Search

Summary Here, we elucidate the mechanism for Al2O3 atomic layer deposition (ALD) on LiMn2O4 (LMO) cathodes for lithium-ion batteries by using in situ and ex situ experimental characterization coupled with density functional theory (DFT) calculations. We demonstrate that not only does Al2O3 coat the LMO, but the Al heteroatom of the trimethylaluminum (TMA) precursor also dopes to interstitial sites on the LMO surface, thereby reducing the oxidation state of near-surface Mn ions. DFT calculations further suggest facile transfer of methyl groups from the TMA precursor to oxygen atoms on the LMO surface, which blocks adsorption sites for subsequent TMA adsorption. These predictions are supported by quartz crystal microbalance experiments demonstrating inhibited growth below ten ALD Al2O3 cycles, suggesting that sub-monolayer coverages of alumina are present on the LMO surface in the early stages of film growth. In comparison with fully conformal films, these sub-monolayer coatings show enhanced electrochemical capacity when cycled in coin cells.

Anhydrous liquid-phase exfoliation of germanium sulfide to provide few-layer germanium sulfide, as can be incorporated into electronic devices such as but not limited to batteries and cells comprising such materials.

Memristors are two-terminal passive circuit elements that have been developed for use in non-volatile resistive random-access memory and may also be useful in neuromorphic computing. Memristors have higher endurance and faster read/write times than flash memory and can provide multi-bit data storage. However, although two-terminal memristors have demonstrated capacity for basic neural functions, synapses in the human brain outnumber neurons by more than a thousandfold, which implies that multi-terminal memristors are needed to perform complex functions such as heterosynaptic plasticity. Previous attempts to move beyond two-terminal memristors, such as the three-terminal Widrow-Hoff memristor and field-effect transistors with nanoionic gates or floating gates, did not achieve memristive switching in the transistor. Here we report the experimental realization of a multi-terminal hybrid memristor and transistor (that is, a memtransistor) using polycrystalline monolayer molybdenum disulfide (MoS2) in a scalable fabrication process. The two-dimensional MoS2 memtransistors show gate tunability in individual resistance states by four orders of magnitude, as well as large switching ratios, high cycling endurance and long-term retention of states. In addition to conventional neural learning behaviour of long-term potentiation/depression, six-terminal MoS2 memtransistors have gate-tunable heterosynaptic functionality, which is not achievable using two-terminal memristors. For example, the conductance between a pair of floating electrodes (pre- and post-synaptic neurons) is varied by a factor of about ten by applying voltage pulses to modulatory terminals. In situ scanning probe microscopy, cryogenic charge transport measurements and device modelling reveal that the bias-induced motion of MoS2 defects drives resistive switching by dynamically varying Schottky barrier heights. Overall, the seamless integration of a memristor and transistor into one multi-terminal device could enable complex neuromorphic learning and the study of the physics of defect kinetics in two-dimensional materials.

Lithium metal anodes can largely enhance the energy density of rechargeable batteries because of the high theoretical capacity and the high negative potential. However, the problem of lithium dendrite formation and low Coulombic efficiency (CE) during electrochemical cycling must be solved before lithium anodes can be widely deployed. Herein, a new atomic layer deposition (ALD) chemistry to realize the low-temperature synthesis of homogeneous and stoichiometric lithium fluoride (LiF) is reported, which then for the first time, as far as we know, is deposited directly onto lithium metal. The LiF preparation is performed at 150 °C yielding 0.8 A/cycle. The LiF films are found to be crystalline, highly conformal, and stoichiometric with purity levels >99%. Nanoindentation measurements demonstrate the LiF achieving a shear modulus of 58 GPa, 7 times higher than the sufficient value to resist lithium dendrites. When used as the protective coating on lithium, it enables a stable Coulombic efficiency as high as 99.5% for over 170 cycles, about 4 times longer than that of bare lithium anodes. The remarkable battery performance is attributed to the nanosized LiF that serves two critical functions simultaneously: (1) the high dielectric value creates a uniform current distribution for excellent lithium stripping/plating and ultrahigh mechanical strength to suppress lithium dendrites; (2) the great stability and electrolyte isolation by the pure LiF on lithium prevents parasitic reactions for a much improved CE. This new ALD chemistry for conformal LiF not only offers a promising avenue to implement lithium metal anodes for high-capacity batteries but also paves the way for future studies to investigate failure and evolution mechanisms of solid electrolyte interphase (SEI) using our LiF on anodes such as graphite, silicon, and lithium.

The recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semi-metallic graphene and insulating boron nitride, has enabled the fabrication of all 2D van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integration with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS2. The resulting p-n heterojunction is gate-tunable and shows asymmetric control over the anti-ambipolar transfer characteristic. In addition, the pentacene-MoS2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS2 can function as an acceptor in hybrid solar cells., Comment: 5 figures and supporting information. To appear in Nano Letters

Two-dimensional covalent organic frameworks often π stack into crystalline solids that allow precise spatial positioning of molecular building blocks. Inspired by the hydrogen-bonded G-quadruplexes found frequently in guanine-rich DNA, here we show that this structural motif can be exploited to guide the self-assembly of naphthalene diimide and perylene diimide electron acceptors end-capped with two guanine electron donors into crystalline G-quadruplex-based organic frameworks, wherein the electron donors and acceptors form ordered, segregated π-stacked arrays. Time-resolved optical and electron paramagnetic resonance spectroscopies show that photogenerated holes and electrons in the frameworks have long lifetimes and display recombination kinetics typical of dissociated charge carriers. Moreover, the reduced acceptors form polarons in which the electron is shared over several molecules. The G-quadruplex frameworks also demonstrate potential as cathode materials in Li-ion batteries because of the favourable electron- and Li-ion-transporting capacity provided by the ordered rylene diimide arrays and G-quadruplex structures, respectively.

Unencapsulated, exfoliated black phosphorus (BP) flakes are found to chemically degrade upon exposure to ambient conditions. Atomic force microscopy, electrostatic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are employed to characterize the structure and chemistry of the degradation process, suggesting that O2 saturated H2O irreversibly reacts with BP to form oxidized phosphorus species. This interpretation is further supported by the observation that BP degradation occurs more rapidly on hydrophobic octadecyltrichlorosilane self-assembled monolayers and on H-Si(111), versus hydrophilic SiO2. For unencapsulated BP field-effect transistors, the ambient degradation causes large increases in threshold voltage after 6 hours in ambient, followed by a ~10^3 decrease in FET current on/off ratio and mobility after 48 hours. Atomic layer deposited AlOx overlayers effectively suppress ambient degradation, allowing encapsulated BP FETs to maintain high on/off ratios of ~10^3 and mobilities of ~100 cm2/(V*s) for over two weeks in ambient. This work shows that the ambient degradation of BP can be managed effectively when the flakes are sufficiently passivated. In turn, our strategy for enhancing BP environmental stability will accelerate efforts to implement BP in electronic and optoelectronic applications., Comment: Accepted at Nano Letters; 18 pages, 5 figures, and 23 figure supporting information

Efficient energy storage systems based on lithium-ion batteries represent a critical technology across many sectors including consumer electronics, electrified transportation, and a smart grid accommodating intermittent renewable energy sources. Nanostructured electrode materials present compelling opportunities for high-performance lithium-ion batteries, but inherent problems related to the high surface area to volume ratios at the nanometer-scale have impeded their adoption for commercial applications. Here, we demonstrate a materials and processing platform that realizes high-performance nanostructured lithium manganese oxide (nano-LMO) spinel cathodes with conformal graphene coatings as a conductive additive. The resulting nanostructured composite cathodes concurrently resolve multiple problems that have plagued nanoparticle-based lithium-ion battery electrodes including low packing density, high additive content, and poor cycling stability. Moreover, this strategy enhances the intrinsic advantages of nano-LMO, resulting in extraordinary rate capability and low temperature performance. With 75% capacity retention at a 20C cycling rate at room temperature and nearly full capacity retention at -20 °C, this work advances lithium-ion battery technology into unprecedented regimes of operation.

Oxide conversion reactions in lithium ion batteries are challenged by substantial irreversibility associated with significant volume change during the phase separation of an oxide into lithia and metal species (e.g., NiO + 2Li(+) + 2e(-) → Ni + Li2O). We demonstrate that the confinement of nanometer-scale NiO layers within a Ni/NiO multilayer electrode can direct lithium transport and reactivity, leading to coherent expansion of the multilayer. The morphological changes accompanying lithiation were tracked in real-time by in-operando X-ray reflectivity (XRR) and ex-situ cross-sectional transmission electron microscopy on well-defined periodic Ni/NiO multilayers grown by pulsed-laser deposition. Comparison of pristine and lithiated structures reveals that the nm-thick nickel layers help initiate the conversion process at the interface and then provide an architecture that confines the lithiation to the individual oxide layers. XRR data reveal that the lithiation process starts at the top and progressed through the electrode stack, layer by layer resulting in a purely vertical expansion. Longer term cycling showed significant reversible capacity (∼800 mA h g(-1) after ∼100 cycles), which we attribute to a combination of the intrinsic bulk lithiation capacity of the NiO and additional interfacial lithiation capacity. These observations provide new insight into the role of metal/metal oxide interfaces in controlling lithium ion conversion reactions by defining the relationships between morphological changes and film architecture during reaction.

Real-time label-free electrical detection of proteins, including cardiac troponin (cTn), is demonstrated using functionalized SnO2 nanobelt field-effect transistors (FETs) with integrated microfluidics. Selective biomolecular functionalization of the active SnO2 nanobelt channel and effective passivation of the substrate surface were realized and verified through fluorescence microscopy. The validation/verification of the sensing scheme was initially demonstrated via detection of biotin–streptavidin binding: devices with single biotinylated SnO2 nanobelts showed pronounced conductance changes in response to streptavidin binding. Importantly, the pH-dependence of the conductance changes was fully consistent with the charged states of streptavidin at different pH. Moreover, the specificity of the sensors’ electrical responses was confirmed by co-labeling with quantum dots. Finally, the sensing platform was successfully applied for detection of the cardiac troponin I (cTnI) subunit within cTn, a clinically important protein marker for myocardial infarction.

With a semiconducting band gap and high charge carrier mobility, two-dimensional (2D) black phosphorus (BP), often referred to as phosphorene, holds significant promise for next generation electronics and optoelectronics. However, as a 2D material, it possesses a higher surface area to volume ratio than bulk BP, suggesting that its chemical and thermal stability will be modified. Herein, an atomic-scale microscopic and spectroscopic study is performed to characterize the thermal degradation of mechanically exfoliated 2D BP. From in situ scanning/transmission electron microscopy, decomposition of 2D BP is observed to occur at ~400 {\deg}C in vacuum, in contrast to the 550 {\deg}C bulk BP sublimation temperature. This decomposition initiates via eye-shaped cracks along the [001] direction and then continues until only a thin, amorphous red phosphorous like skeleton remains. In situ electron energy loss spectroscopy, energy-dispersive X-ray spectroscopy, and energy-loss near-edge structure changes provide quantitative insight into this chemical transformation process., Comment: In press: 4 figures in main manuscript, 27 pages with supporting information

The thickness-dependent band structure of MoS2 implies that discontinuities in energy bands exist at the interface of monolayer (1L) and multilayer (ML) thin films. The characteristics of such heterojunctions are analyzed here using current versus voltage measurements, scanning photocurrent microscopy, and finite element simulations of charge carrier transport. Rectifying I-V curves are consistently observed between contacts on opposite sides of 1L-ML junctions, and a strong bias-dependent photocurrent is observed at the junction. Finite element device simulations with varying carrier concentrations and electron affinities show that a type II band alignment at single layer/multi-layer junctions reproduces both the rectifying electrical characteristics and the photocurrent response under bias. However, the zero-bias junction photocurrent and its energy dependence are not explained by conventional photovoltaic and photothermoelectric mechanisms, indicating the contributions of hot carriers., Comment: 5 figures plus supplement

Solution dispersions of two-dimensional (2D) black phosphorus (BP), often referred to as phosphorene, are achieved by solvent exfoliation. These pristine, electronic-grade BP dispersions are produced with anhydrous, organic solvents in a sealed tip ultrasonication system, which circumvents BP degradation that would otherwise occur via solvated oxygen or water. Among conventional solvents, n-methyl-pyrrolidone (NMP) is found to provide stable, highly concentrated (~0.4 mg/mL) BP dispersions. Atomic force microscopy, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy show that the structure and chemistry of solvent-exfoliated BP nanosheets are comparable to mechanically exfoliated BP flakes. Additionally, residual NMP from the liquid-phase processing suppresses the rate of BP oxidation in ambient conditions. Solvent-exfoliated BP nanosheet field-effect transistors (FETs) exhibit ambipolar behavior with current on/off ratios and mobilities up to ~10000 and ~50 cm^2/(V*s), respectively. Overall, this study shows that stable, highly concentrated, electronic-grade 2D BP dispersions can be realized by scalable solvent exfoliation, thereby presenting opportunities for large-area, high-performance BP device applications., Comment: 6 figures, 31 pages, including supporting information

Dissolution of transition metal (TM) cations into organic electrolytes is a significant impediment to capacity retention in various lithium ion battery electrode materials. Interfaces engineered via substitutional doping and protective coatings, however, have been demonstrated to be effective techniques to reduce TM dissolution, preventing counterelectrode crossover1–3. In this work, we present an integrated theoretical and experimental approach to gain a molecular level understanding towards the functionality of protective thin films. As a model system, we consider Al2O3 film growth by atomic layer deposition (ALD) on spinel LiMn2O4 (LMO), a cathode material exhibiting the well-documented capacity fade mechanism of Mn dissolution. Using first principles DFT+U calculations in concert with in situ experimental characterization, the mechanisms for Al2O3 ALD film growth by trimethylaluminum (TMA) and H2O half-reactions are evaluated. Using thermodynamically stable low-index surface truncations, as well as stepped defect features4, we identify facile pathways for full demethylation of the TMA precursor on the LMO surface. Trends from microbalance experiments indicate sub-monolayer film coverage for ~10 ALD cycles, wherein film growth is initially slow, but gradually increases until the limit of a fully formed Al2O3 film is reached. DFT calculations suggest that sluggish film growth at the onset is predicated by site blocking from decomposed CH3 groups. An electronic structure descriptor is presented to demonstrate evidence that, in early ALD pulses, Al2O3 preferentially nucleates at sites on LMO that are most susceptible to Mn dissolution. The chemical nature of these relevant defect sites will be discussed further in the context of Mn dissolution through charge disproportionation, with enhanced stability by selective nucleation of the protective films. The unique mechanisms for ALD on LMO lead to modest enhancements in electrochemical performance for only ~1-2 ALD cycles, whereas cycling capabilities reduce with further TMA/H2O pulses in the limit of a fully formed coating on the substrate. This research was supported as part of the Center for Electrochemical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.

Memristors with gate-tunable charge transport characteristics are fabricated from monolayer MoS2 by exploiting specific grain boundary configurations with respect to the electrodes. Continued progress in high-speed computing depends on breakthroughs in both materials synthesis and device architectures1,2,3,4. The performance of logic and memory can be enhanced significantly by introducing a memristor5,6, a two-terminal device with internal resistance that depends on the history of the external bias voltage5,6,7. State-of-the-art memristors, based on metal–insulator–metal (MIM) structures with insulating oxides, such as TiO2, are limited by a lack of control over the filament formation and external control of the switching voltage3,4,6,8,9. Here, we report a class of memristors based on grain boundaries (GBs) in single-layer MoS2 devices10,11,12. Specifically, the resistance of GBs emerging from contacts can be easily and repeatedly modulated, with switching ratios up to ∼103 and a dynamic negative differential resistance (NDR). Furthermore, the atomically thin nature of MoS2 enables tuning of the set voltage by a third gate terminal in a field-effect geometry, which provides new functionality that is not observed in other known memristive devices.

Solid-state supercapacitors and microsupercapacitors comprising printed graphene electrodies and related method of fabricating a graphene capacitor, said method comprising providing a graphene ink composition comprising graphene and an ethyl cellulose, said composition not prepared from graphene oxide, depositing said graphene ink composition on a substrate, annealing said graphene ink composition to decompose said ethyl cellulose and provide an electrode component comprising graphene, and coupling electrolyte and metallic lead components to said electrode component.

Sensing biological agents at the genomic level, while enhancing the response time for biodetection over commonly used, optics-based techniques such as nucleic acid microarrays or enzyme-linked immunosorbent assays (ELISAs), is an important criterion for new biosensors. Here, we describe the successful detection of a 35-base, single-strand nucleic acid target by Hall-based magnetic transduction as a mimic for pathogenic DNA target detection. The detection platform has low background, large signal amplification following target binding and can discriminate a single, 350 nm superparamagnetic bead labeled with DNA. Detection of the target sequence was demonstrated at 364 pM (μM nontarget (noncomplementary) DNA (

Real-time label-free electrical detection of proteins, including cardiac troponin (cTn), is demonstrated using functionalized SnO₂ nanobelt field-effect transistors (FETs) with integrated microfluidics. Selective biomolecular functionalization of the active SnO₂ nanobelt channel and effective passivation of the substrate surface were realized and verified through fluorescence microscopy. The validation/verification of the sensing scheme was initially demonstrated via detection of biotin-streptavidin binding: devices with single biotinylated SnO₂ nanobelts showed pronounced conductance changes in response to streptavidin binding. Importantly, the pH-dependence of the conductance changes was fully consistent with the charged states of streptavidin at different pH. Moreover, the specificity of the sensors' electrical responses was confirmed by co-labeling with quantum dots. Finally, the sensing platform was successfully applied for detection of the cardiac troponin I (cTnI) subunit within cTn, a clinically important protein marker for myocardial infarction.

The detection of reagent-free specific biomolecular interactions through sensing of nanoscopic magnetic labels provides one of the most promising routes to biosensing with solid-state devices. In particular, Hall sensors based on semiconductor heterostructures have shown exceptional magnetic moment sensitivity over a large dynamic field range suitable for magnetic biosensing using superparamagnetic labels. Here we demonstrate the capability of such micro-Hall sensors to detect specific molecular binding using biotin-streptavidin as a model system. We apply dip-pen nanolithography to selectively biotinylate the active areas of InAs micro-Hall devices with nanoscale precision. Specific binding of complementarily functionalized streptavidin-coated superparamagnetic beads to the Hall crosses occurs via molecular recognition, and magnetic detection of the assembled beads is achieved at room temperature using phase sensitive micro-Hall magnetometry. The experiment constitutes the first unambiguous demonstration of magnetic detection of specific biomolecular interactions with semiconductor micro-Hall sensors, and the selective molecular functionalization and resulting localized bead assembly demonstrate the possibility of multiplexed sensing of multiple target molecules using a single device with an array of micro-Hall sensors.