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Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. However, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. To understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figures reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. This mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications. [ABSTRACT FROM AUTHOR]

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational variability and spatial correlation. Our model offers a predictive approach to connecting processing conditions with transport behavior. [ABSTRACT FROM AUTHOR]

We have developed and have applied a mobility edge model that takes drift and diffusion currents to characterize the space-charge-limited current in organic semiconductors into account. The numerical solution of the drift-diffusion equation allows the utilization of asymmetric contacts to describe the built-in potential within the device. The model has been applied to extract information of the distribution of traps from experimental current-voltage measurements of a rubrene single crystal from Krellner et al. [Phys. Rev. B 75, 245115 (2007)] showing excellent agreement across several orders of magnitude in the current. Although the two contacts are made of the same metal, an energy offset of 580 meV between them, ascribed to differences in the deposition techniques (lamination vs evaporation) was essential to correctly interpret the shape of the current-voltage characteristics at low voltage. A band mobility of 0.13 cm² V-1 s-1 for holes is estimated, which is consistent with transport along the long axis of the orthorhombic unit cell. The total density of traps deeper than 0.1 eV was 2.2 x 1016 cm-3. The sensitivity analysis and error estimation in the obtained parameters show that it is not possible to accurately resolve the shape of the trap distribution for energies deeper than 0.3 eV or shallower than 0.1 eV above the valence-band edge. The total number of traps deeper than 0.3 eV, however, can be estimated. Contact asymmetry and the diffusion component of the current play an important role in the description of the device at low bias and are required to obtain reliable information about the distribution of deep traps. [ABSTRACT FROM AUTHOR]

Polymeric semiconductors have attracted much attention because of their possible use as active materials in printed electronics. Thin-film transistors (TFTs) are a convenient tool for studying charge-transport physics in conjugated polymers. Two families of materials are reviewed here: fluorene copolymers and polythiophenes. Because charge transport is highly anisotropic in molecular conductors, the electrical properties of conjugated polymers are strongly dependent on microstructure. Molecular weight, polydispersity, and regioregularity all affect morphology and charge-transport in these materials. Charge transport models based on microstructure are instrumental in identifying the electrical bottlenecks in these materials. [Copyright &y& Elsevier]

Presents evidence for the role of nitric oxide in the discharge of acontial nematocytes. Measurement of nitric oxide synthase activity; Localization of nitric oxide synthase; Perfusion of in situ or isolated nematocytes with exogenous.

Investigates the activation properties of in situ nematocytes of Pelagia noctiluca of Scyphozoa. Calcium ion dependence of nematocyte activation; Inhibitory action of gadolinium.

An organic/inorganic hybrid sensing device is proposed based on a dual-gate organic thin film transistor architecture using polythiophenes as semiconductors and AlOx as the top dielectric. When a polar molecule adsorbs on the top dielectric, the threshold voltage of the bottom gate transistor shifts leading to several orders of magnitude increase of the current at an appropriately chosen gate voltage. The devices are tested by exposing them to a saturated water atmosphere, which leads to a four orders of magnitude current increase within one minute. This sensor design maintains some advantages of organic semiconductors such as low-temperature processing and fabrication on flexible substrates. Finally, it can be operated at low voltages with the potential for extremely low-power operation. [ABSTRACT FROM AUTHOR]

The true structure of alternating conjugated polymers—the state‐of‐the‐art materials for many organic electronics—often deviates from the idealized picture. Homocoupling defects are in fact inherent to the widely used cross‐coupling polymerization methods. Nevertheless, many polymers still perform excellently in the envisaged applications, which raises the question if one should really care about these imperfections. This article looks at the relevance of chemical precision (and lack thereof) in conjugated polymers covering the entire spectrum from the molecular scale, to the micro and mesostructure, up to the device level. The different types of polymerization errors for the alkoxylated variant of the benchmark (semi)crystalline polymer poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (PBTTT) are identified, visualized, and quantified and a general strategy to avoid homocoupling is introduced. Through a combination of experiments and supported by simulations, it is shown that these coupling defects hinder fullerene intercalation and limit device performance as compared to the homocoupling‐free analog. This clearly demonstrates that structural defects do matter and should be generally avoided, in particular when the geometrical regularity of the polymer is essential. These insights likely go beyond the specific PBTTT derivatives studied here and are of general relevance for the wider organic electronics field. [ABSTRACT FROM AUTHOR]

The authors suggest avoidance of kinks when measuring mobility of charge carriers in electronic devices and organic semiconductors. They comment on the measurement of carrier mobility using field-effect transistors (FET), transfer characteristics of a semiconductor device on which carrier mobility is derived, and irregularities in the characteristics of previously reported high performance organic FETs.

The article offers information on enhancement of electronic mobility with plasmonic antennas in organic semiconductors. Topics discussed include proportional relation between rate of charge carrier mobility and coupled electronic structure, use of surface plasmon resonance and analysis of electron's drift velocity.

We present a model of charge transport in polycrystalline electronic films, which considers details of the microscopic scale while simultaneously allowing realistically sized films to be simulated. We discuss the approximations and assumptions made by the model, and rationalize its application to thin films of directionally crystallized poly(3-hexylthiophene). In conjunction with experimental data, we use the model to characterize the effects of defects in these films. Our findings support the hypothesis that it is the directional crystallization of these films, rather than their defects, which causes anisotropic mobilities. [ABSTRACT FROM AUTHOR]

The development of sensor electrode materials for the detection of metabolites will enable point‐of‐care diagnostic devices for the monitoring and treatment of metabolic diseases such as diabetes. Current state‐of‐the‐art glucose sensing electrodes employ the organic salt tetrathiafulvene tetracyanoquinodimethane (TTF TCNQ) to receive electrons directly from enzymatic reactions of glucose. However, TTF TCNQ is insoluble in most solvents, making it challenging to deposit high‐quality electrodes. Furthermore, its hydrophobicity hinders its interface with aqueous solutions in physiological environments. To overcome these issues, TCNQ derivatives are introduced into an electron‐rich and hydrophilic conjugated polymer. Thus, a polymeric electrode is demonstrated that is easily solution processible and can undergo volumetric direct electron transfer with glucose reactions throughout its bulk. This study further elucidates the electron transfer mechanism during chemical doping and metabolite sensing reactions to inform general design rules for this new class of glucose sensing materials. [ABSTRACT FROM AUTHOR]

This communication reports on a versatile and substrate‐agnostic method to tune the surface chemistry of conducting polymers with the aim of bridging the chemical mismatch between bioelectronic devices and biological systems. As a proof of concept, the surface of poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) is grafted with a short‐chain oligoethylene glycol monolayer to favor the formation of cell‐derived supported lipid bilayers (SLBs). This method is tuned to optimize the affinity between the supported lipid bilayer and the conducting polymer, leading to significant improvements in bilayer quality and therefore electronic readouts. To validate the impact of surface functionalization on the system's ability to transduce biological phenomena into quantifiable electronic signals, the activity of a virus commonly used as a surrogate for SARS‐CoV‐2 (mouse hepatitis virus) is monitored with and without surface treatment. The functionalized devices exhibit significant improvements in electronic output, stemming from the improved SLB quality, therefore strengthening the case for the use of such an approach in membrane‐on‐a‐chip systems. [ABSTRACT FROM AUTHOR]

Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film. [ABSTRACT FROM AUTHOR]

Performance of nonfullerene‐based organic solar cells is largely dependent on the donor:acceptor blend morphology, which is initially tuned by composition. However, morphological design rules are difficult to identify due to the complex relationship between composition‐dependent phase behavior and performance properties. In this study, the authors are able to establish a direct link between PM6:Y6 film morphology and device properties by combining grazing‐incidence wide‐angle X‐ray scattering with highly sensitive Fourier transform photocurrent spectroscopy. By analyzing properties across the full composition range, interfacial microstructure and the corresponding charge transfer (CT) states are identified and direct structure–property relationships are established. The results indicate that open‐circuit voltage is controlled by the CT state at amorphous‐PM6:crystalline‐Y6 interfaces. Crystalline Y6 is found to increase both transport and non‐radiative recombination, suggesting that morphological tradeoffs may be necessary for overall device optimization. [ABSTRACT FROM AUTHOR]

We present a universal model for the transient drain current response in organic electrochemical transistors (OECTs). Using equivalent circuits and charge injection physics, we are able to predict the drain current in OECT devices upon application of a gate voltage input. The model is applicable to both plain and membrane-functionalized devices, and allows us to extract useful physical quantities such as resistances and capacitances, which are related to functional properties of the system. We are also able to use the model to reconstruct the magnitude and shape in time of an applied voltage source based on the observed drain current response. This was experimentally demonstrated for drain current measurements under an applied action potential. [ABSTRACT FROM AUTHOR]

A grand challenge in materials science is to identify the impact of molecular composition and structure across a range of length scales on macroscopic properties. We demonstrate a unified experimental-theoretical framework that coordinates experimental measurements of mesoscale structure with molecular-level physical modeling to bridge multiple scales of physical behavior. Here we apply this framework to understand charge transport in a semiconducting polymer. Spatially-resolved nanodiffraction in a transmission electron microscope is combined with a self-consistent framework of the polymer chain statistics to yield a detailed picture of the polymer microstructure ranging from the molecular to device relevant scale. Using these data as inputs for charge transport calculations, the combined multiscale approach highlights the underrepresented role of defects in existing transport models. Short-range transport is shown to be more chaotic than is often pictured, with the drift velocity accounting for a small portion of overall charge motion. Local transport is sensitive to the alignment and geometry of polymer chains. At longer length scales, large domains and gradual grain boundaries funnel charges preferentially to certain regions, creating inhomogeneous charge distributions. While alignment generally improves mobility, these funneling effects negatively impact mobility. The microstructure is modified in silico to explore possible design rules, showing chain stiffness and alignment to be beneficial while local homogeneity has no positive effect. This combined approach creates a flexible and extensible pipeline for analyzing multiscale functional properties and a general strategy for extending the accesible length scales of experimental and theoretical probes by harnessing their combined strengths. [ABSTRACT FROM AUTHOR]

2D hybrid perovskites are attractive for optoelectronic devices. In thin films, the color of optical emission and the texture of crystalline domains are often difficult to control. Here, a method for extinguishing or enhancing different emission features is demonstrated for the family of 2D Ruddlesden–Popper perovskites (EA1−xFAx)4Pb3Br10 (EA = ethylammonium, FA = formamidinium). When grown from aqueous hydrobromic acid, crystals of (EA1−xFAx)4Pb3Br10 retain all the emission features of their parent compound, (EA)4Pb3Br10. Surprisingly, when grown from dimethylformamide (DMF), an emission feature, likely self‐trapped exciton (STE), near 2.7 eV is missing. Extinction of this feature is correlated with DMF being incorporated between the 2D Pb‐Br sheets, forming (EA1−xFAx)4Pb3Br10∙(DMF)y. Without FA, films grown from DMF form (EA)4Pb3Br10, retain little solvent, and have strong emission near 2.7 eV. Slowing the kinetics of film growth strengthens a different emission feature, likely a different type of STE, which is much broader and present in all compositions. Films of (EA1−xFAx)4Pb3Br10∙(DMF)y have large, micron‐sized domains and homogeneous orientation of the semiconducting sheets, resulting in low electronic disorder near the absorption edge. The ability to selectively strengthen or extinguish different emission features in films of (EA1−xFAx)4Pb3Br10∙(DMF)y reveals a pathway to tune the emission color in these compounds. [ABSTRACT FROM AUTHOR]

Organic ternary heterojunction photovoltaic blends are sometimes observed to undergo a gradual evolution in open-circuit voltage (Voc) with increasing amounts of a second donor or an acceptor. The Voc is strongly correlated with the energy of the charge transfer state in the blend, but this value depends on both local and mesoscopic orders. In this work, the behavior of Voc in the presence of a wide range of interfacial electronic states is investigated. The key charge transfer state interfaces responsible for Voc in several model systems with varying morphology are identified. Systems consisting of one donor with two fullerene molecules and of one acceptor with a donor polymer of varying regio-regularity are used. The effects from the changing energetic disorder in the material and from the variation due to a law of simple mixtures are quantified. It has been found that populating the higher-energy charge transfer states is not responsible for the observed change in Voc upon the addition of a third component. Aggregating polymers and miscible fullerenes are compared, and it has been concluded that in both cases charge delocalization, aggregation, and local polarization effects shift the lowestenergy charge transfer state distribution. [ABSTRACT FROM AUTHOR]

Synaptic devices with linear high‐speed switching can accelerate learning in artificial neural networks (ANNs) embodied in hardware. Conventional resistive memories however suffer from high write noise and asymmetric conductance tuning, preventing parallel programming of ANN arrays. Electrochemical random‐access memories (ECRAMs), where resistive switching occurs by ion insertion into a redox‐active channel, aim to address these challenges due to their linear switching and low noise. ECRAMs using 2D materials and metal oxides however suffer from slow ion kinetics, whereas organic ECRAMs enable high‐speed operation but face challenges toward on‐chip integration due to poor temperature stability of polymers. Here, ECRAMs using 2D titanium carbide (Ti3C2Tx) MXene that combine the high speed of organics and the integration compatibility of inorganic materials in a single high‐performance device are demonstrated. These ECRAMs combine the speed, linearity, write noise, switching energy, and endurance metrics essential for parallel acceleration of ANNs, and importantly, they are stable after heat treatment needed for back‐end‐of‐line integration with Si electronics. The high speed and performance of these ECRAMs introduces MXenes, a large family of 2D carbides and nitrides with more than 30 stoichiometric compositions synthesized to date, as promising candidates for devices operating at the nexus of electrochemistry and electronics. [ABSTRACT FROM AUTHOR]

Synaptic devices with linear high‐speed switching can accelerate learning in artificial neural networks (ANNs) embodied in hardware. Conventional resistive memories however suffer from high write noise and asymmetric conductance tuning, preventing parallel programming of ANN arrays. Electrochemical random‐access memories (ECRAMs), where resistive switching occurs by ion insertion into a redox‐active channel, aim to address these challenges due to their linear switching and low noise. ECRAMs using 2D materials and metal oxides however suffer from slow ion kinetics, whereas organic ECRAMs enable high‐speed operation but face challenges toward on‐chip integration due to poor temperature stability of polymers. Here, ECRAMs using 2D titanium carbide (Ti3C2Tx) MXene that combine the high speed of organics and the integration compatibility of inorganic materials in a single high‐performance device are demonstrated. These ECRAMs combine the speed, linearity, write noise, switching energy, and endurance metrics essential for parallel acceleration of ANNs, and importantly, they are stable after heat treatment needed for back‐end‐of‐line integration with Si electronics. The high speed and performance of these ECRAMs introduces MXenes, a large family of 2D carbides and nitrides with more than 30 stoichiometric compositions synthesized to date, as promising candidates for devices operating at the nexus of electrochemistry and electronics. [ABSTRACT FROM AUTHOR]

The performance of polymer:fullerenesolar cells is strongly affectedby the active layer morphology and polymer microstructure. In thisPerspective, we review ongoing research on how structural factorsinfluence the photogeneration and collection of charge carriers aswell as charge carrier recombination and the related open-circuitvoltage. We aim to highlight unexplored research opportunities andprovide some guidelines for the synthesis of new conjugated polymersfor high-efficiency solar cells. [ABSTRACT FROM AUTHOR]

The effect of strain and oxygen deficiency on the Raman spectrum of monoclinic HfO2 is investigated theoretically using first-principles calculations. 1% in-plane compressive strain applied to a and c axes is found to blue shift the phonon frequencies, while 1% tensile strain does the opposite. The simulations are compared, and good agreement is found with the experimental results of Raman frequencies greater than 110 cm-1 for 50 nm HfO2 thin films. Several Raman modes measured below 110 cm-1 and previously assigned to HfO2 are found to be rotational modes of gases present in air ambient (nitrogen and oxygen). However, localized vibrational modes introduced by threefold-coordinated oxygen (O3) vacancies are identified at 96.4 cm-1computationally. These results are important for a deeper understanding of vibrational modes in HfO2, which has technological applications in transistors and particularly in resistive random-access memory whose operation relies on oxygen-deficient HfOx. [ABSTRACT FROM AUTHOR]

In organic mixed ionic–electronic conductors (OMIECs), it is critical to understand the motion of ions in the electrolyte and OMIEC. Generally, the focus is on the movement of net charge during gating, and the motion of neutral anion–cation pairs is seldom considered. Uptake of mobile ion pairs by the semiconductor before electrochemical gating (passive uptake) can be advantageous as this can improve device speed, and both ions can participate in charge compensation during gating. Here, such passive ion pair uptake in high‐speed solid‐state devices is demonstrated using an ion gel electrolyte. This is compared to a polymerized ionic liquid (PIL) electrolyte to understand how ion pair uptake affects device characteristics. Using X‐ray photoelectron spectroscopy, the passive uptake of ion pairs from the ion gel into the OMIEC is detected, whereas no uptake is observed with a PIL electrolyte. This is corroborated by X‐ray scattering, which reveals morphological changes to the OMIEC from the uptake of ion pairs. With in situ Raman, a reorganization of both anions and cations is then observed during gating. Finally, the speed and retention of OMIEC‐based neuromorphic devices are tuned by controlling the freedom of charge motion in the electrolyte. [ABSTRACT FROM AUTHOR]

Weinvestigate solution based fabrication of high-k ZrO2thinfilms for low-voltage-operated organic field effect transistors(OFETs). An alternative UV curing method for the densification ofZr-based gel films, which allows for low-temperature processing, iscompared to the conventional thermal annealing method. Elemental andmicrostructural analysis shows that UV-curing induces the decompositionof organic-metal bonds and causes the densification of the metal oxidefilm, just as the conventional thermal annealing of gel films does,resulting in a high-k dielectric layer from Zr-based solutions. Furthermore,we found that the low temperature associated with UV-curing preventsthe interface layer from intermixing with the substrate. FabricatedZrO2films (5–6 nm in thickness) treated with anoctadecylphosphonic acid self-assembled monolayer exhibit low leakagecurrent density (below 10–6to 10–7A/cm2) at 3 V and high dielectric breakdown strength(V> 4 V). Using this dielectric layer, solutionprocessable polymer OFETs with PBTTT-C-14 as the organic semiconductorfunction well at low voltage (below −3 V.) The effect of self-assembledmonolayers (SAMs)on the morphology and microstructure of the organic semiconductordeposited on the ZrO2dielectrics are investigated. Finally,we demonstrate solution-processable, low-temperature fabrication ofOFETs on a flexible substrate. [ABSTRACT FROM AUTHOR]

Crystallite orientations, molecular packing disorder, and hole mobility of poly(3-hexylthiophene) thin films that are spin casted from different solvents are studied as a function of film thickness. Grazing incidence x-ray diffraction reveals that films consist of an ultrathin layer of ordered, edge-on oriented aggregates and a more disordered, face-on oriented bulk region. Diffraction and optical absorption spectroscopy elucidate the film-forming process. Field-effect hole mobility provides evidence for interconnecting aggregates as the mechanism for efficient charge transport. [ABSTRACT FROM AUTHOR]

We used a mobility edge transport model and solved the drift-diffusion equation to characterize the space-charge-limited current of a rubrene single-crystal hole-only diode. The current-voltage characteristics suggest that current is injection-limited at high voltage when holes are injected from the bottom contact (reverse bias). In contrast, the low-voltage regime shows that the current is higher when holes are injected from the bottom contact as compared to hole injection from the top contact (forward bias), which does not exhibit injection-limited current in the measured voltage range. This behavior is attributed to an asymmetric distribution of trap states in the semiconductor, specifically, a distribution of traps located near the top contact. Accounting for a localized trap distribution near the contact allows us to reproduce the temperature-dependent current-voltage characteristics in forward and reverse bias simultaneously, i.e., with a single set of model parameters. We estimated that the local trap distribution contains 1.19 × 1011 cm-2 states and decays as exp(--x/32.3 nm) away from the semiconductor-contact interface. The local trap distribution near one contact mainly affects injection from the same contact, hence breaking the symmetry in the charge transport. The model also provides information of the band mobility, energy barrier at the contacts, and bulk trap distribution with their corresponding confidence intervals. [ABSTRACT FROM AUTHOR]

The high performance of polycrystalline CdTethin film solar cells is enabled by annealing in the presence of Cl. This process is typically carried out for tens of minutes resulting in reduction of defect states within the bandgap among other beneficial effects. In this work, we investigate laser annealing as a means of rapidly annealing CdTe using a continuous wave sub-bandgap 1064 nm laser. The partial transmission of the beam allows us to monitor the annealing process in-situ and in real time. We find that optoelectronic and structural changes occur through two distinct kinetic processes resulting in the removal of deep defects and twinned regions, respectively. A multilayer optical model including surface roughness is used to interpret both the in-situ transmission as well as ex-situreflectivitymeasurements. These experiments demonstrate beneficial material changes resulting from sub-bandgap laser-driven CdCl2 treatment of CdTe in minutes, which is an important step towards accelerating the processing of the CdTe absorber layer. [ABSTRACT FROM AUTHOR]

Neuromorphic computing is becoming increasingly prominent as artificial intelligence (AI) facilitates progressively seamless interaction between humans and machines. The conventional von Neumann architecture and complementary metal-oxide-semiconductor transistor scaling are unable to meet the highly demanding computational density and energy efficiency requirements of AI. Neuromorphic computing aims to address these challenges by using brain-like computing architectures and novel synaptic memories that coallocate information storage and computation, thereby enabling low latency at high energy efficiency and high memory density. Though various emerging memory devices have been extensively studied to emulate the functionality of biological synapses, there is currently no material/device system that encompasses both the needed metrics for high-performance neuromorphic computing and the required biocompatibility for potential body-computer integration. In this review, we aim to equip the reader with general design principles and materials requirements for realizing high-performance organic neuromorphic devices. We use instructive examples from recent literature to discuss each requirement, illustrating the challenges as well as future research opportunities. Though organic devices still face many challenges to become major players in neuromorphic computing, mostly due to their lack of compliance with back-end-of-line processes required for integration with digital logic, we propose that their biocompatibility and mechanical conformability give them an advantage for creating adaptive biointerfaces, brain-machine interfaces, and biology-inspired prosthetics. [ABSTRACT FROM AUTHOR]

Electrochemically induced volume changes in organic mixed ionic‐electronic conductors (OMIECs) are particularly important for their use in dynamic microfiltration systems, biomedical machinery, and electronic devices. Although significant advances have been made to maximize the dimensional changes that can be accomplished by OMIECs, there is currently limited understanding of how changes in their molecular structures impact their underpinning fundamental processes and their performance in electronic devices. Herein, a series of ethylene glycol functionalized conjugated polymers is synthesized, and their electromechanical properties are evaluated through a combined approach of experimental measurements and molecular dynamics simulations. As demonstrated, alterations in the molecular structure of OMIECs impact numerous processes occurring during their electrochemical swelling, with sidechain length shortening decreasing the number of incorporated water molecules, reducing the generated void volumes and promoting the OMIECs to undergo different phase transitions. Ultimately, the impact of these combined molecular processes is assessed in organic electrochemical transistors, revealing that careful balancing of these phenomena is required to maximize device performance. [ABSTRACT FROM AUTHOR]

Organic electrochemical transistors (OECTs) have exhibited promising performance as transducers and amplifiers of low potentials due to their exceptional transconductance, enabled by the volumetric charging of organic mixed ionic/electronic conductors (OMIECs) employed as the channel material. OECT performance in aqueous electrolytes as well as the OMIECs' redox activity has spurred a myriad of studies employing OECTs as chemical transducers. However, the OECT's large (potentiometrically derived) transconductance is not fully leveraged in common approaches that directly conduct chemical reactions amperometrically within the OECT electrolyte with direct charge transfer between the analyte and the OMIEC, which results in sub‐unity transduction of gate to drain current. Hence, amperometric OECTs do not truly display current gains in the traditional sense, falling short of the expected transistor performance. This study demonstrates an alternative device architecture that separates chemical transduction and amplification processes on two different electrochemical cells. This approach fully utilizes the OECT's large transconductance to achieve current gains of 103 and current modulations of four orders of magnitude. This transduction mechanism represents a general approach enabling high‐gain chemical OECT transducers. [ABSTRACT FROM AUTHOR]

Since reports that silicon nanocrystals (Si-NCs) can exhibit direct transition emission, the silicon laser field is at a juncture where the importance of this discovery needs to be evaluated. Most theoretical models predicted a monotonic increase in the bandgap and experimental information currently available on the electronic structure at the Γ valley of these promising materials is circumstantial as it is obtained from emission measurements where competing non-radiative relaxation and recombination processes only provide an incomplete picture of the electronic structure of Si-NCs. Optical absorption, the most immediate probe of the electronic structure beyond the band-edges, showing the evolution of the Γ valley states with nanocrystal size has not been measured. Here, we show such measurements, performed with high dynamic range, allowing us to observe directly the effect of crystal size on the Γ valley splitting far above the band-edges. We show that the splitting is 100 s of meV more pronounced than predicted by pseudo potential calculations and Luttinger-Kohn model. We also show that ultrafast red-shifting emission can be observed in plasma enhanced chemical vapor deposition prepared Si-NCs. [ABSTRACT FROM AUTHOR]

Thin-film transistors (TFTs) of polymeric semiconductors were fabricated using selective dewetting in the patterning process. The process consists of: (i) patterning the wettability of the substrate using a protective layer of printed wax and a self-assembled monolayer, and (ii) patterning a polymeric semiconductor by selective dewetting from an organic solution. The method has been used to fabricate small arrays of TFTs with a regioregular poly(thiophene) and poly(9-9′-dioctyl-fluorene-co-bithiophene). The TFTs exhibited mobilities of 0.5-1.0 x 10[SUP-3] cm[SUP2] V[SUP-1] s[SUP-1] and on-to-off ratios on the order of 10[SUP4]. [ABSTRACT FROM AUTHOR]

The correlation between morphology and optoelectronic performance in organic thin‐film transistors based on blends of photochromic diarylethenes (DAE) and poly(3‐hexylthiophene) (P3HT) is investigated by varying molecular weight (Mw = 20–100 kDa) and regioregularity of the conjugated polymer as well as the temperature of thermal annealing (rt‐160 °C) in thin films. Semicrystalline architectures of P3HT/DAE blends comprise crystalline domains, ensuring efficient charge transport, and less aggregated regions, where DAEs are located as a result of their spontaneous expulsion from the crystalline domains during the self‐assembly. The best compromise between field‐effect mobility (μ) and switching capabilities is observed in blends containing P3HT with Mw = 50 kDa, exhibiting μ as high as 1 × 10−3 cm2 V−1 s−1 combined with a >50% photoswitching ratio. Higher or lower Mw than 50 kDa are found to be detrimental for field‐effect mobility and to lead to reduced device current switchability. The microstructure of the regioregular P3HT blend is found to be sensitive to the thermal annealing temperature, with an increase in μ and a decrease in current modulation being observed as a response to the light‐stimulus likely due to an increased P3HT‐DAE segregation, partially hindering DAE photoisomerization. The findings demonstrate the paramount importance of fine tuning the structure and morphology of bicomponent films for leveraging the multifunctional nature of optoelectronic devices. [ABSTRACT FROM AUTHOR]

Conjugated polymers that support mixed (electronic and ionic) conduction are in demand for applications spanning from bioelectronics to energy harvesting and storage. To design polymer mixed conductors for high‐performance electrochemical devices, relationships between the chemical structure, charge transport, and morphology must be established. A polymer series bearing the same p‐type conjugated backbone with increasing percentage of hydrophilic, ethylene glycol side chains is synthesized, and their performance in aqueous electrolyte gated organic electrochemical transistors (OECTs) is studied. By using device physics principles and electrochemical analyses, a direct relationship is found between the OECT performance and the balanced mixed conduction. While hydrophilic side chains are required to facilitate ion transport—thus enabling OECT operation—swelling of the polymer is not de facto beneficial for balancing mixed conduction. It is shown that heterogeneous water uptake disrupts the electronic conductivity of the film, leading to OECTs with lower transconductance and slower response times. The combination of in situ electrochemical and structural techniques shown here contributes to the establishment of the structure–property relations necessary to improve the performance of polymer mixed conductors and subsequently of OECTs. [ABSTRACT FROM AUTHOR]

Cell membranes are fundamental for cellular function as they protect the cell and control passage in and out of the cell. Despite their clear significance, cell membranes are often difficult to study, due to their complexity and the lack of available technologies to interface with them and transduce their functions. Overcoming this complexity by developing simple, reductionist models can facilitate their study. Indeed, lipid layers represent a simplified yet representative model for a cell membrane. Lipid layers are highly insulating, a property that is directly affected by changes in lipid packing or membrane fluidity. Such physical changes in the membrane models can be characterized by coupling them with an electronic transducer. Herein, a lipid monolayer that is stabilized between two immiscible solvents is integrated with an organic electrochemical transistor, which is capable of operating in a biphasic solvent mixture. The platform is used to evaluate how lidocaine, a widely used anesthetic the working mechanism of which is still a matter of debate, interacts with the cell membrane. The present study provides evidence that the anesthetic directly interacts with the lipids in the membrane, affecting their packing and therefore the monolayer permeability. The proposed platform provides an elegant solution for studying compound–membrane interactions. [ABSTRACT FROM AUTHOR]

• A metal-oxide pyramid texture is converted into the non-resonant optical metasurfaces. • Metasurfaces are realized through the templated growth electrodeposition of nanowires. • A J SC gain of 10-25% is achieved as compared to the planar device. • Energy conversion efficiencies of perovskite/perovskite TSCs can reach over 30%. • Optics of solar cells is investigated by FDTD optical simulations. The short-circuit current density and energy conversion efficiency of single-junction perovskite and perovskite/perovskite tandem solar cells can be increased by photon management. In this study, optical metasurfaces were investigated as potential light trapping structures oppose to commonly used pyramidal surface textures. Herein, metal oxide-based non-resonant metasurfaces were investigated as potential light-trapping structures in perovskite solar cells. The zinc oxide nanowire-based building blocks of the metasurface can be prepared by a templated electrodeposition through a mask of resist. The phase of the incident light can be controlled by the edge length of the subwavelength large zinc oxide nanowires. An array of zinc oxide nanowires was prepared and characterized in the current study. Three-dimensional (3D) finite-difference time-domain (FDTD) optical simulations were used to compare solar cells covered with non-resonant metasurfaces with commonly used light trapping structures. As compared to the solar cells covered with zinc oxide pyramid surface texture, solar cells with the integrated non-resonant metasurfaces exhibit almost identical quantum efficiencies and short-circuit current densities. Investigations of such metasurfaces will not only improve the photon absorption in perovskite solar cells but also reveal a pathway to make high-efficiency next-generation solar cells. Detailed guidelines for the realization of non-resonant metal oxide metasurfaces will be provided. [ABSTRACT FROM AUTHOR]

The analysis of transparent conducting oxide nanostructures suffers from a lack of high throughput yet quantitatively sensitive set of analytical techniques that can properly assess their electrical properties and serve both as characterization and diagnosis tools. This is addressed by applying a comprehensive set of characterization techniques to study the electrical properties of solution-grown Al-doped ZnO nanowires as a function of composition from 0 to 4 at. % Al:Zn. Carrier mobility and charge density extracted from sensitive optical absorption measurements are in agreement with those extracted from single-wire field-effect transistor devices. The mobility in undoped nanowires is 28 cm2/V s and decreases to ∼14 cm2/V s at the highest doping density, though the carrier density remains approximately constant (1020 cm-3) due to limited dopant activation or the creation of charge-compensating defects. Additionally, the local geometry of the Al dopant is studied by nuclear magnetic resonance, showing the occupation of a variety of dopant sites. [ABSTRACT FROM AUTHOR]

The article discusses research on the use of scalable neuromorphic computers in relation to the parallel programming of ionic floating-gate (IFG) memory arrays. Topics include the role of conductive-bridge memory (CBM), the use of artificial neural network (ANN) learning, and complementary metal oxide semiconductor (CMOS). The use of a redox transistor array is noted.

A variety of optical applications rely on the absorption and reemission of light. The quantum yield of this process often plays an essential role. When the quantum yield deviates from unity by significantly less than 1%, applications such as luminescent concentrators and optical refrigerators become possible. To evaluate such high performance, we develop a measurement technique for luminescence efficiency with sufficient accuracy below one part per thousand. Photothermal threshold quantum yield is based on the quantization of light to minimize overall measurement uncertainty. This technique is used to guide a procedure capable of making ensembles of near-unity emitting cadmium selenide/cadmium sulfide (CdSe/CdS) core-shell quantum dots. We obtain a photothermal threshold quantum yield luminescence efficiency of 99.6 ± 0.2%, indicating nearly complete suppression of nonradiative decay channels. [ABSTRACT FROM AUTHOR]

Abstract: Poly (3‐hexylthiophene) (P3HT) was an early frontrunner in the development of donor polymers to be used in organic photovoltaics. A relatively straightforward and inexpensive synthesis suggests that it may be the most viable donor polymer to use in large‐scale commercial organic solar cells. Replacing fullerenes with new electron acceptors has led to significant improvements in device performance and stability, with devices now able to exceed an efficiency of 7%. Past studies have reported a dependence of device performance on the molecular weight of the polymer in fullerene‐containing blends, however, with nonfullerene acceptors now showing promise a similar study was needed. P3HT blends, with two nonfullerene acceptors (O‐IDTBR and EH‐IDTBR), were probed using a number of polymer batches with varying molecular weights. O‐IDTBR was shown to exhibit a dependence on the polymer molecular weight, with optimal performance achieved with a 34 kDa polymer, while EH‐IDTBR displayed an independence in performance with varying polymer molecular weight. Probing the thermal and morphological behavior of the P3HT:O‐IDTBR blends suggests that an optimal morphology with pronounced donor and acceptor domains was only achieved with the 34 kDa polymer, and a greater degree of mixing was exhibited in the other blends, likely leading to poorer device performance. [ABSTRACT FROM AUTHOR]

The article focuses on a study regarding molecularly selective nanoporous membrane-based wearable organic electrochemical device for noninvasive cortisol sensing. It mentions that wearable biosensors have emerged as an alternative evolutionary development in the field of healthcare technology due to their potential to change conventional medical diagnostics and health monitoring.

We demonstrate a facile method to improve upconversion quantum yields in Yb,Er-based nanoparticles via emission dye-sensitization. Using the commercially available dye ATTO 542, chosen for its high radiative rate and significant spectral overlap with the green emission of Er3+, we decorate the surfaces of sub-25 nm hexagonal-phase Na(Y/Gd/Lu)0.8F4:Yb0.18Er0.02 upconverting nanoparticles with varying dye concentrations. Upconversion photoluminescence and absorption spectroscopy provide experimental confirmation of energy transfer to and emission from the dye molecules. Upconversion quantum yield is observed to increase with dye sensitization, with the highest enhancement measured for the smallest particles investigated (10.9 nm in diameter); specifically, these dye-decorated particles are more than 2× brighter than are unmodified, organic-soluble nanoparticles and more than 10× brighter than are water-soluble nanoparticles. We also observe 3× lifetime reductions with dye adsorption, confirming the quantum yield enhancement to result from the high radiative rate of the dye. The approach detailed in this work is widely implementable, renders the nanoparticles water-soluble, and most significantly improves sub-15 nm nanoparticles, making our method especially attractive for biological imaging applications. [ABSTRACT FROM AUTHOR]

In this review we focus on demonstrating how organic electronic materials can solve key problems in biosensing thanks to their unique material properties and implementation in innovative device configurations. We highlight specific examples where these materials solve multiple issues related to complex sensing environments, and we benchmark these examples by comparing them to state-of-the-art commercially available sensing using alternative technologies. We have categorized our examples by sample type, focusing on sensing from body fluids in vitro and on wearable sensors, which have attracted significant interest owing to their integration with everyday life activities. We finish by describing a future trend for in vivo , implantable sensors, which aims to build on current progress from sensing in biological fluids ex vivo . [ABSTRACT FROM AUTHOR]

In organic solar cells (OSCs), the energy of the charge-transfer (CT) complexes at the donor-acceptor interface, ECT, determines the maximum open-circuit voltage ( VOC). The coexistence of phases with different degrees of order in the donor or the acceptor, as in blends of semi-crystalline donors and fullerenes in bulk heterojunction layers, influences the distribution of CT states and the VOC enormously. Yet, the question of how structural heterogeneities alter CT states and the VOC is seldom addressed systematically. In this work, we combine experimental measurements of vacuum-deposited rubrene/C60 bilayer OSCs, with varying microstructure and texture, with density functional theory calculations to determine how relative molecular orientations and extents of structural order influence ECT and VOC. We find that varying the microstructure of rubrene gives rise to CT bands with varying energies. The CT band that originates from crystalline rubrene lies up to ≈0.4 eV lower in energy compared to the one that arises from amorphous rubrene. These low-lying CT states contribute strongly to VOC losses and result mainly from hole delocalization in aggregated rubrene. This work points to the importance of realizing interfacial structural control that prevents the formation of low ECT configurations and maximizes VOC. [ABSTRACT FROM AUTHOR]

Intercalated molecules can dramatically modify the electronic band structure of layered semiconductors, significantly altering the optical properties of the material. In the layered monochalcogenide Gallium Telluride (GaTe), exposure to air induces a nearly 1 eV reduction of its band gap due to the interlayer diffusion and chemisorption of oxygen. The effect of oxygen chemisorption at the Te-terminated surfaces on the structure of GaTe, however, is much less known. To better understand the structure-property relationship of intercalated GaTe, a systematic, long-term, X-ray diffraction study has been performed on GaTe exfoliated crystals exposed to ambient conditions. It is observed that the structural changes are not limited to a previously observed short-term increase in lattice expansion. Over the course of months and even years after exfoliation, the oxygen adsorbates continue to modify the structure of GaTe, inducing significant disorder and grain reorientation. It is estimated that approximately one out of every two grains is slightly displaced by the intercalating oxygen, demonstrating a significant increase in grain mosaicity, while still maintaining the original {−2 0 1} out-of-plane texture. Correlating these structural transformations to observed changes in electrical and optical properties will enable capitalization of the use of adsorbates to engineer novel properties in these layered materials. [ABSTRACT FROM AUTHOR]

Doping of organic bulk heterojunction solar cells has the potential to improve their power conversion efficiency (PCE). Deconvoluting the effect of doping on charge transport, recombination, and energetic disorder remains challenging. It is demonstrated that molecular doping has two competing effects: on one hand, dopant ions create additional traps while on the other hand free dopant-induced charges fill deep states possibly leading to VOC and mobility increases. It is shown that molar dopant concentrations as low as a few parts per million can improve the PCE of organic bulk heterojunctions. Higher concentrations degrade the performance of the cells. In doped cells where PCE is observed to increase, such improvement cannot be attributed to better charge transport. Instead, the VOC increase in unannealed P3HT:PCBM cells upon doping is indeed due to trap filling, while for annealed P3HT:PCBM cells the change in VOC is related to morphology changes and dopant segregation. In PCDTBT:PC70BM cells, the enhanced PCE upon doping is explained by changes in the thickness of the active layer. This study highlights the complexity of bulk doping in organic solar cells due to the generally low doping efficiency and the constraint on doping concentrations to avoid carrier recombination and adverse morphology changes. [ABSTRACT FROM AUTHOR]

The energy landscape in organic semiconducting materials greatly influences charge and exciton behavior, which are both critical to the operation of organic electronic devices. These energy landscapes can change dramatically depending on the phases of material present, including pure phases of one molecule or polymer and mixed phases exhibiting different degrees of order and composition. In this work, ultraviolet photoelectron spectroscopy measurements of ionization energies (IEs) and external quantum efficiency measurements of charge-transfer (CT) state energies ( ECT) are applied to molecular photovoltaic material systems to characterize energy landscapes. The results show that IEs and ECT values are highly dependent on structural order and phase composition. In the sexithiophene:C60 system both the IEs of sexithiophene and C60 shift by over 0.4 eV while ECT shifts by 0.5 eV depending on molecular composition. By contrast, in the rubrene:C60 system the IE of rubrene and C60 vary by ≤0.11 eV and ECT varies by ≤0.04 eV as the material composition varies. These results suggest that energy landscapes can exist whereby the binding energies of the CT states are overcome by energy offsets between charges in CT states in mixed regions and free charges in pure phases. [ABSTRACT FROM AUTHOR]

Charge carrier mobilities in conjugated semicrystalline polymers depend on morphological parameters such as crystallinity, crystal orientation, and connectivity between ordered regions. Despite recent progress in the development of conducting polymers, the complex interplay between the aforementioned parameters and their impact on charge transport is not fully understood. By varying the casting solvents and thermal annealing, we have systematically modulated the crystallization of poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly[2,5-bis(3-hexadecylthiophen-2-yl)thieno(3,2-b)thiophene] (PBTTT) thin films to examine the role of microstructure on charge mobilities. In particular, we achieve equal crystallinities through different processing routes to examine the role of structural parameters beyond the crystallinity on charge mobilities. As expected, a universal relationship does not exist between the crystallinity in either P3HT and PBTTT active layers and the charge mobility in devices. In P3HT films, higher boiling point solvents yield longer conjugation lengths, an indicator of stronger intracrystalline order, and therefore higher device mobilities. In contrast, the charge mobilities of PBTTT devices depend on the interconnectivity between crystallites and intercrystalline order in the active layer. [ABSTRACT FROM AUTHOR]

Tunable aliovalent doping is critical to controlling the optoelectronic properties of semiconductor nanocrystal systems. However, unintentional dopant-induced shape evolution and kinetically limited doping reactions in low-temperature nanocrystal syntheses make it difficult to independently control shape and incorporate dopants in colloidal metal oxide nanocrystals. Here, we demonstrate a synthetic strategy for achieving simultaneous control of both nanorod shape and dopant concentration in colloidal zinc oxide nanorods. We show that this approach succeeds in doping zinc oxide nanorods using Group III dopants (indium or aluminum) in varying concentrations, and we quantify the effects of dopant incorporation on the structural, optical, and plasmonic properties of the nanorods. The synthesis of undoped zinc oxide nanorod templates and subsequent addition of dopant salts to the ongoing reaction enables both shape retention and dopant incorporation. Subsequent growth of an undoped shell on the nanorods incorporates surface segregated dopants with high efficiency. This "core/shell" doping strategy presents a general route to achieving controlled dopant incorporation and morphological retention in anisotropic metal oxide nanocrystal systems. [ABSTRACT FROM AUTHOR]