High-efficiency two-dimensional Ruddlesden-Popper perovskite solar cells.

Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single­junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Shockley-Queisser triangle predicts the thermodynamic efficiency limits of arbitrarily complex multijunction bifacial solar cells.

As monofacial, single-junction solar cells approach their fundamental limits, there has been significant interest in tandem solar cells in the presence of concentrated sunlight or tandem bifacial solar cells with back-reflected albedo. The bandgap sequence and thermodynamic efficiency limits of these complex cell configurations require sophisticated numerical calculation. Therefore, the analyses of specialized cases are scattered throughout the literature. In this paper, we show that a powerful graphical approach called the normalized "Shockley-Queisser (S-Q) triangle" (i.e., [Formula: see text]) is sufficient to calculate the bandgap sequence and efficiency limits of arbitrarily complex photovoltaic (PV) topologies. The results are validated against a wide variety of specialized cases reported in the literature and are accurate within a few percent. We anticipate that the widespread use of the S-Q triangle will illuminate the deeper physical principles and design trade-offs involved in the design of bifacial tandem solar cells under arbitrary concentration and series resistance.

Steep-Slope WSe2 Negative Capacitance Field-Effect Transistor.

P-type two-dimensional steep-slope negative capacitance field-effect transistors are demonstrated for the first time with WSe2 as channel material and ferroelectric hafnium zirconium oxide in gate dielectric stack. F4-TCNQ is used as p-type dopant to suppress electron leakage current and to reduce Schottky barrier width for holes. WSe2 negative capacitance field-effect transistors with and without internal metal gate structures and the internal field-effect transistors are compared and studied. Significant SS reduction is observed in WSe2 negative capacitance field-effect transistors by inserting the ferroelectric hafnium zirconium oxide layer, suggesting the existence of internal amplification (∼10) due to the negative capacitance effect. Subthreshold slope less than 60 mV/dec (as low as 14.4 mV/dec) at room temperature is obtained for both forward and reverse gate voltage sweeps. Negative differential resistance is observed at room temperature on WSe2 negative capacitance field-effect-transistors as the result of negative capacitance induced negative drain-induced-barrier-lowering effect.

Analyzing Thermal Stability of Cell Membrane of Salmonella Using Time-Multiplexed Impedance Sensing.

Heat treatment is one of the most widely used methods for inactivation of bacteria in food products. Heat-induced loss of bacterial viability has been variously attributed to protein denaturation, oxidative stress, or membrane leakage; indeed, it is likely to involve a combination of these processes. We examine the effect of mild heat stress (50-55°C for ≤12 min) on cell permeability by directly measuring the electrical conductance of samples of Salmonella enterica serovar Typhimurium to answer a fundamental biophysical question, namely, how bacteria die under mild heat stress. Our results show that when exposed to heat shock, the cell membrane is damaged and cells die mainly due to the leakage of small cytoplasmic species to the surrounding media without lysis (confirmed by fluorescent imaging). We measured the conductance change, ΔY, of wild-type versus genetically modified heat-resistant (HR) cells in response to pulse and ramp heating profiles with different thermal time constants. In addition, we developed a phenomenological model to correlate the membrane damage, cytoplasmic leakage, and cell viability. This model traces the differential viability and ΔY of wild-type and HR cells to the difference in the effective activation energies needed to permeabilize the cells, implying that HR cells are characterized by stronger lateral interactions between molecules, such as lipids, in their cell envelope.

Real-time characterization of uptake kinetics of glioblastoma vs. astrocytes in 2D cell culture using microelectrode array.

Extracellular measurement of uptake/release kinetics and associated concentration dependencies provides mechanistic insight into the underlying biochemical processes. Due to the recognized importance of preserving the natural diffusion processes within the local microenvironment, measurement approaches which provide uptake rate and local surface concentration of adherent cells in static media are needed. This paper reports a microelectrode array device and a methodology to measure uptake kinetics as a function of cell surface concentration in adherent 2D cell cultures in static fluids. The microelectrode array simultaneously measures local concentrations at five positions near the cell surface in order to map the time-dependent concentration profile which in turn enables determination of surface concentrations and uptake rates, via extrapolation to the cell plane. Hydrogen peroxide uptake by human astrocytes (normal) and glioblastoma multiforme (GBM43, cancer) was quantified for initial concentrations of 20 to 500 µM over time intervals of 4000 s. For both cell types, the overall uptake rate versus surface concentration relationships exhibited non-linear kinetics, well-described by a combination of linear and Michaelis-Menten mechanisms and in agreement with the literature. The GBM43 cells showed a higher uptake rate over the full range of concentrations, primarily due to a larger linear component. Diffusion-reaction models using the non-linear parameters and standard first-order relationships are compared. In comparison to results from typical volumetric measurements, the ability to extract both uptake rate and surface concentration in static media provides kinetic parameters that are better suited for developing reaction-diffusion models to adequately describe behavior in more complex culture/tissue geometries. The results also highlight the need for characterization of the uptake rate over a wider range of cell surface concentrations in order to evaluate the potential therapeutic role of hydrogen peroxide in cancerous cells.

Modeling and designing multilayer 2D perovskite / silicon bifacial tandem photovoltaics for high efficiencies and long-term stability.

A key challenge in photovoltaics today is to develop cell technologies with both higher efficiencies and lower fabrication costs than incumbent crystalline silicon (c-Si) single-junction cells. While tandem cells have higher efficiencies than c-Si alone, it is generally challenging to find a low-cost, high-performance material to pair with c-Si. However, the recent emergence of 22% efficient perovskite photovoltaics has created a tremendous opportunity for high-performance, low-cost perovskite / crystalline silicon tandem photovoltaic cells. Nonetheless, two key challenges remain. First, integrating perovskites into tandem structures has not yet been demonstrated to yield performance exceeding commercially available crystalline silicon modules. Second, the stability of perovskites is inconsistent with the needs of most end-users, who install photovoltaic modules to produce power for 25 years or more. Making these cells viable thus requires innovation in materials processing, device design, fabrication, and yield. We will address these two gaps in the photovoltaic literature by investigating new types of 2D perovskite materials with n-butylammonium spacer layers, and integrating these materials into bifacial tandem solar cells providing at least 30% normalized power production. We find that an optimized 2D perovskite ((BA)2(MA)3(Sn0.6Pb0.4)4I13)/silicon bifacial tandem cell, given a globally average albedo of 30%, yields a normalized power production of 30.31%, which should be stable for extended time periods without further change in materials or encapsulation.

Droplet-based non-faradaic impedance sensors for assessment of susceptibility of Escherichia coli to ampicillin in 60 min.

Direct antibiotic susceptibility tests (AST) are essential for rapid detection of bacterial infection and administration of appropriate antibiotics. Conventional AST systems are usually slow as they rely on cell growth for an indirect assessment of antibiotics' effectiveness. Therefore, a faster method is desirable, especially for emergency cases. In this work, we studied the performance of label-free, droplet-based impedance sensors for rapid characterization of the effects of ampicillin (Amp) on Escherichia coli. Ampicillin damages cell wall integrity and makes cells permeable (leaky). The leakage results in significant increase of the electrical conductance measured directly by the microfabricated sensing unit. We studied the conductance signal as a function of both antibiotic treatment time and dosage and demonstrated susceptibility testing within 60 min. These findings demonstrate the potential of droplet-based electrical chips for the realization of electrical antibiotic susceptibility testing (e-AST) for early-stage diagnostic/treatment, and consequently, preventing antibiotic misuse/overuse.

Evidence of Universal Temperature Scaling in Self-Heated Percolating Networks.

During routine operation, electrically percolating nanocomposites are subjected to high voltages, leading to spatially heterogeneous current distribution. The heterogeneity implies localized self-heating that may (self-consistently) reroute the percolation pathways and even irreversibly damage the material. In the absence of experiments that can spatially resolve the current distribution and a nonlinear percolation model suitable to interpret them, one relies on empirical rules and safety factors to engineer these materials. In this paper, we use ultrahigh resolution thermo-reflectance imaging, coupled with a new imaging processing technique, to map the spatial distribution ΔT(x, y; I) and histogram f(ΔT) of temperature rise due to self-heating in two types of 2D networks (percolating and copercolating). Remarkably, we find that the self-heating can be described by a simple two-parameter Weibull distribution, even under voltages high enough to reconfigure the percolation pathways. Given the generality of the phenomenological argument supporting the distribution, other percolating networks are likely to show similar stress distribution in response to sufficiently large stimuli. Furthermore, the spatial evolution of the self-heating of network was investigated by analyzing the spatial distribution and spatial correlation, respectively. An estimation of degree of hotspot clustering reveals a mechanism analogous to crystallization physics. The results should encourage nonlinear generalization of percolation models necessary for predictive engineering of nanocomposite materials.

Flexure-FET biosensor to break the fundamental sensitivity limits of nanobiosensors using nonlinear electromechanical coupling.

In this article, we propose a Flexure-FET (flexure sensitive field effect transistor) ultrasensitive biosensor that utilizes the nonlinear electromechanical coupling to overcome the fundamental sensitivity limits of classical electrical or mechanical nanoscale biosensors. The stiffness of the suspended gate of Flexure-FET changes with the capture of the target biomolecules, and the corresponding change in the gate shape or deflection is reflected in the drain current of FET. The Flexure-FET is configured to operate such that the gate is biased near pull-in instability, and the FET-channel is biased in the subthreshold regime. In this coupled nonlinear operating mode, the sensitivity (S) of Flexure-FET with respect to the captured molecule density (N(s)) is shown to be exponentially higher than that of any other electrical or mechanical biosensor. In other words, while S(Flexure) ~ e(γ1 [square root]Ns-γ2Ns), classical electrical or mechanical biosensors are limited to S(classical) ~ γ(3)N(S) or γ(4) ln(N(S)), where γ(i) are sensor-specific constants. In addition, the proposed sensor can detect both charged and charge-neutral biomolecules, without requiring a reference electrode or any sophisticated instrumentation, making it a potential candidate for various low-cost, point-of-care applications.

Enhanced light trapping in solar cells with a meta-mirror following generalized Snell's law.

As the performance of photovoltaic cells approaches the Shockley-Queisser limit, appropriate schemes are needed to minimize the losses without compromising the current performance. In this paper we propose a planar absorber-mirror light trapping structure where a conventional mirror is replaced by a meta-mirror with asymmetric light scattering properties. The meta-mirror is tailored to have reflection in asymmetric modes that stay outside the escape cone of the dielectric, hence trapping light with unit probability. Ideally, the meta-mirror can be designed to have such light trapping for any angle of incidence onto the absorber-mirror structure. We illustrate the concept by using a simple gap-plasmon meta-mirror. Even though the response of the mirror is non-ideal with the unwanted scattering modes reducing the light absorption, we observe an order of magnitude enhancement compared to single pass absorption in the absorber. The bandwidth of the enhancement can be matched with the range of wavelengths close to the solar cell absorber band-edge where improved light absorption is required.

Medium-scale carbon nanotube thin-film integrated circuits on flexible plastic substrates.

The ability to form integrated circuits on flexible sheets of plastic enables attributes (for example conformal and flexible formats and lightweight and shock resistant construction) in electronic devices that are difficult or impossible to achieve with technologies that use semiconductor wafers or glass plates as substrates. Organic small-molecule and polymer-based materials represent the most widely explored types of semiconductors for such flexible circuitry. Although these materials and those that use films or nanostructures of inorganics have promise for certain applications, existing demonstrations of them in circuits on plastic indicate modest performance characteristics that might restrict the application possibilities. Here we report implementations of a comparatively high-performance carbon-based semiconductor consisting of sub-monolayer, random networks of single-walled carbon nanotubes to yield small- to medium-scale integrated digital circuits, composed of up to nearly 100 transistors on plastic substrates. Transistors in these integrated circuits have excellent properties: mobilities as high as 80 cm(2) V(-1) s(-1), subthreshold slopes as low as 140 m V dec(-1), operating voltages less than 5 V together with deterministic control over the threshold voltages, on/off ratios as high as 10(5), switching speeds in the kilohertz range even for coarse (approximately 100-microm) device geometries, and good mechanical flexibility-all with levels of uniformity and reproducibility that enable high-yield fabrication of integrated circuits. Theoretical calculations, in contexts ranging from heterogeneous percolative transport through the networks to compact models for the transistors to circuit level simulations, provide quantitative and predictive understanding of these systems. Taken together, these results suggest that sub-monolayer films of single-walled carbon nanotubes are attractive materials for flexible integrated circuits, with many potential areas of application in consumer and other areas of electronics.

Theory of nanostructured sensors integrated in/on microneedles for diagnostics and therapy.

Efficient real-time diagnostics and on-demand drug delivery are essential components in modern healthcare, especially for managing chronic diseases. The lack of a rapid and effective sensing and therapeutic system can result in analyte level deviations, leading to severe complications. Minimally invasive microneedle (MN)-based patches integrating nanostructures (NSs) in their volume or on their surface have emerged as a biocompatible technology for delay-free analyte sensing and therapy. However, a quantitative relationship for the signal response in NS-assisted reactions remains elusive. Existing generalized formalisms are derived for in-vitro applications, raising questions about their direct applicability to in-situ wearable sensors. In this study, we apply the reaction-diffusion theory to establish a generalized physics-guided framework for NS-in-MN platforms in wearable applications. The model relates the signal response to analyte concentration, incorporating geometric, physical, and catalytic platform properties. Approximating the model under NS (binding or catalytic) and environmental (mass transport) limitations, we validate it against numerical simulations and various experimental results from diverse conditions - analyte sensing (glucose, lactic acid, pyocyanin, miRNA, etc.) in artificial and in-vivo environments (humans, mice, pigs, plants, etc.) through electrochemical and optical/colorimetric, enzymatic and non-enzymatic platforms. The results plotted in the scaled response show that (a) NS-limited platforms exhibit a linear dependence, (b) Mass transport-limited platforms saturate to 1, (c) a one-to-one mapping against traditional sensitivity plots unifies the scattered data points reported in literature. The universality of the model provides insightful perspectives for the design and optimization of MN-based sensing technologies, with potential extensions to dissolvable MNs as part of analyte-responsive closed-loop therapeutic applications.

Two-dimensional perovskite templates for durable, efficient formamidinium perovskite solar cells.

We present a design strategy for fabricating ultrastable phase-pure films of formamidinium lead iodide (FAPbI3) by lattice templating using specific two-dimensional (2D) perovskites with FA as the cage cation. When a pure FAPbI3 precursor solution is brought in contact with the 2D perovskite, the black phase forms preferentially at 100°C, much lower than the standard FAPbI3 annealing temperature of 150°C. X-ray diffraction and optical spectroscopy suggest that the resulting FAPbI3 film compresses slightly to acquire the (011) interplanar distances of the 2D perovskite seed. The 2D-templated bulk FAPbI3 films exhibited an efficiency of 24.1% in a p-i-n architecture with 0.5-square centimeter active area and an exceptional durability, retaining 97% of their initial efficiency after 1000 hours under 85°C and maximum power point tracking.

A compact analytical formalism for current transients in electrochemical systems.

Micro- and nanostructured electrodes form an integral part of a wide variety of electrochemical systems for biomolecular detection, batteries, solar cells, scanning electrochemical microscopy, etc. Given the complexity of the electrode structures, the Butler-Volmer formalism of redox reactions, and the diffusion transport of redox species, it is hardly surprising that only a few problems are amenable to closed-form, compact analytical solutions. While numerical solutions are widely used, it is often difficult to integrate the insights gained into the design and optimization of electrochemical systems. In this article, we develop a comprehensive analytical formalism for current transients that not only anticipate the responses of complex electrode structures to complicated voltammetry measurements, but also intuitively interpret diverse experiments such as redox detection of molecules at nanogap electrodes, scanning electrochemical microscopy, etc. The results from the analytical model, well supported through detailed numerical simulations and experimental data from the literature, have broad implications in the design and optimization of nanostructured electrodes for healthcare and energy storage applications.

Wavelength-dependent absorption in structurally tailored randomly branched vertical arrays of InSb nanowires.

Arrays of semiconductor nanowires are of potential interest for applications including photovoltaic devices and IR detectors/imagers. While nominally uniform arrays have typically been studied, arrays containing nanowires with multiple diameters and/or random distributions of diameters could allow tailoring of the photonic properties of the arrays. In this Letter, we demonstrate the growth and optical properties of randomly branched InSb nanowire arrays. The structure mentioned can be approximated as three vertically stacked regions, with average diameters of 20, 100, and 150 nm within the respective layers. Reflectance and transmittance measurements on structures with different average nanowire lengths have been performed over the wavelength range of 300-2000 nm, and absorbance has been calculated from these measurements. The structures show low reflectance over the visible and IR regions and wavelength-dependent absorbance in the IR region. A model considering the diameter-dependent photonic coupling (at a given wavelength) and random distribution of nanowire diameters within the regions has been developed. The diameter-dependent photonic coupling results in a roll-off in the absorbance spectra at wavelengths well below the bulk cutoff of ∼7 µm, and randomness is observed to broaden the absorbance response. Varying the average diameters would allow tailoring of the wavelength dependent absorption within various layers, which could be employed in photovoltaic devices or wavelength-dependent IR imagers.

In Situ Drift Monitoring and Calibration of Field-Deployed Potentiometric Sensors Using Temperature Supervision.

Potentiometric ion-selective electrodes (ISEs) have broad applications in personalized healthcare, smart agriculture, oil/gas exploration, and environmental monitoring. However, high-precision potentiometric sensing is difficult with field-deployed sensors due to time-dependent voltage drift and the need for frequent calibration. In the laboratory setting, these issues are resolved by repeated calibration by measuring the voltage response at multiple standard solutions at a constant temperature. For field-deployed sensors, it is difficult to frequently interrupt operation and recalibrate with standard solutions. Moreover, the constant surrounding temperature constraint imposed by the traditional calibration process makes it unsuitable for temperature-varying field use. To address the challenges of traditional calibration for field-deployed sensors, in this study, we propose a novel in situ calibration approach in which we use natural/external temperature variation in the field to obtain the time-varying calibration parameters, without having to relocate the sensors or use any complex system. We also develop a temperature-supervised monitoring method to detect the drift of the sensor during operation. Collectively, the temperature-based drift monitoring and in situ calibration methods allow us to monitor the drift of sensors and correct them periodically to achieve high-precision sensing. We demonstrate our approach in three testbeds: (1) under controlled temperature variation in the lab, (2) under natural temperature variation in a greenhouse, and (3) in the field to monitor nitrate activity of an agricultural site. In the laboratory study, we validate that the calibration parameters of printed nitrate ISEs can be reproduced by our proposed calibration process; therefore, it can serve as an alternative to traditional calibration processes. In the greenhouse, we show the use of natural temperature variation to calibrate the sensors and detect the drift in a fixed concentration nitrate solution. Finally, we demonstrate the use of the method to monitor the nitrate activity of an agricultural field within 10% of laboratory-based measurements (i.e., a sensitivity of 0.03 mM) for a period of 22 days. The findings highlight the prospect of temperature-based calibration and drift monitoring for high-precision sensing with field-deployed ISEs.

A new paradigm of reliable sensing with field-deployed electrochemical sensors integrating data redundancy and source credibility.

For a continuous healthcare or environmental monitoring system, it is essential to reliably sense the analyte concentration reported by electrochemical sensors. However, environmental perturbation, sensor drift, and power-constraint make reliable sensing with wearable and implantable sensors difficult. While most studies focus on improving sensor stability and precision by increasing the system's complexity and cost, we aim to address this challenge using low-cost sensors. To obtain the desired accuracy from low-cost sensors, we borrow two fundamental concepts from communication theory and computer science. First, inspired by reliable data transmission over a noisy communication channel by incorporating redundancy, we propose to measure the same quantity (i.e., analyte concentration) with multiple sensors. Second, we estimate the true signal by aggregating the output of the sensors based on their credibility, a technique originally developed for "truth discovery" in social sensing applications. We use the Maximum Likelihood Estimation to estimate the true signal and the credibility index of the sensors over time. Using the estimated signal, we develop an on-the-fly drift-correction method to make unreliable sensors reliable by correcting any systematic drifts during operation. Our approach can determine solution pH within 0.09 pH for more than three months by detecting and correcting the gradual drift of pH sensors as a function of gamma-ray irradiation. In the field study, we validate our method by measuring nitrate levels in an agricultural field onsite over 22 days within 0.06 mM of a high-precision laboratory-based sensor. We theoretically demonstrate and numerically validate that our approach can estimate the true signal even when the majority (~ 80%) of the sensors are unreliable. Moreover, by restricting wireless transmission to high-credible sensors, we achieve near-perfect information transfer at a fraction of the energy cost. The high-precision sensing with low-cost sensors at reduced transmission cost will pave the way for pervasive in-field sensing with electrochemical sensors. The approach is general and can improve the accuracy of any field-deployed sensors undergoing drift and degradation during operation.

Wearable Sensor Patch with Hydrogel Microneedles for In Situ Analysis of Interstitial Fluid.

Continuous real-time monitoring of biomarkers in interstitial fluid is essential for tracking metabolic changes and facilitating the early detection and management of chronic diseases such as diabetes. However, developing minimally invasive sensors for the in situ analysis of interstitial fluid and addressing signal delays remain a challenge. Here, we introduce a wearable sensor patch incorporating hydrogel microneedles for rapid, minimally invasive collection of interstitial fluid from the skin while simultaneously measuring biomarker levels in situ. The sensor patch is stretchable to accommodate the swelling of the hydrogel microneedles upon extracting interstitial fluid and adapts to skin deformation during measurements, ensuring consistent sensing performance in detecting model biomarker concentrations, such as glucose and lactate, in a mouse model. The sensor patch exhibits in vitro sensitivities of 0.024 ± 0.002 µA mM-1 for glucose and 0.0030 ± 0.0004 µA mM-1 for lactate, with corresponding linear ranges of 0.1-3 and 0.1-12 mM, respectively. For in vivo glucose sensing, the sensor patch demonstrates a sensitivity of 0.020 ± 0.001 µA mM-1 and a detection range of 1-8 mM. By integrating a predictive model, the sensor patch can analyze and compensate for signal delays, improving calibration reliability and providing guidance for potential optimization in sensing performance. The sensor patch is expected to serve as a minimally invasive platform for the in situ analysis of multiple biomarkers in interstitial fluid, offering a promising solution for continuous health monitoring and disease management.

Prospects for nanowire-doped polycrystalline graphene films for ultratransparent, highly conductive electrodes.

Traditional transparent conducting materials such as ITO are expensive, brittle, and inflexible. Although alternatives like networks of carbon nanotubes, polycrystalline graphene, and metallic nanowires have been proposed, the transparency-conductivity trade-off of these materials makes them inappropriate for broad range of applications. In this paper, we show that the conductivity of polycrystalline graphene is limited by high resistance grain boundaries. We demonstrate that a composite based on polycrystalline graphene and a subpercolating network of metallic nanowires offers a simple and effective route to reduced resistance while maintaining high transmittance. This new approach of "percolation-doping by nanowires" has the potential to beat the transparency-conductivity constraints of existing materials and may be suitable for broad applications in photovoltaics, flexible electronics, and displays.

Moore's law: The journey ahead.

High-performance electronics will focus on increasing the rate of computation.