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Liquid organic hydrogen carriers such as alcohols and polyols are a high-capacity means of transporting and reversibly storing hydrogen that demands effective catalysts to drive the (de)hydrogenation reactions under mild conditions. We employed a combined theory/experiment approach to develop MOF-74 catalysts for alcohol dehydrogenation and examine the performance of the open metal sites (OMS), which have properties analogous to the active sites in high-performance single-site catalysts and homogeneous catalysts. Methanol dehydrogenation was used as a model reaction system for assessing the performance of five monometallic M-MOF-74 variants (M = Co, Cu, Mg, Mn, Ni). Co-MOF-74 and Ni-MOF-74 give the highest H2 productivity. However, Ni-MOF-74 is unstable under reaction conditions and forms metallic nickel particles. To improve catalyst activity and stability, bimetallic (NixMg1-x)-MOF-74 catalysts were developed that stabilize the Ni OMS and promote the dehydrogenation reaction. An optimal composition exists at (Ni0.32Mg0.68)-MOF-74 that gives the greatest H2 productivity, up to 203 mL gcat-1 min-1 at 300 °C, and maintains 100% selectivity to CO and H2 between 225-275 °C. The optimized catalyst is also active for the dehydrogenation of other alcohols. DFT calculations reveal that synergistic interactions between the open metal site and the organic linker lead to lower reaction barriers in the MOF catalysts compared to the open metal site alone. This work expands the suite of hydrogen-related reactions catalyzed by MOF-74 which includes recent work on hydroformulation and our earlier reports of aryl-ether hydrogenolysis. Moreover, it highlights the use of bimetallic frameworks as an effective strategy for stabilizing a high density of catalytically active open metal sites. This journal is

Any electrical signal propagating in a metallic conductor loses amplitude due to the natural resistance of the metal. Compensating for such losses presently requires repeatedly breaking the conductor and interposing amplifiers that consume and regenerate the signal. This century-old primitive severely constrains the design and performance of modern interconnect-dense chips 1 . Here we present a fundamentally different primitive based on semi-stable edge of chaos (EOC) 2,3 , a long-theorized but experimentally elusive regime that underlies active (self-amplifying) transmission in biological axons 4,5 . By electrically accessing the spin crossover in LaCoO 3 , we isolate semi-stable EOC, characterized by small-signal negative resistance and amplification of perturbations 6,7 . In a metallic line atop a medium biased at EOC, a signal input at one end exits the other end amplified, without passing through a separate amplifying component. While superficially resembling superconductivity, active transmission offers controllably amplified time-varying small-signal propagation at normal temperature and pressure, but requires an electrically energized EOC medium. Operando thermal mapping reveals the mechanism of amplification-bias energy of the EOC medium, instead of fully dissipating as heat, is partly used to amplify signals in the metallic line, thereby enabling spatially continuous active transmission, which could transform the design and performance of complex electronic chips., (© 2024. The Author(s).)

Heat dissipation is a natural consequence of operating any electronic system. In nearly all computing systems, such heat is usually minimized by design and cooling. Here, we show that the temporal dynamics of internally produced heat in electronic devices can be engineered to both encode information within a single device and process information across multiple devices. In our demonstration, electronic NbO x Mott neurons, integrated on a flexible organic substrate, exhibit 18 biomimetic neuronal behaviours and frequency-based nociception within a single component by exploiting both the thermal dynamics of the Mott transition and the dynamical thermal interactions with the organic substrate. Further, multiple interconnected Mott neurons spatiotemporally communicate purely via heat, which we use for graph optimization by consuming over 10 6 times less energy when compared with the best digital processors. Thus, exploiting natural thermal processes in computing can lead to functionally dense, energy-efficient and radically novel mixed-physics computing primitives., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

There is growing interest in material candidates with properties that can be engineered beyond traditional design limits. Compositionally complex oxides (CCO), often called high entropy oxides, are excellent candidates, wherein a lattice site shares more than four cations, forming single-phase solid solutions with unique properties. However, the nature of compositional complexity in dictating properties remains unclear, with characteristics that are difficult to calculate from first principles. Here, compositional complexity is demonstrated as a tunable parameter in a spin-transition oxide semiconductor La 1- x (Nd, Sm, Gd, Y) x/4 CoO 3 , by varying the population x of rare earth cations over 0.00≤ x≤ 0.80. Across the series, increasing complexity is revealed to systematically improve crystallinity, increase the amount of electron versus hole carriers, and tune the spin transition temperature and on-off ratio. At high a population (x = 0.8), Seebeck measurements indicate a crossover from hole-majority to electron-majority conduction without the introduction of conventional electron donors, and tunable complexity is proposed as new method to dope semiconductors. First principles calculations combined with angle resolved photoemission reveal an unconventional doping mechanism of lattice distortions leading to asymmetric hole localization over electrons. Thus, tunable complexity is demonstrated as a facile knob to improve crystallinity, tune electronic transitions, and to dope semiconductors beyond traditional means., (© 2024 Wiley‐VCH GmbH.)

Neuromorphic computing promises an energy-efficient alternative to traditional digital processors in handling data-heavy tasks, primarily driven by the development of both volatile (neuronal) and nonvolatile (synaptic) resistive switches or memristors. However, despite their energy efficiency, memristor-based technologies presently lack functional tunability, thus limiting their competitiveness with arbitrarily programmable (general purpose) digital computers. This work introduces a two-terminal bilayer memristor, which can be tuned among neuronal, synaptic, and hybrid behaviors. The varying behaviors are accessed via facile control over the filament formed within the memristor, enabled by the interplay between the two active ionic species (oxygen vacancies and metal cations). This solution is unlike single-species ion migration employed in most other memristors, which makes their behavior difficult to control. By reconfiguring a single crossbar array of hybrid memristors, two different applications that usually require distinct types of devices are demonstrated - reprogrammable heterogeneous reservoir computing and arbitrary non-Euclidean graph networks. Thus, this work outlines a potential path toward functionally reconfigurable postdigital computers.

Realizing rechargeable cells with practical energy and power density requires electrodes with high active material loading, a remaining challenge for solid-state batteries. Here, we present a new strategy based on ionogel-derived solid-state electrolytes (SSEs) to form composite electrodes that enable high active material loading (>10 mg/cm 2 , ~9 mA/cm 2 at 1C) in a scalable approach for fabricating Li-ion cells. By tuning the precursor and active materials composition incorporated into the composite lithium titanate electrodes, we achieve near-theoretical capacity utilization at C/5 rates and cells capable of stable cycling at 5.85 mA/cm 2 (11.70 A/g) with over 99% average Coulombic efficiency at room temperature. Finally, we demonstrate a complete polymeric solid-state cell with a composite anode and a composite lithium iron phosphate cathode with ionogel SSEs, which is capable of stable cycling at a 1C rate.

While digital computers rely on software-generated pseudo-random number generators, hardware-based true random number generators (TRNGs), which employ the natural physics of the underlying hardware, provide true stochasticity, and power and area efficiency. Research into TRNGs has extensively relied on the unpredictability in phase transitions, but such phase transitions are difficult to control given their often abrupt and narrow parameter ranges (e.g., occurring in a small temperature window). Here we demonstrate a TRNG based on self-oscillations in LaCoO 3 that is electrically biased within its spin crossover regime. The LaCoO 3 TRNG passes all standard tests of true stochasticity and uses only half the number of components compared to prior TRNGs. Assisted by phase field modeling, we show how spin crossovers are fundamentally better in producing true stochasticity compared to traditional phase transitions. As a validation, by probabilistically solving the NP-hard max-cut problem in a memristor crossbar array using our TRNG as a source of the required stochasticity, we demonstrate solution quality exceeding that using software-generated randomness., (© 2024. The Author(s).)

Understanding the limits of spatiotemporal carrier dynamics, especially in III-V semiconductors, is key to designing ultrafast and ultrasmall optoelectronic components. However, identifying such limits and the properties controlling them has been elusive. Here, using scanning ultrafast electron microscopy, in bulk n-GaAs and p-InAs, we simultaneously measure picosecond carrier dynamics along with three related quantities: subsurface band bending, above-surface vacuum potentials, and surface trap densities. We make two unexpected observations. First, we uncover a negative-time contrast in secondary electrons resulting from an interplay among these quantities. Second, despite dopant concentrations and surface state densities differing by many orders of magnitude between the two materials, their carrier dynamics, measured by photoexcited band bending and filling of surface states, occur at a seemingly common timescale of about 100 ps. This observation may indicate fundamental kinetic limits tied to a multitude of material and surface properties of optoelectronic III-V semiconductors and highlights the need for techniques that simultaneously measure electro-optical kinetic properties.

Aluminum nitride (AlN) is one of the few electrically insulating materials with excellent thermal conductivity, but high-quality films typically require exceedingly hot deposition temperatures (>1000 °C). For thermal management applications in dense or high-power integrated circuits, it is important to deposit heat spreaders at low temperatures (<500 °C), without affecting the underlying electronics. Here, we demonstrate 100 nm to 1.7 μm thick AlN films achieved by low-temperature (<100 °C) sputtering, correlating their thermal properties with their grain size and interfacial quality, which we analyze by X-ray diffraction, transmission X-ray microscopy, as well as Raman and Auger spectroscopy. Controlling the deposition conditions through the partial pressure of reactive N 2 , we achieve an ∼3× variation in thermal conductivity (∼36-104 W m -1 K -1 ) of ∼600 nm films, with the upper range representing one of the highest values for such film thicknesses at room temperature, especially at deposition temperatures below 100 °C. Defect densities are also estimated from the thermal conductivity measurements, providing insight into the thermal engineering of AlN that can be optimized for application-specific heat spreading or thermal confinement.

Rugged Pd-metal-insulator-semiconductor (Pd-MIS) hydrogen sensors for detecting charge-exchange particles in fusion reactors have been constructed by utilizing a novel patterned adhesion layer. Poor adhesion at the interface between Pd and SiO 2 is a common failure mode for Pd-MIS devices, severely limiting the Pd thickness and their usefulness as hydrogen sensors. The mechanical integrity of the Pd coatings is of particular importance in magnetic fusion energy research where the Pd-MIS diodes are used to measure hydrogen charge-exchange neutral fluence at the wall in tokamaks. In this application, particularly thick Pd contacts are desirable to prevent damage caused by high-energy particles; however, such thick Pd coatings are prone to mechanical failure due to blistering and wire bond detachment during construction or operation. A continuous Ti or Cr adhesion layer is not possible for this application since it would interfere with H uptake at the SiO 2 interface, which is essential for the device to generate a response. In this work, we demonstrate that a patterned Cr interlayer substantially improves adhesion while still providing access for hydrogen to reach the SiO 2 -Pd interface.

Non-von-Neumann computing using neuromorphic systems based on two-terminal resistive nonvolatile memory elements has emerged as a promising approach, but its full potential has not been realized due to the lack of materials and devices with the appropriate attributes. Unlike memristors, which require large write currents to drive phase transformations or filament growth, electrochemical random access memory (ECRAM) decouples the "write" and "read" operations using a "gate" electrode to tune the conductance state through charge-transfer reactions, and every electron transferred through the external circuit in ECRAM corresponds to the migration of ≈1 ion used to store analogue information. Like static dopants in traditional semiconductors, electrochemically inserted ions modulate the conductivity by locally perturbing a host's electronic structure; however, ECRAM does so in a dynamic and reversible manner. The resulting change in conductance can span orders of magnitude, from gradual increments needed for analog elements, to large, abrupt changes for dynamically reconfigurable adaptive architectures. In this in-depth perspective, the history of ECRAM, the recent progress in devices spanning organic, inorganic, and 2D materials, circuits, architectures, the rich portfolio of challenging, fundamental questions, and how ECRAM can be harnessed to realize a new paradigm for low-power neuromorphic computing are discussed., (© 2022 Wiley-VCH GmbH.)

Emerging concepts for neuromorphic computing, bioelectronics, and brain-computer interfacing inspire new research avenues aimed at understanding the relationship between oxidation state and conductivity in unexplored materials. This report expands the materials playground for neuromorphic devices to include a mixed valence inorganic 3D coordination framework, a ruthenium Prussian blue analog (RuPBA), for flexible and biocompatible artificial synapses that reversibly switch conductance by more than four orders of magnitude based on electrochemically tunable oxidation state. The electrochemically tunable degree of mixed valency and electronic coupling between N-coordinated Ru sites controls the carrier concentration and mobility, as supported by density functional theory computations and application of electron transfer theory to in situ spectroscopy of intervalence charge transfer. Retention of programmed states is improved by nearly two orders of magnitude compared to extensively studied organic polymers, thus reducing the frequency, complexity, and energy costs associated with error correction schemes. This report demonstrates dopamine-mediated plasticity of RuPBA synapses and biocompatibility of RuPBA with neuronal cells, evoking prospective application for brain-computer interfacing., (© 2022 Wiley-VCH GmbH.)

We report a novel delithiation process for epitaxial thin films of LiCoO 2 (001) cathodes using only physical methods, based on ion sputtering and annealing cycles. Preferential Li sputtering followed by annealing produces a surface layer with a Li molar fraction in the range 0.5 < x < 1, characterized by good crystalline quality. This delithiation procedure allows the unambiguous identification of the effects of Li extraction without chemical byproducts and experimental complications caused by electrolyte interaction with the LiCoO 2 surface. An analysis by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) provides a detailed description of the delithiation process and the role of O and Co atoms in charge compensation. We observe the simultaneous formation of Co 4+ ions and of holes localized near O atoms upon Li removal, while the surface shows a (2 × 1) reconstruction. The delithiation method described here can be applied to other crystalline battery elements and provide information on their properties that is otherwise difficult to obtain.

Solar-powered photochemical water splitting using suspensions of photocatalyst nanoparticles is an attractive route for economical production of green hydrogen. SrTiO 3 -based photocatalysts have been intensely investigated due to their stability and recently demonstrated near-100% external quantum yield (EQY) for water splitting using wavelengths below 360 nm. To extend the optical absorption into the visible, SrTiO 3 nanoparticles have been doped with various transition metals. Here we demonstrate that doping SrTiO 3 nanoparticles with 1% Rh introduces midgap acceptor states which reduce the free electron concentration by 5 orders of magnitude, dramatically reducing built-in potentials which could otherwise separate electron-hole (e-h) pairs. Rhodium states also function as recombination centers, reducing the photocarrier lifetime by nearly 2 orders of magnitude and the maximum achievable EQY to 10%. Furthermore, the absence of built-in electric fields within Rh-doped SrTiO 3 nanoparticles suggests that modest e-h separation can be achieved by exploiting a difference in mobility between electrons and holes.

Li-metal batteries (LMBs) employing conversion cathode materials (e.g., FeF 3 ) are a promising way to prepare inexpensive, environmentally friendly batteries with high energy density. Pseudo-solid-state ionogel separators harness the energy density and safety advantages of solid-state LMBs, while alleviating key drawbacks (e.g., poor ionic conductivity and high interfacial resistance). In this work, a pseudo-solid-state conversion battery (Li-FeF 3 ) is presented that achieves stable, high rate (1.0 mA cm -2 ) cycling at room temperature. The batteries described herein contain gel-infiltrated FeF 3 cathodes prepared by exchanging the ionic liquid in a polymer ionogel with a localized high-concentration electrolyte (LHCE). The LHCE gel merges the benefits of a flexible separator (e.g., adaptation to conversion-related volume changes) with the excellent chemical stability and high ionic conductivity (∼2 mS cm -1 at 25 °C) of an LHCE. The latter property is in contrast to previous solid-state iron fluoride batteries, where poor ionic conductivities necessitated elevated temperatures to realize practical power levels. The stable, room-temperature Li-FeF 3 cycling performance obtained with the LHCE gel at high current densities paves the way for exploring a range of architectures including flexible, three-dimensional, and custom shape batteries.

Encapsulation of electrocatalysts and photocatalysts with semipermeable nanoscopic oxide overlayers that exhibit selective transport properties is an attractive approach to achieve high redox selectivity. However, defects within the overlayers─such as pinholes, cracks, or particle inclusions─may facilitate local high rates of parasitic reactions by creating pathways for facile transport of undesired reactants to exposed active sites. Scanning electrochemical microscopy (SECM) is an attractive method to determine the influence of defects on macroscopic performance metrics thanks to its ability to measure the relative rates of competing electrochemical reactions with high spatial resolution over the electrode. Here, we report the use of SECM to determine the influence of overlayer defects on the selectivity of silicon oxide (SiO x ) encapsulated platinum thin-film electrocatalysts operated under conditions where two competing reactions─the hydrogen evolution and Fe(III) reduction reactions─can occur. After an SECM methodology is described to determine spatially resolved selectivity, representative selectivity maps are correlated with the location of defects that are characterized by optical, electron, and atomic force microscopies. This analysis reveals that certain types of defects in the oxide overlayer are responsible for ∼60-90% of the partial current density toward the undesired Fe(III) reduction reaction. By correcting for defect contributions to Fe(III) reduction rates, true Fe(III) permeability values for the SiO x overlayers were determined to be over an order of magnitude lower than permeabilities determined from analyses that ignore the presence of defects. Finally, different types of defects were studied revealing that defect morphology can have varying influence on both redox selectivity and calculated permeability. This work highlights the need for spatially resolved measurements to evaluate the performance of oxide-encapsulated catalysts and understand their performance limits.

Li x CoO 2 (LCO) is a common battery cathode material that has recently emerged as a promising material for other applications including electrocatalysis and as electrochemical random access memory (ECRAM). During charge-discharge cycling LCO exhibits phase transformations that are significantly complicated by electron correlation. While the bulk phase diagram for an ensemble of battery particles has been studied extensively, it remains unclear how these phases scale to nanometer dimensions and the effects of strain and diffusional anisotropy at the single-particle scale. Understanding these effects is critical to modeling battery performance and for predicting the scalability and performance of electrocatalysts and ECRAM. Here we investigate isolated, epitaxial LiCoO 2 islands grown by pulsed laser deposition. After electrochemical cycling of the islands, conductive atomic force microscopy (c-AFM) is used to image the spatial distribution of conductive and insulating phases. Above 20 nm island thicknesses, we observe a kinetically arrested state in which the phase boundary is perpendicular to the Li-planes; we propose a model and present image analysis results that show smaller LCO islands have a higher conductive fraction than larger area islands, and the overall conductive fraction is consistent with the lithiation state. Thinner islands (14 nm), with a larger surface to volume ratio, are found to exhibit a striping pattern, which suggests surface energy can dominate below a critical dimension. When increasing force is applied through the AFM tip to strain the LCO islands, significant shifts in current flow are observed, and underlying mechanisms for this behavior are discussed. The c-AFM images are compared with photoemission electron microscopy images, which are used to acquire statistics across hundreds of particles. The results indicate that strain and morphology become more critical to electrochemical performance as particles approach nanometer dimensions.

Additive manufacturing can enable the fabrication of batteries in nonconventional form factors, enabling higher practical energy density due to improved material packing efficiency of power sources in devices. Furthermore, energy density can be improved by transitioning from conventional Li-ion battery materials to lithium metal anodes and conversion cathodes. Iron disulfide (FeS 2 ) is a prominent conversion cathode of commercial interest; however, the direct-ink-write (DIW) printing of FeS 2 inks for custom-form battery applications has yet to be demonstrated or optimized. In this work, DIW printing of FeS 2 inks is used to systematically investigate the impact of ink solid concentration on rheology, film shape retention on arbitrary surfaces, cathode morphology, and electrochemical cell performance. We find that cathodes with a ridged interface, produced from the filamentary extrusion of highly concentrated FeS 2 inks (60-70% solids w/w%), exhibit optimal power, uniformity, and stability when cycled at higher rates (in excess of C/10). Meanwhile, cells with custom-form, wave-shaped electrodes (printed FeS 2 cathodes and pressed lithium anodes) are demonstrated and shown to exhibit similar performance to comparable cells in planar configurations, demonstrating the feasibility of printing onto complex geometries. Overall, the DIW printing of FeS 2 inks is shown to be a viable path toward the making of custom-form conversion lithium batteries. More broadly, ridging is found to optimize rate capability, a finding that may have a broad impact beyond FeS 2 and syringe extrusion.

Electronic transport models for conducting polymers (CPs) and blends focus on the arrangement of conjugated chains, while the contributions of the nominally insulating components to transport are largely ignored. In this work, an archetypal CP blend is used to demonstrate that the chemical structure of the non-conductive component has a substantial effect on charge carrier mobility. Upon diluting a CP with excess insulator, blends with as high as 97.4 wt % insulator can display carrier mobilities comparable to some pure CPs such as polyaniline and low regioregularity P3HT. In this work, we develop a single, multiscale transport model based on the microstructure of the CP blends, which describes the transport properties for all dilutions tested. The results show that the high carrier mobility of primarily insulator blends results from the inclusion of aromatic rings, which facilitate long-range tunneling (up to ca. 3 nm) between isolated CP chains. This tunneling mechanism calls into question the current paradigm used to design CPs, where the solubilizing or ionically conducting component is considered electronically inert. Indeed, optimizing the participation of the nominally insulating component in electronic transport may lead to enhanced electronic mobility and overall better performance in CPs.

Conversion cathodes represent a viable route to improve rechargeable Li + battery energy densities, but their poor electrochemical stability and power density have impeded their practical implementation. Here, we explore the impact cell fabrication, electrolyte interaction, and current density have on the electrochemical performance of FeS 2 /Li cells by deconvoluting the contributions of the various conversion and intercalation reactions to the overall capacity. By varying the slurry composition and applied pressure, we determine that the capacity loss is primarily due to the large volume changes during (de)lithiation, leading to a degradation of the conductive matrix. Through the application of an external pressure, the loss is minimized by maintaining the conductive matrix. We further determine that polysulfide loss can be minimized by increasing the current density (>C/10), thus reducing the sulfur formation period. Analysis of the kinetics determines that the conversion reactions are rate-limiting, specifically the formation of metallic iron at rates above C/8. While focused on FeS 2 , our findings on the influence of pressure, electrolyte interaction, and kinetics are broadly applicable to other conversion cathode systems.

Flexible electronic skin with features that include sensing, processing, and responding to stimuli have transformed human-robot interactions. However, more advanced capabilities, such as human-like self-protection modalities with a sense of pain, sign of injury, and healing, are more challenging. Herein, a novel, flexible, and robust diffusive memristor based on a copolymer of chlorotrifluoroethylene and vinylidene fluoride (FK-800) as an artificial nociceptor (pain sensor) is reported. Devices composed of Ag/FK-800/Pt have outstanding switching endurance >10 6  cycles, orders of magnitude higher than any other two-terminal polymer/organic memristors in literature (typically 10 2 -10 3 cycles). In situ conductive atomic force microscopy is employed to dynamically switch individual filaments, which demonstrates that conductive filaments correlate with polymer grain boundaries and FK-800 has superior morphological stability under repeated switching cycles. It is hypothesized that the high thermal stability and high elasticity of FK-800 contribute to the stability under local Joule heating associated with electrical switching. To mimic biological nociceptors, four signature nociceptive characteristics are demonstrated: threshold triggering, no adaptation, relaxation, and sensitization. Lastly, by integrating a triboelectric generator (artificial mechanoreceptor), memristor (artificial nociceptor), and light emitting diode (artificial bruise), the first bioinspired injury response system capable of sensing pain, showing signs of injury, and healing, is demonstrated., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

FeF 3 conversion cathodes, paired with Li metal, are promising for use in next-generation secondary batteries and offer a remarkable theoretical energy density of 1947 Wh kg -1 compared to 690 Wh kg -1 for LiNi 0.5 Mn 1.5 O 4 ; however, many successful studies on FeF 3 cathodes are performed in cells with a large (>90-fold) excess of Li that disguises the effects of tested variables on the anode and decreases the practical energy density of the battery. Herein, it is demonstrated that for full-cell compatibility, the electrolyte must produce both a protective solid-electrolyte interphase and cathode-electrolyte interphase and that an electrolyte composed of 1:1.3:3 (m/m) LiFSI, 1,2-dimethoxyethane, and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether fulfills both these requirements. This work demonstrates the importance of verifying electrode level solutions on the full-cell level when developing new battery chemistries and represents the first full cell demonstration of a Li/FeF 3 cell, with both limited Li and high capacity FeF 3 utilization., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

An intriguing new class of two-dimensional (2D) materials based on metal-organic frameworks (MOFs) has recently been developed that displays electrical conductivity, a rarity among these nanoporous materials. The emergence of conducting MOFs raises questions about their fundamental electronic properties, but few studies exist in this regard. Here, we present an integrated theory and experimental investigation to probe the effects of metal substitution on the charge transport properties of M-HITP, where M = Ni or Pt and HITP = 2,3,6,7,10,11-hexaiminotriphenylene. The results show that the identity of the M-HITP majority charge carrier can be changed without intentional introduction of electronically active dopants. We observe that the selection of the metal ion substantially affects charge transport. Using the known structure, Ni-HITP, we synthesized a new amorphous material, a- Pt-HITP, which although amorphous is nevertheless found to be porous upon desolvation. Importantly, this new material exhibits p-type charge transport behavior, unlike Ni-HITP, which displays n-type charge transport. These results demonstrate that both p- and n-type materials can be achieved within the same MOF topology through appropriate choice of the metal ion.

The controlled fabrication of vertical, tapered, and high-aspect ratio GaN nanowires via a two-step top-down process consisting of an inductively coupled plasma reactive ion etch followed by a hot, 85% H 3 PO 4 crystallographic wet etch is explored. The vertical nanowires are oriented in the[0001]direction and are bound by sidewalls comprising of{336¯2}semipolar planes which are at a 12° angle from the [0001] axis. High temperature H 3 PO 4 etching between 60 °C and 95 °C result in smooth semipolar faceting with no visible micro-faceting, whereas a 50 °C etch reveals a micro-faceted etch evolution. High-angle annular dark-field scanning transmission electron microscopy imaging confirms nanowire tip dimensions down to 8-12 nanometers. The activation energy associated with the etch process is 0.90 ± 0.09 eV, which is consistent with a reaction-rate limited dissolution process. The exposure of the{336¯2}type planes is consistent with etching barrier index calculations. The field emission properties of the nanowires were investigated via a nanoprobe in a scanning electron microscope as well as by a vacuum field emission electron microscope. The measurements show a gap size dependent turn-on voltage, with a maximum current of 33 nA and turn-on field of 1.92 V nm -1 for a 50 nm gap, and uniform emission across the array., (© 2021 IOP Publishing Ltd.)

We report on the delithiation of LiCoO 2 thin films using oxalic acid (C 2 H 2 O 4 ) with the goal of understanding the structural degradation of an insertion oxide associated with Li chemical extraction. Using a multi-technique approach that includes synchrotron radiation X-ray diffraction, scanning electron microscopy, micro Raman spectroscopy, photoelectron spectroscopy and conductive atomic force microscopy we reveal the balance between selective Li extraction and structural damage. We identify three different delithiation regimes, related to surface processes, bulk delithiation and damage generation. We find that only a fraction of the grains is affected by the delithiation process, which may create local inhomogeneities. However, the bulk delithiation regime is effective to delithiate the LCO film. All experimental evidence collected indicates that the delithiation process in this regime mimics the behavior of LCO upon electrochemical delithiation. We discard the formation of Co oxalate during the chemical extraction process. In conclusion, the chemical route to Li extraction provides additional opportunities to investigate delithiation while avoiding the complications associated with electrolyte breakdown and simplifying in-situ measurements.

In-memory computing based on non-volatile resistive memory can significantly improve the energy efficiency of artificial neural networks. However, accurate in situ training has been challenging due to the nonlinear and stochastic switching of the resistive memory elements. One promising analog memory is the electrochemical random-access memory (ECRAM), also known as the redox transistor. Its low write currents and linear switching properties across hundreds of analog states enable accurate and massively parallel updates of a full crossbar array, which yield rapid and energy-efficient training. While simulations predict that ECRAM based neural networks achieve high training accuracy at significantly higher energy efficiency than digital implementations, these predictions have not been experimentally achieved. In this work, we train a 3 × 3 array of ECRAM devices that learns to discriminate several elementary logic gates (AND, OR, NAND). We record the evolution of the network's synaptic weights during parallel in situ (on-line) training, with outer product updates. Due to linear and reproducible device switching characteristics, our crossbar simulations not only accurately simulate the epochs to convergence, but also quantitatively capture the evolution of weights in individual devices. The implementation of the first in situ parallel training together with strong agreement with simulation results provides a significant advance toward developing ECRAM into larger crossbar arrays for artificial neural network accelerators, which could enable orders of magnitude improvements in energy efficiency of deep neural networks., Competing Interests: YL, TX, CB, EI, HT, MM, EF, and AT were employed at Sandia National Laboratories by NTESS. The authors declare that this study received funding from the sources listed in the “funding sources” section. Sandia National Laboratories/NTESS verified that this study contains no classified information in order to approve its submission for publication. Otherwise, the funders were not involved in the study design, collection, analysis, interpretation of data, the writing of this article, or the decision to submit it for publication. The handling editor declared a past co-authorship with several of the authors AM, AT, AS, and EF., (Copyright © 2021 Li, Xiao, Bennett, Isele, Melianas, Tao, Marinella, Salleo, Fuller and Talin.)

The III-nitride semiconductors have many attractive properties for field-emission vacuum electronics, including high thermal and chemical stability, low electron affinity, and high breakdown fields. Here, we report top-down fabricated gallium nitride (GaN)-based nanoscale vacuum electron diodes operable in air, with record ultralow turn-on voltages down to ∼0.24 V and stable high field-emission currents, tested up to several microamps for single-emitter devices. We leverage a scalable, top-down GaN nanofabrication method leading to damage-free and smooth surfaces. Gap-dependent and pressure-dependent studies provide new insights into the design of future, integrated nanogap vacuum electron devices. The results show promise for a new class of high-performance and robust, on-chip, III-nitride-based vacuum nanoelectronics operable in air or reduced vacuum.

Recent progress in artificial intelligence is largely attributed to the rapid development of machine learning, especially in the algorithm and neural network models. However, it is the performance of the hardware, in particular the energy efficiency of a computing system that sets the fundamental limit of the capability of machine learning. Data-centric computing requires a revolution in hardware systems, since traditional digital computers based on transistors and the von Neumann architecture were not purposely designed for neuromorphic computing. A hardware platform based on emerging devices and new architecture is the hope for future computing with dramatically improved throughput and energy efficiency. Building such a system, nevertheless, faces a number of challenges, ranging from materials selection, device optimization, circuit fabrication and system integration, to name a few. The aim of this Roadmap is to present a snapshot of emerging hardware technologies that are potentially beneficial for machine learning, providing the Nanotechnology readers with a perspective of challenges and opportunities in this burgeoning field.

Digital computing is nearing its physical limits as computing needs and energy consumption rapidly increase. Analogue-memory-based neuromorphic computing can be orders of magnitude more energy efficient at data-intensive tasks like deep neural networks, but has been limited by the inaccurate and unpredictable switching of analogue resistive memory. Filamentary resistive random access memory (RRAM) suffers from stochastic switching due to the random kinetic motion of discrete defects in the nanometer-sized filament. In this work, this stochasticity is overcome by incorporating a solid electrolyte interlayer, in this case, yttria-stabilized zirconia (YSZ), toward eliminating filaments. Filament-free, bulk-RRAM cells instead store analogue states using the bulk point defect concentration, yielding predictable switching because the statistical ensemble behavior of oxygen vacancy defects is deterministic even when individual defects are stochastic. Both experiments and modeling show bulk-RRAM devices using TiO 2- X switching layers and YSZ electrolytes yield deterministic and linear analogue switching for efficient inference and training. Bulk-RRAM solves many outstanding issues with memristor unpredictability that have inhibited commercialization, and can, therefore, enable unprecedented new applications for energy-efficient neuromorphic computing. Beyond RRAM, this work shows how harnessing bulk point defects in ionic materials can be used to engineer deterministic nanoelectronic materials and devices., (© 2020 Wiley-VCH GmbH.)

Plasmonic antennas and metasurfaces can effectively control light-matter interactions, and this facilitates a deterministic design of optical materials properties, including structural color. However, these optical properties are generally fixed after synthesis and fabrication, while many modern-day optics applications require active, low-power, and nonvolatile tuning. These needs have spurred broad research activities aimed at identifying materials and resonant structures capable of achieving large, dynamic changes in optical properties, especially in the challenging visible spectral range. In this work, we demonstrate dynamic tuning of polarization-dependent gap plasmon resonators that contain the electrochromic oxide WO 3 . Its refractive index in the visible changes continuously from n = 2.1 to 1.9 upon electrochemical lithium insertion and removal in a solid-state device. By incorporating WO 3 into a gap plasmon resonator, the resonant wavelength can be shifted continuously and reversibly by up to 58 nm with less than 2 V electrochemical bias voltage. The resonator can remain in a tuned state for tens of minutes under open circuit conditions.

Neuromorphic computers based on analogue neural networks aim to substantially lower computing power by reducing the need to shuttle data between memory and logic units. Artificial synapses containing nonvolatile analogue conductance states enable direct computation using memory elements; however, most nonvolatile analogue memories require high write voltages and large current densities and are accompanied by nonlinear and unpredictable weight updates. Here, we develop an inorganic redox transistor based on electrochemical lithium-ion insertion into Li X TiO 2 that displays linear weight updates at both low current densities and low write voltages. The write voltage, as low as 200 mV at room temperature, is achieved by minimizing the open-circuit voltage and using a low-voltage diffusive memristor selector. We further show that the Li X TiO 2 redox transistor can achieve an extremely sharp transistor subthreshold slope of just 40 mV/decade when operating in an electrochemically driven phase transformation regime.

Neuromorphic computers could overcome efficiency bottlenecks inherent to conventional computing through parallel programming and readout of artificial neural network weights in a crossbar memory array. However, selective and linear weight updates and <10-nanoampere read currents are required for learning that surpasses conventional computing efficiency. We introduce an ionic floating-gate memory array based on a polymer redox transistor connected to a conductive-bridge memory (CBM). Selective and linear programming of a redox transistor array is executed in parallel by overcoming the bridging threshold voltage of the CBMs. Synaptic weight readout with currents <10 nanoamperes is achieved by diluting the conductive polymer with an insulator to decrease the conductance. The redox transistors endure >1 billion write-read operations and support >1-megahertz write-read frequencies., (Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

HKUST-1 or Cu 3 BTC 2 (BTC = 1,3,5-benzenetricarboxylate) is a prototypical metal-organic framework (MOF) that holds a privileged position among MOFs for device applications, as it can be deposited as thin films on various substrates and surfaces. Recently, new potential applications in electronics have emerged for this material when HKUST-1 was demonstrated to become electrically conductive upon infiltration with 7,7,8,8-tetracyanoquinodimethane (TCNQ). However, the factors that control the morphology and reactivity of the thin films are unknown. Here, we present a study of the thin-film growth process on indium tin oxide and amorphous Si prior to infiltration. From the unusual bimodal, non-log-normal distribution of crystal domain sizes, we conclude that the nucleation of new layers of Cu 3 BTC 2 is greatly enhanced by surface defects and thus difficult to control. We then show that these films can react with methanolic TCNQ solutions to form dense films of the coordination polymer Cu(TCNQ). This chemical conversion is accompanied by dramatic changes in surface morphology, from a surface dominated by truncated octahedra to randomly oriented thin platelets. The change in morphology suggests that the chemical reaction occurs in the liquid phase and is independent of the starting surface morphology. The chemical transformation is accompanied by 10 orders of magnitude change in electrical conductivity, from <10 -11 S/cm for the parent Cu 3 BTC 2 material to 10 -1 S/cm for the resulting Cu(TCNQ) film. The conversion of Cu 3 BTC 2 films, which can be grown and patterned on a variety of (nonplanar) substrates, to Cu(TCNQ) opens the door for the facile fabrication of more complex electronic devices.

The host-guest system TCNQ@Cu 3 BTC 2 (TCNQ = 7,7,8,8-tetracyanoquinodimethane, BTC = 1,3,5-benzenetricarboxylate) is a striking example of how semiconductivity can be introduced by guest incorporation in an otherwise insulating parent material. Exhibiting both microporosity and semiconducting behavior such materials offer exciting opportunities as next-generation sensor materials. Here, we apply a solvent-free vapor phase loading under rigorous exclusion of moisture, obtaining a series of the general formula x TCNQ@Cu 3 BTC 2 (0 ≤ x ≤ 1.0). By using powder X-ray diffraction, infrared and X-ray absorption spectroscopy together with scanning electron microscopy and porosimetry, we provide the first structural evidence for a systematic preferential arrangement of TCNQ along the (111) lattice plane and the bridging coordination motif to two neighbouring Cu-paddlewheels, as was predicted by theory. For 1.0TCNQ@Cu 3 BTC 2 we find a specific electrical conductivity of up to 1.5 × 10 -4 S cm -1 whilst maintaining a high BET surface area of 573.7 m 2 g -1 . These values are unmatched by MOFs with equally high electrical conductivity, making the material attractive for applications such as super capacitors and chemiresistors. Our results represent the crucial missing link needed to firmly establish the structure-property relationship revealed in TCNQ@Cu 3 BTC 2 , thereby creating a sound basis for using this as a design principle for electrically conducting MOFs.

Because of their extraordinary surface areas and tailorable porosity, metal-organic frameworks (MOFs) have the potential to be excellent sensors of gas-phase analytes. MOFs with open metal sites are particularly attractive for detecting Lewis basic atmospheric analytes, such as water. Here, we demonstrate that thin films of the MOF HKUST-1 can be used to quantitatively determine the relative humidity (RH) of air using a colorimetric approach. HKUST-1 thin films are spin-coated onto rigid or flexible substrates and are shown to quantitatively determine the RH within the range of 0.1-5% RH by either visual observation or a straightforward optical reflectivity measurement. At high humidity (>10% RH), a polymer/MOF bilayer is used to slow the transport of H 2 O to the MOF film, enabling quantitative determination of RH using time as the distinguishing metric. Finally, the sensor is combined with an inexpensive light-emitting diode light source and Si photodiode detector to demonstrate a quantitative humidity detector for low humidity environments.

Detailed understanding of solid-solid interface structure-function relationships is critical for the improvement and wide deployment of all-solid-state batteries. The interfaces between lithium phosphorous oxynitride (LiPON) solid electrolyte material and lithium metal anode, and between LiPON and Li x CoO 2 cathode, have been reported to generate solid-electrolyte interphase (SEI)-like products and/or disordered regions. Using electronic structure calculations and crystalline LiPON models, we predict that LiPON models with purely P-N-P backbones are kinetically inert towards lithium at room temperature. In contrast, transfer of oxygen atoms from low-energy Li x CoO 2 (104) surfaces to LiPON is much faster under ambient conditions. The mechanisms of the primary reaction steps, LiPON structural motifs that readily reacts with lithium metal, experimental results on amorphous LiPON to partially corroborate these predictions, and possible mitigation strategies to reduce degradations are discussed. LiPON interfaces are found to be useful case studies for highlighting the importance of kinetics-controlled processes during battery assembly at moderate processing temperatures., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Three-dimensional thin-film solid-state batteries (3D TSSB) were proposed by Long et al. in 2004 as a structure-based approach to simultaneously increase energy and power densities. Here, we report experimental realization of fully conformal 3D TSSBs, demonstrating the simultaneous power-and-energy benefits of 3D structuring. All active battery components-electrodes, solid electrolyte, and current collectors-were deposited by atomic layer deposition (ALD) onto standard CMOS processable silicon wafers microfabricated to form arrays of deep pores with aspect ratios up to approximately 10. The cells utilize an electrochemically prelithiated LiV 2 O 5 cathode, a very thin (40-100 nm) Li 2 PO 2 N solid electrolyte, and a SnN x anode. The fabrication process occurs entirely at or below 250 °C, promising compatibility with a variety of substrates as well as integrated circuits. The multilayer battery structure enabled all-ALD solid-state cells to deliver 37 μAh/cm 2 ·μm (normalized to cathode thickness) with only 0.02% per-cycle capacity loss. Conformal fabrication of full cells over 3D substrates increased the areal discharge capacity by an order of magnitude while simulteneously improving power performance, a trend consistent with a finite element model. This work shows that the exceptional conformality of ALD, combined with conventional semiconductor fabrication methods, provides an avenue for the successful realization of long-sought 3D TSSBs which provide power performance scaling in regimes inaccessible to planar form factor cells.

Li metal is the preferred anode material for all-solid-state Li batteries. However, a stable plating and stripping of Li metal at the anode-solid electrolyte interface remains a significant challenge particularly at practically feasible current densities. This problem usually relates to high and/or inhomogeneous Li-electrode-electrolyte interfacial impedance and formation and growth of high-aspect-ratio dendritic Li deposits at the electrode-electrolyte interface, which eventually shunt the battery. To better understand details of Li metal plating, we use operando electron microscopy and Auger spectroscopy to probe nucleation, growth, and stripping of Li metal during cycling of a model solid-state Li battery as a function of current density and oxygen pressure. We find a linear correlation between the nucleation density of Li clusters and the charging rate in an ultrahigh vacuum, which agrees with a classical nucleation and growth model. Moreover, the trace amount of oxidizing gas (≈10 -6 Pa of O 2 ) promotes the Li growth in a form of nanowires due to a fine balance between the ion current density and a growth rate of a thin lithium-oxide shell on the surface of the metallic Li. Interestingly, increasing the partial pressure of O 2 to 10 -5 Pa resumes Li plating in a form of 3D particles. Our results demonstrate the importance of trace amounts of preexisting or ambient oxidizing species on lithiation processes in solid-state batteries.

Ni 3 (2,3,6,7,10,11-hexaiminotriphenylene) 2 is a π-stacked layered metal-organic framework material with extended π-conjugation that is analogous to graphene. Published experimental results indicate that the material is semiconducting, but all theoretical studies to date predict the bulk material to be metallic. Given that previous experimental work was carried out on specimens containing complex nanocrystalline microstructures and the tendency for internal interfaces to introduce transport barriers, we apply DFT to investigate the influence of internal interface defects on the electronic structure of Ni 3 (HITP) 2 . The results show that interface defects can introduce a transport barrier by breaking the π-conjugation and/or decreasing the dispersion of the electronic bands near the Fermi level. We demonstrate that the presence of defects can open a small gap, in the range of 15-200 meV, which is consistent with the experimentally inferred hopping barrier.

The family of three-dimensional topological insulators opens new avenues to discover novel photophysics and to develop novel types of photodetectors. ZrTe 5 has been shown to be a Dirac semimetal possessing unique topological, electronic, and optical properties. Here, we present spatially resolved photocurrent measurements on devices made of nanoplatelets of ZrTe 5 , demonstrating the photothermoelectric origin of the photoresponse. Because of the high electrical conductivity and good Seebeck coefficient, we obtain noise-equivalent powers as low as 42 pW/Hz 1/2 , at room temperature for visible light illumination, at zero bias. We also show that these devices suffer from significant ambient reactivity, such as the formation of a Te-rich surface region driven by Zr oxidation as well as severe reactions with the metal contacts. This reactivity results in significant stresses in the devices, leading to unusual geometries that are useful for gaining insight into the photocurrent mechanisms. Our results indicate that both the large photothermoelectric response and reactivity must be considered when designing or interpreting photocurrent measurements in these systems.

The atomic force microscope (AFM) offers a rich observation window on the nanoscale, yet many dynamic phenomena are too fast and too weak for direct AFM detection. Integrated cavity-optomechanics is revolutionizing micromechanical sensing; however, it has not yet impacted AFM. Here, we make a groundbreaking advance by fabricating picogram-scale probes integrated with photonic resonators to realize functional AFM detection that achieve high temporal resolution (<10 ns) and picometer vertical displacement uncertainty simultaneously. The ability to capture fast events with high precision is leveraged to measure the thermal conductivity (η), for the first time, concurrently with chemical composition at the nanoscale in photothermal induced resonance experiments. The intrinsic η of metal-organic-framework individual microcrystals, not measurable by macroscale techniques, is obtained with a small measurement uncertainty (8%). The improved sensitivity (50×) increases the measurement throughput 2500-fold and enables chemical composition measurement of molecular monolayer-thin samples. Our paradigm-shifting photonic readout for small probes breaks the common trade-off between AFM measurement precision and ability to capture transient events, thus transforming the ability to observe nanoscale dynamics in materials.

Correction for 'An updated roadmap for the integration of metal-organic frameworks with electronic devices and chemical sensors' by Ivo Stassen et al., Chem. Soc. Rev., 2017, DOI: 10.1039/c7cs00122c.

Nonvolatile redox transistors (NVRTs) based upon Li-ion battery materials are demonstrated as memory elements for neuromorphic computer architectures with multi-level analog states, "write" linearity, low-voltage switching, and low power dissipation. Simulations of backpropagation using the device properties reach ideal classification accuracy. Physics-based simulations predict energy costs per "write" operation of <10 aJ when scaled to 200 nm × 200 nm., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Demonstration of three-dimensional all-solid-state Li-ion batteries (3D SSLIBs) has been a long-standing goal for numerous researchers in the battery community interested in developing high power and high areal energy density storage solutions for a variety of applications. Ideally, the 3D geometry maximizes the volume of active material per unit area, while keeping its thickness small to allow for fast Li diffusion. In this paper, we describe experimental testing and simulation of 3D SSLIBs fabricated using materials and thin-film deposition methods compatible with semiconductor device processing. These 3D SSLIBs consist of Si microcolumns onto which the battery layers are sequentially deposited using physical vapor deposition. The power performance of the 3D SSLIBs lags significantly behind that of similarly prepared planar SSLIBs. Analysis of the experimental results using finite element modeling indicates that the origin of the poor power performance is the structural inhomogeneity of the 3D SSLIB, coupled with low electrolyte ionic conductivity and diffusion rate in the cathode, which lead to highly nonuniform internal current density distribution and poor cathode utilization.

With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light--propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer--present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer.

Carbon nanotubes (CNTs) have emerged as promising materials for visible, infrared, and terahertz photodetectors. Further development of these photodetectors requires a fundamental understanding of the mechanisms that govern their behavior as well as the establishment of figures of merit for technology applications. Recently, a number of CNT detectors have been shown to operate based on the photothermoelectric effect. Here we present a figure of merit for these detectors, which includes the properties of the material and the device. In addition, we use a suite of experimental characterization methods for the thorough analysis of the electrical, thermoelectric, electrothermal, and photothermal properties of the CNT thin-film devices. Our measurements determine the quantities that enter the figure of merit and allow us to establish a path toward future performance improvements.