decoration of the polyanionic conducting polymer poly(4-(2,3-dihydrothieno [3,4-b]-[1,4]dioxin-2-yl-methoxy)-1-butanesulfonic acid (PEDOT-S) is enhanced after coating the negatively charged cellulose helix with a polycationic polyethyleneimine. Microscopy techniques and two-point probe are used to image the structure and measure the conductivity of the helix. Analysis of the optical and electrical properties of the coated helix in the terahertz (THz) frequency range shows a resonance close to 1 THz and a broad shoulder that extends to 3.5 THz, consistent with electromagnetic models. Moreover, as helical antennas, it is shown that both axial and normal modes are present, which are correlated to the orientation and antenna electrical lengths of the coated helices. This work opens the possibility of designing tunable terahertz antennas through simple control of their dimensions and orientation.

Nanocomposites of metal nanoparticles (NPs) and bacterial nanocellulose (BC) enable fabrication of soft and biocompatible materials for optical, catalytic, electronic, and biomedical applications. Current BC-NP nanocomposites are typically prepared by in situ synthesis of the NPs or electrostatic adsorption of surface functionalized NPs, which limits possibilities to control and tune NP size, shape, concentration, and surface chemistry and influences the properties and performance of the materials. Here a self-assembly strategy is described for fabrication of complex and well-defined BC-NP composites using colloidal gold and silver NPs of different sizes, shapes, and concentrations. The self-assembly process results in nanocomposites with distinct biophysical and optical properties. In addition to antibacterial materials and materials with excellent senor performance, materials with unique mechanoplasmonic properties are developed. The homogenous incorporation of plasmonic gold NPs in the BC enables extensive modulation of the optical properties by mechanical stimuli. Compression gives rise to near-field coupling between adsorbed NPs, resulting in tunable spectral variations and enhanced broadband absorption that amplify both nonlinear optical and thermoplasmonic effects and enables novel biosensing strategies.

Here, an unidentified type of micropillar growth is described at room temperature during conventional direct-current magnetron sputtering (DC-MS) deposition from a Li4Ti5O12+graphite sputter target under negative substrate bias and high operating pressure. These fabricated carbon-Li2O-TiO2 microstructures consisting of various Li4Ti5O12/Li2TiO3/LixTiO2 crystalline phases are demonstrated as an anode material in Li-ion microbatteries. The described micropillar fabrication method is a low-cost, substrate independent, single-step, room-temperature vacuum process utilizing a mature industrial complementary metal-oxide-semiconductor (CMOS)-compatible technology. Furthermore, tentative consideration is given to the effects of selected deposition parameters and the growth process, as based on extensive physical and chemical characterization. Additional studies are, however, required to understand the exact processes and interactions that form the micropillars. If this facile method is further extended to other similar metal oxide-carbon systems, it could offer alternative low-cost fabrication routes for microporous high-surface area materials in electrochemistry and microelectronics.

Systematic investigation of the contact resistance in electrolyte-gated organic field-effect transistors (OFETs) demonstrates a dependence of source charge injection versus gate electrode work function. This analysis reveals contact-limitations at the source metal-semiconductor interface and shows that the contact resistance increases as low work function metals are used as the gate electrode. These findings are attributed to the establishment of a built-in potential that is high enough to prevent the Fermi-level pinning at the metal-organic interface. This results in an unfavorable energetic alignment of the source electrode with the valence band of the organic semiconductor. Since the operating voltage in the electrolyte-gated devices is on the same order as the variation of the work functions, it is possible to tune the contact resistance over more than one order of magnitude by varying the gate metal.

The color of polymer solar cells using an opaque electrode is given by the reflected light, which depends on the composition and thickness of each layer of the device. Metal-oxide-based optical spacers are intensively studied in polymer solar cells aiming to optimize the light absorption. However, the low conductivity of materials such as ZnO and TiO2 limits the thickness of such optical spacers to tenths of nanometers. A novel synthesis route of cluster-free Al-doped ZnO (AZO) nanocrystals (NCs) is presented for solution processing of highly conductive layers without the need of temperature annealing, including thick optical spacers on top of polymer blends. The processing of 80 nm thick optical spacers based on AZO nanocrystal solutions on top of 200 nm thick polymer blend layer is demonstrated leading to improved photocurrent density of 17% compared to solar cells using standard active layers of 90 nm in combination with thin ZnO-based optical spacers. These AZO NCs also open new opportunities for the processing of high-efficiency color tuned solar cells. For the first time, it is shown that applying solution-processed thick optical spacer with polymer blends of different thicknesses can process solar cells of similar efficiency over 7% but of different colors.

It has been a hindering issue in perovskite solar cells that the interfaces between the perovskite and charge transport layers show significantly high concentrations of defects with an amount about 100 times more than inside the bulk perovskite layer. The issue causes substantial reduction in both the efficiency and stability of the devices. Herein, a solid-solid contact approach is demonstrated to realize a multifunctional ion-lock layer with strong chemical interaction to the perovskite layer. The multifunctional ion-lock layer remarkably suppresses the interface defects and tunes the work function, contributing to promoting the carrier extraction, increasing the open-circuit voltage, and enlarging the photocurrent. In addition, the multifunctional ion-lock layer successfully locks ions from movement and thus improves the stability of the devices. Finally, with a multifunctional ion-lock layer, the perovskite solar cells deliver an efficiency of up to 23.13% along with desirable long-term operational, storage, and humidity stability. Consequently, the work offers guidelines for establishing defect-suppressed interfaces between perovskites and hole transport layers.

Organic electrochemical transistors formed by in operando electropolymerization of the semiconducting channel are increasingly becoming recognized as a simple and effective implementation of synapses in neuromorphic hardware. However, very few studies have reported the requirements that must be met to ensure that the polymer spreads along the substrate to form a functional conducting channel. The nature of the interface between the substrate and various monomer precursors of conducting polymers through molecular dynamics simulations is investigated, showing that monomer adsorption to the substrate produces an increase in the effective monomer concentration at the surface. By evaluating combinatorial couples of monomers baring various sidechains with differently functionalized substrates, it is shown that the interactions between the substrate and the monomer precursor control the lateral growth of a polymer film along an inert substrate. This effect has implications for fabricating synaptic systems on inexpensive, flexible substrates.

Enhancing low-energy emitting Cu(I)-ionic transition metal complexes (iTMCs) light-emitting electrochemical cells (LECs) is of utmost importance towards Cu(I)-iTMC-based white-emitting LECs. Here, the ancillary ligand design includes (i) extension of & pi;-systems and (ii) insertion of S-bridge between heteroaromatics rings. This led to two novel heteroleptic Cu(I)-iTMCs: 2-(pyridin-2-yl-l2-azanyl)quinoline (CuN2) and 2-(naphthalen-2-ylthio)quinoline (CuS2) as N<^>N and bis[(2-diphenylphosphino)phenyl] ether as P<^>P, exhibiting improved photoluminescence quantum yields (& phi;) and thermally activated delayed fluorescence processes compared to their reference Cu(I)-iTMCs: di(pyridin-2-yl)-l2-azane (CuN1) and di(pyridin-2-yl)sulfane (CuS1). Despite CuS2 stands out with the highest & phi; (38% vs 17 / 14 / 1% for CuN1 / CuN2 / CuS1), only CuN2-LECs show the expected enhanced performance (0.35 cd A(-1) at luminance of 117 cd m(-2)) compared to CuN1-LECs (0.02 cd A(-1) at6 cd m(-2)), while CuS2-LECs feature low performances (0.04 cd A(-1) at 10 cd m(-2)). This suggests that conventional chemical design rules are not effective towards enhancing device performance. Herein, nonconventional multivariate statistical analysis and electrochemical impedance spectroscopy studies allow to rationalize the mismatch between chemical design and device performance bringing to light a hidden design rule: polarizability of the ancillary ligand is key for an efficient Cu(I)-iTMC-LECs. All-in-all, this study provides fresh insights for the design of Cu-iTMCs fueling research on sustainable ion-based lighting sources.

The remarkable success of lead halide perovskites (LHPs) in photovoltaics and other optoelectronics is significantly linked to their defect tolerance, although this correlation remains not fully clear. The tendency of LHPs to decompose into toxic lead-containing compounds in the presence of humid air calls for the need of low-toxicity LHP alternatives comprising of cations with stable oxidation states. To this aim, a plethora of low-dimensional and wide-bandgap perovskite-inspired materials (PIMs) are proposed. Unfortunately, the optoelectronic performance of PIMs currently lags behind that of their LHP-based counterparts, with a key limiting factor being the high concentration of defects in PIMs, whose rich and complex chemistry is still inadequately understood. This review discusses the defect chemistry of relevant PIMs belonging to the halide elpasolite, vacancy-ordered double perovskite, pnictogen-based metal halide, Ag-Bi-I, and metal chalcohalide families of materials. The defect-driven optical and charge-carrier transport properties of PIMs and their device performance within and beyond photovoltaics are especially discussed. Finally, a view on potential solutions for advancing the research on wide-bandgap PIMs is provided. The key insights of this review will help to tackle the commercialization challenges of these emerging semiconductors with low toxicity and intrinsic air stability.

Large scale synthesis and delamination of 2D Mo2CTx (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary transition metal carbide Mo2Ga2C. Different synthesis and delamination routes result in different flake morphologies. The resistivity of free-standing Mo2CTx films increases by an order of magnitude as the temperature is reduced from 300 to 10 K, suggesting semiconductor-like behavior of this MXene, in contrast to Ti3C2Tx which exhibits metallic behavior. At 10 K, the magnetoresistance is positive. Additionally, changes in electronic transport are observed upon annealing of the films. When 2 mu m thick films are tested as electrodes in supercapacitors, capacitances as high as 700 F cm(-3) in a 1 M sulfuric acid electrolyte and high capacity retention for at least 10,000 cycles at 10 A g(-1) are obtained. Free-standing Mo2CTx films, with approximate to 8 wt% carbon nanotubes, perform well when tested as an electrode material for Li-ions, especially at high rates. At 20 and 131 C cycling rates, stable reversible capacities of 250 and 76 mAh g(-1), respectively, are achieved for over 1000 cycles.

The evolution of the society is characterized by an increasing flow of information from things to the internet. Sensors have become the cornerstone of the internet-of-everything as they track various parameters in the society and send them to the cloud for analysis, forecast, or learning. With the many parameters to sense, sensors are becoming complex and difficult to manufacture. To reduce the complexity of manufacturing, one can instead create advanced functional materials that react to multiple stimuli. To this end, conducting polymer aerogels are promising materials as they combine elasticity and sensitivity to pressure and temperature. However, the challenge is to read independently pressure and temperature output signals without cross-talk. Here, a strategy to fully decouple temperature and pressure reading in a dual-parameter sensor based on thermoelectric polymer aerogels is demonstrated. It is found that aerogels made of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) can display properties of semiconductors lying at the transition between insulator and semimetal upon exposure to high boiling point polar solvents, such as dimethylsulfoxide (DMSO). Importantly, because of the temperature-independent charge transport observed for DMSO-treated PEDOT-based aerogel, a decoupled pressure and temperature sensing can be achieved without cross-talk in the dual-parameter sensor devices.

The nanoscale morphology in polymer:PCBM based photovoltaic devices is a major contributor to overall device performance. The disordered nature of the phase-separated structure, in combination with the small length scales involved and the inherent difficulty of reproducing the exact morphologies when spin-coating and annealing thin blend films, have greatly hampered the development of a detailed understanding of how morphology impacts photo voltaic device functioning. In this paper we demonstrate a double nanoimprinting process that allows the formation of nanostructured polymer: PCBM heterojunctions of composition and morphology that can be selected independently. We fabricated photovoltaic (PV) devices with extremely high densities (10(14) mm(-2)) of interpenetrating nanoscale columnar features (as small as 25 nm; at or below the exciton diffusion length) in the active layer. By comparing device results of different feature sizes and two different polymer: PCBM combinations, we demonstrate how double imprinting can be a powerful tool to systematically study different parameters in polymer photovoltaic devices.

Recently, a 2D metal boride - boridene - has been experimentally realized in the form of single-layer molybdenum boride sheets with ordered metal vacancies, through selective etching of the nanolaminated 3D parent borides (Mo_2/3Y_1/3)₂AlB₂ and (Mo_2/3Sc_1/3)₂AlB₂. The chemical formula of the boridene was suggested to be Mo_4/3B_2-xT_z, where T_z denotes surface terminations. Here, the termination composition and material properties of Mo_4/3B_2-xT_z from both theoretical and experimental perspectives are investigated. Termination sites are considered theoretically for termination species T = O, OH, and F, and the energetically favored termination configuration is identified at z = 2 for both single species terminations and binary termination mixes of different stoichiometries in ordered and disordered configurations. Mo_4/3B_2-xT_z is shown to be dynamically stable for multiple termination stoichiometries, displaying semiconducting, semimetallic, or metallic behavior depending on how different terminations are combined. The approximate chemical formula of a freestanding film of boridene is attained as Mo_1.33B_1.9O_0.3(OH)_1.5F_0.7 from X-ray photoelectron spectroscopy (XPS) analysis which, within error margins, is consistent with the theoretical results. Finally, metallic and additive-free Mo_4/3B_2-xT_z shows high catalytic performance for the hydrogen evolution reaction, with an onset potential of 0.15 V versus the reversible hydrogen electrode.

In this study, it is demonstrated that a finer nanostructure produced under a rapid rate of solvent removal significantly improves charge separation in a high-performance polymer: fullerene bulk-heterojunction blend. During spin-coating, variations in solvent evaporation rate give rise to lateral phase separation gradients with the degree of coarseness decreasing away from the center of rotation. As a result, across spin-coated thin films the photocurrent at the first interference maximum varies as much as 25%, which is much larger than any optical effect. This is investigated by combining information on the surface morphology of the active layer imaged by atomic force microscopy, the 3D nanostructure imaged by electron tomography, film formation during the spin coating process imaged by optical interference and photocurrent generation distribution in devices imaged by a scanning light pulse technique. The observation that the nanostructure of organic photovoltaic blends can strongly vary across spin-coated thin films will aid the design of solvent mixtures suitable for high molecular-weight polymers and of coating techniques amenable to large area processing.

While photovoltaic blends based on non-fullerene acceptors are touted for their thermal stability, this type of acceptor tends to crystallize, which can result in a gradual decrease in photovoltaic performance and affects the reproducibility of the devices. Two halogenated indacenodithienothiophene-based acceptors that readily co-crystallize upon mixing are studied, which indicates that the use of an acceptor mixture alone does not guarantee the formation of a disordered mixture. The addition of the donor polymer to the acceptor mixture readily suppresses the crystallization, which results in a fine-grained ternary blend with nanometer-sized domains that do not coarsen due to a highT(g)approximate to 200 degrees C. As a result, annealing at temperatures of up to 170 degrees C does not markedly affect the photovoltaic performance of ternary devices, in contrast to binary devices that suffer from acceptor crystallization in the active layer. The results indicate that the ternary approach enables the use of high-temperature processing protocols, which are needed for upscaling and high-throughput fabrication of organic solar cells. Further, ternary devices display a stable photovoltaic performance at 130 degrees C for at least 205 h, which indicates that the use of acceptor mixtures allows to fabricate devices with excellent thermal stability.

The design of the earth-abundant, nonprecious, efficient, and stable electrocatalysts for efficient hydrogen evolution reaction (HER) in alkaline media is a hot research topic in the field of renewable energies. A heterostructured system composed of MoSx deposited on NiO nanostructures (MoSx@NiO) as a robust catalyst for water splitting is proposed here. NiO nanosponges are applied as cocatalyst for MoS2 in alkaline media. Both NiO and MoS2@NiO composites are prepared by a hydrothermal method. The NiO nanostructures exhibit sponge-like morphology and are completely covered by the sheet-like MoS2. The NiO and MoS2 exhibit cubic and hexagonal phases, respectively. In the MoSx@NiO composite, the HER experiment in 1 m KOH electrolyte results in a low overpotential (406 mV) to produce 10 mA cm(-2) current density. The Tafel slope for that case is 43 mV per decade, which is the lowest ever achieved for MoS2-based electrocatalyst in alkaline media. The catalyst is highly stable for at least 13 h, with no decrease in the current density. This simple, cost-effective, and environmentally friendly methodology can pave the way for exploitation of MoSx@NiO composite catalysts not only for water splitting, but also for other applications such as lithium ion batteries, and fuel cells.

Lead-free halide double perovskites (A(2)B(I)B(III)X(6)) with attractive optical and electronic features are considered to be a promising candidate to overcome the toxicity and stability issues of lead halide perovskites (APbX(3)). However, their poor absorption profiles limit device performance. Here the absorption band edge of Cs(2)AgBiBr(6)double perovskite to the near-infrared range is significantly broadened by developing doped double perovskites, Cs-2(Ag:Cu)BiBr6. The partial replacement of Ag ions by Cu ions in the crystal lattice is confirmed by the X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (ssNMR) measurements. Cu doping barely affects the bandgap of Cs2AgBiBr6; instead it introduces subbandgap states with strong absorption to the near-infrared range. More interestingly, the near-infrared absorption can generate band carriers upon excitation, as indicated by the photoconductivity measurement. This work sheds new light on the absorption modulation of halide double perovskites for future efficient optoelectronic devices.

High quality opal-like photonic crystals containing graphene are fabricated using evaporation-driven self-assembly of soft polymer colloids. A miniscule amount of pristine graphene within a colloidal crystal lattice results in the formation of colloidal crystals with a strong angle-dependent structural color and a stop band that can be reversibly shifted across the visible spectrum. The crystals can be mechanically deformed or can reversibly change color as a function of their temperature, hence their sensitive mechanochromic and thermochromic response make them attractive candidates for a wide range of visual sensing applications. In particular, it is shown that the crystals are excellent candidates for visual strain sensors or integrated time-temperature indicators which act over large temperature windows. Given the versatility of these crystals, this method represents a simple, inexpensive, and scalable approach to produce multifunctional graphene infused synthetic opals and opens up exciting applications for novel solution-processable nanomaterial based photonics.

Graphene pn-junctions offer a rich portfolio of intriguing physical phenomena. They stand as the potential building blocks for a broad spectrum of future technologies, ranging from electronic lenses analogous to metamaterials in optics, to high-performance photodetectors important for a variety of optoelectronic applications. The production of graphene pn-junctions and their precise structuring at the nanoscale remains to be a challenge. In this work, a scalable method for fabricating periodic nanoarrays of graphene pn-junctions on a technologically viable semiconducting SiC substrate is introduced. Via H-intercalation, 1D confined armchair graphene nanoribbons are transformed into a single 2D graphene sheet rolling over 6H-SiC mesa structures. Due to the different surface terminations of the basal and vicinal SiC planes constituting the mesa structures, different types of charge carriers are locally induced into the graphene layer. Using angle-resolved photoelectron spectroscopy, the electronic band structure of the two graphene regions are selectively measured, finding two symmetrically doped phases with p-type being located on the basal planes and n-type on the facets. The results demonstrate that through a careful structuring of the substrate, combined with H-intercalation, integrated networks of graphene pn-junctions could be engineered at the nanoscale, paving the way for the realization of novel optoelectronic device concepts.

Clinical translation of polymer-based nanocarriers for systemic delivery of RNA has been limited due to poor colloidal stability in the blood stream and intracellular delivery of the RNA to the cytosol. To address these limitations, this study reports a new strategy incorporating photocrosslinking of bioreducible nanoparticles for improved stability extracellularly and rapid release of RNA intracellularly. In this design, the polymeric nanocarriers contain ester bonds for hydrolytic degradation and disulfide bonds for environmentally triggered small interfering RNA (siRNA) release in the cytosol. These photocrosslinked bioreducible nanoparticles (XbNPs) have a shielded surface charge, reduced adsorption of serum proteins, and enable superior siRNA-mediated knockdown in both glioma and melanoma cells in high-serum conditions compared to non-crosslinked formulations. Mechanistically, XbNPs promote cellular uptake and the presence of secondary and tertiary amines enables efficient endosomal escape. Following systemic administration, XbNPs facilitate targeting of cancer cells and tissue-mediated siRNA delivery beyond the liver, unlike conventional nanoparticle-based delivery. These attributes of XbNPs facilitate robust siRNA-mediated knockdown in vivo in melanoma tumors colonized in the lungs following systemic administration. Thus, biodegradable polymeric nanoparticles, via photocrosslinking, demonstrate extended colloidal stability and efficient delivery of RNA therapeutics under physiological conditions, and thereby potentially advance systemic delivery technologies for nucleic acid-based therapeutics.

Designing broadband enhanced chirality is of strong interest to the emerging fields of chiral chemistry and sensing, or to control the spin orbital momentum of photons in recently introduced nanophotonic chiral quantum and classical optical applications. However, chiral light-matter interactions have an extremely weak nature, are difficult to control and enhance, and cannot be made tunable or broadband. In addition, planar ultrathin nanophotonic structures to achieve strong, broadband, and tunable chirality at the technologically important visible to ultraviolet spectrum still remain elusive. Here, these important problems are tackled by experimentally demonstrating and theoretically verifying spectrally tunable, extremely large, and broadband chiroptical response by nanohelical metamaterials. The reported new designs of all-dielectric and dielectric-metallic (hybrid) plasmonic metamaterials permit the largest and broadest ever measured chiral Kuhns dissymmetry factor achieved by a large-scale nanophotonic structure. In addition, the strong circular dichroism of the presented bottom-up fabricated optical metamaterials can be tuned by varying their dimensions and proportions between their dielectric and plasmonic helical subsections. The currently demonstrated ultrathin optical metamaterials are expected to provide a substantial boost to the developing field of chiroptics leading to significantly enhanced and broadband chiral light-matter interactions at the nanoscale.

The thermodynamic parameter pressure is ideal for producing novel ultraincompressible and superhard materials as it promotes the formation of polymeric frameworks and higher atomic coordination. In this regard, carbon and nitrogen are particularly attractive elements as they can produce extended arrangements of strong covalent bonds. In this study, a previously unobserved C3N4 polymorph, denoted as oP28-C3N4 (Pnnm, #58), is synthesized at pressures between 73 and 104 GPa in laser-heated diamond anvil cells and found recoverable to ambient conditions and stable in air. The crystal structure of oP28-C3N4, comprised of corner-sharing CN4 tetrahedra, is solved and refined using synchrotron single-crystal X-ray diffraction. With a bulk modulus of 334(3) GPa deduced from experimental data, the compound is highly incompressible. Based on macroscopic and microscopic calculations, its hardness may achieve 47.5 or 79.7 GPa, respectively, making it a superhard material. Incompressibility of CN4 tetrahedra in all experimentally observed C3N4 polymorphs is found to be greater than that of the CC4 and BN4 tetrahedra forming the structures of diamond and cubic boron nitride. Density functional theory calculations provide further insight into the electronic, vibrational, and mechanical properties of oP28-C3N4, as well as their stability relative to other C & horbar;N phases.

Electrolyte-gated organic field-effect transistors (OFETs) hold promise for robust printed electronics operating at low voltages. The polarization mechanism of thin solid electrolyte films, the gate insulator in such OFETs, is still unclear and appears to limit the transient current characteristics of the transistors. Here, the polarization response of a thin proton membrane, a poly(styrenesulfonic acid) film, is controlled by varying the relative humidity. The formation of the conducting transistor channel follows the polarization of the polyelectrolyte, such that the drain transient current characteristics versus the time are rationalized by three different polarization mechanisms: the dipolar relaxation at high frequencies, the ionic relaxation (migration) at intermediate frequencies, and the electric double-layer formation at the polyelectrolyte interfaces at low frequencies. The electric double layers of polyelectrolyte capacitors are formed in 1 µs at humid conditions and an effective capacitance per area of 10 µF cm^-2 is obtained at 1 MHz, thus suggesting that this class of OFETs might operate at up to 1 MHz at 1 V.

Cs2AgBiBr6, as a benchmark lead-free double perovskite, has emerged as a promising alternative to lead-based perovskites because of its high stability, non-toxicity, exceptional optoelectronic properties, and multifunctionality. To encourage further research on Cs2AgBiBr6 and its broad applications, in this review, its fundamental properties including the structure-property relation, synthesis, stability, origin of absorption and photoluminescence, electron-phonon coupling, role of defects, charge carrier dynamics, and bandgap modulation are comprehensively emphasized. The recent progress on the wide applications including solar cells, light/X-ray detectors, and ferroelectric/magnetic devices are highlighted. Moreover, the challenges of Cs2AgBiBr6 materials and related applications are discussed and perspectives are provided for guiding the future development of this research area.

A zipper-like on/off-switchable molecularly imprinted polymer is reported. This unique imprinted polymer was composed of template-imprinted polymeric networks that incorporate zipper-like interactions between poly(acrylamide) (PAAm) and poly(2-acrylamide-2-methyl propanesulfonic acid) (PAMPS). This polymer showed marginal recognition ability towards the imprint species under low temperature conditions, due to the interpolymer interaction between PAAm and PAMPS, which inhibited access to the imprinted networks. In contrast, at relatively high temperatures (such as 40 degrees C), the polymer demonstrated significant molecular recognition ability towards the imprint species resulting from the dissociation of the interpolymer complexes of PAAm and PAMPS, which enabled access to the imprint networks. Unlike previously reported PNIPAm-based imprinted polymers, which demonstrate alterable molecular recognition simply because of the thermosensitive hydrophilicity/hydrophobicity of PNIPAm, this polymer employed a zipper-like supramolecular architecture between PAAm and PAMPS, thereby enabling switchable molecular recognition.

A catalytic and positively thermosensitive molecularly imprinted polymer is reported. This unique imprinted polymer was composed of 4-nitrophenyl phosphate-imprinted networks that exhibited a thermosensitive interpolymer interaction between poly(2-trifluoromethylacrylic acid) (PTFMA) and poly(1-vinylimidazole) (PVI), which contains catalytically active sites. At a relatively low temperature (such as 20 degrees C), this imprinted polymer did not demonstrate significant catalytic activity for the hydrolysis of 4-nitrophenyl acetate due to the interpolymer complexation between PVI and PTFMA, which blocked access to the active sites of PVI and caused shrinking of the polymer. Conversely, at higher temperatures (such as 40 degrees C), this polymer showed significant catalytic activity resulting from the dissociation of the interpolymer complexes between PVI and PTFMA, which facilitated access to the active sites of PVI and inflated the polymer. Unlike previously reported poly(N-isopropylacrylamide)-based molecularly imprinted polymers, which demonstrated decreased molecular recognition and catalytic activity with increased temperatures, i.e., negatively thermosensitive molecular recognition and catalysis abilities, this imprinted polymer exploits the unique interpolymer interaction between PVI and PTFMA, enabling the reversed thermal responsiveness.

Selective electron transport and extraction are essential to the operation of photovoltaic devices. Electron transport layer (ETL) is therefore critical to organic photovoltaics (OPV). Herein, an ETL configuration is presented comprising a solution-processed n-n organic heterojunction to enhance electron transport and hole blocking, and boost power conversion efficiency (PCE) in OPV. Specifically, the n-n heterojunction is constructed by stacking a narrow-band n-type conjugated polymer layer (PNDIT-F3N) and a wide-band n-type conjugated molecule layer (Phen-NaDPO). Based on the ultraviolet photoelectron spectroscopy measurement and numerical simulation of current density-voltage characteristics, the formation of the built-in potential is investigated. In three OPVs with different active layers, substantial improvements are observed in performance following the introduction of this ETL configuration. The performance enhancement arises from the combination of selective carrier transport properties and reduced recombination. Another contributing factor is the good film-forming quality of the new ETL configuration, where the surface energies of the related materials are well-matched. The n-n organic heterojunction represents a viable and promising ETL construction strategy for efficient OPV devices.

We utilize transient techniques to directly compare the operation of polymer/fullerene, polymer/nanocrystal, and polymer/polymer bulk heterojunction solar cells. For all devices, poly(3-hexylthiophene) (P3HT) is used as the electron donating polymer, in combination with either the fullerene derivative phenyl-C(61)-butyric acid methyl ester (PCBM) in polymer/fullerene cells, CdSe nanoparticles in polymer/nanocrystal cells, or the polyfluorene copolymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3- benzothiadiazole]-2,2-diyl) (F8TBT) in polymer/polymer cells. Transient photocurrent and photovoltage measurements are used to probe the dynamics of charge-separated carriers, with vastly different dynamic behavior observed for polymer/fullerene, polymer/polymer, and polymer/nanocrystal devices on the microsecond to millisecond timescale. Furthermore, by employing transient photocurrent analysis with different applied voltages we are also able to probe the dynamics behavior of these cells from short circuit to open circuit. P3HT/F8TBT and P3HT/CdSe devices are characterized by poor charge extraction of the long-lived carriers attributed to charge trapping. P3HT/PCBM devices, in contrast, show relatively trap-free operation with the variation in the photocurrent decay kinetics with applied bias at low intensity, consistent with the drift of free charges under a uniform electric field. Under solar conditions at the maximum power point, we see direct evidence of bimolecular recombination in the P3HT/PCBM device competing with charge extraction. Transient photovoltage measurements reveal that, at open circuit, photogenerated charges have similar lifetimes in all device types, and hence, the extraction of these long-lived charges is a limiting process in polymer/nanocrystal and polymer/polymer devices.

Transition metal nitrides, particularly those of 5d metals, are known for their outstanding properties, often relevant for industrial applications. Among these metal elements, tungsten is especially attractive given its low cost. In this high-pressure investigation of the W-N system, two novel ultra-incompressible tungsten nitride superconductors, namely W2N3 and W3N5, are successfully synthesized at 35 and 56 GPa, respectively, through a direct reaction between N2 and W in laser-heated diamond anvil cells. Their crystal structure is determined using synchrotron single-crystal X-ray diffraction. While the W2N3 solid's sole constituting nitrogen species are N3- units, W3N5 features both discrete N3- as well as N24- pernitride anions. The bulk modulus of W2N3 and W3N5 is experimentally determined to be 380(3) and 406(7) GPa, and their ultra-incompressible behavior is rationalized by their constituting WN7 polyhedra and their linkages. Importantly, both W2N3 and W3N5 are recoverable to ambient conditions and stable in air. Density functional theory calculations reveal W2N3 and W3N5 to have a Vickers hardness of 30 and 34 GPa, and superconducting transition temperatures at ambient pressure (50 GPa) of 11.6 K (9.8 K) and 9.4 K (7.2 K), respectively. Additionally, transport measurements performed at 50 GPa on W2N3 corroborate with the calculations. Two recoverable tungsten nitrides, namely W2N3 and W3N5, are synthesized using laser-heated diamond anvil cells. Both compounds exhibit a high bulk modulus, hardness, and superconducting transition temperature. image

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

To fabricate stable neat FAPbI(3) perovskite with a pure alpha-phase (pure alpha-FAPbI(3)) is important in the field of photovoltaic commercialization because of its better bandgap than its alloying counterpart with cesium (Cs) or methylammonium (MA) cations. In this work, the first vapor deposited pure alpha-FAPbI(3) thin film solar cell with a power conversion efficiency (PCE) over 20% is achieved by regulating the phase transition process. It is found that under high humidity conditions, a fast phase transition between high-purity alpha- and delta-phase FAPbI(3) can be realized. Moreover, theoretical calculations interestingly reveal a phase transition shortcut induced by the abnormal volume contraction that is ascribed to the formation of double hydrogen bonds at a certain H2O concentration. Therefore, a high-humidity post-treatment strategy is proposed to fabricate alpha-FAPbI(3) solar cells with a champion PCE of 20.19% (0.1 cm(2)) and 18.91% (1 cm(2)), which is currently the highest recorded value in vapor deposited pure alpha-FAPbI(3) perovskite solar cells. This study helps to redefine the effect of a water molecule on FAPbI(3) solar cells. In addition, the demonstrated scaling-up possibility provides another perspective for fabricating uniform high-performance pure alpha-FAPbI(3) perovskite solar cells.