The Impact of Intergrain Phases on the Ionic Conductivity of the LAGP Solid Electrolyte Material Prepared by Spark Plasma Sintering.

Li1.5Al0.5Ge1.5(PO4)3 (LAGP) is a promising oxide solid electrolyte for all-solid-state batteries due to its excellent air stability, acceptable electrochemical stability window, and cost-effective precursor materials. However, further improvement in the ionic conductivity performance of oxide solid-state electrolytes is hindered by the presence of grain boundaries and their associated morphologies and composition. These key factors thus represent a major obstacle to the improved design of modern oxide based solid-state electrolytes. This study establishes a correlation between the influence of the grain boundary phases, their 3D morphology, and compositions formed under different sintering conditions on the overall LAGP ionic conductivity. Spark plasma sintering has been employed to sinter oxide solid electrolyte material at different temperatures with high compacity values, whereas a combined potentiostatic electrochemical impedance spectroscopy, 3D FIB-SEM tomography, XRD, and solid-state NMR/materials modeling approach provides an in-depth analysis of the influence of the morphology, structure, and composition of the grain boundary phases that impact the total ionic conductivity. This work establishes the first 3D FIB-SEM tomography analysis of the LAGP morphology and the secondary phases formed in the grain boundaries at the nanoscale level, whereas the associated 31P and 27Al MAS NMR study coupled with materials modeling reveals that the grain boundary material is composed of Li4P2O7 and disordered Li9Al3(P2O7)3(PO4)2 phases. Quantitative 31P MAS NMR measurements demonstrate that optimal ionic conductivity for the LAGP system is achieved for the 680 °C SPS preparation when the disordered Li9Al3(P2O7)3(PO4)2 phase dominates the grain boundary composition with reduced contributions from the highly ordered Li4P2O7 phases, whereas the 27Al MAS NMR data reveal that minimal structural change is experienced by each phase throughout this suite of sintering temperatures.

Effect of Air Exposure on Electron-Beam-Induced Degradation of Perovskite Films.

Organic-inorganic halide perovskites are interesting candidates for solar cell and optoelectronic applications owing to their advantageous properties such as a tunable band gap, low material cost, and high charge carrier mobilities. Despite making significant progress, concerns about material stability continue to impede the commercialization of perovskite-based technology. In this article, we investigate the impact of environmental parameters on the alteration of structural properties of MAPbI3 (CH3NH3PbI3) thin films using microscopy techniques. These characterizations are performed on MAPbI3 thin films exposed to air, nitrogen, and vacuum environments, the latter being possible by using dedicated air-free transfer setups, after their fabrication into a nitrogen-filled glovebox. We observed that even less than 3 min of air exposure increases the sensitivity to electron beam deterioration and modifies the structural transformation pathway as compared to MAPbI3 thin films which are not exposed to air. Similarly, the time evolution of the optical responses and the defect formation of both air-exposed and non-air-exposed MAPbI3 thin films are measured by time-resolved photoluminescence. The formation of defects in the air-exposed MAPbI3 thin films is first observed by optical techniques at longer timescales, while structural modifications are observed by transmission electron microscopy (TEM) measurements and supported by X-ray photoelectron spectroscopy (XPS) measurements. Based on the complementarity of TEM, XPS, and time-resolved optical measurements, we propose two different degradation mechanism pathways for air-exposed and non-air-exposed MAPbI3 thin films. We find that when exposed to air, the crystalline structure of MAPbI3 shows gradual evolution from its initial tetragonal MAPbI3 structure to PbI2 through three different stages. No significant structural changes over time from the initial structure are observed for the MAPbI3 thin films which are not exposed to air.

Recovery Mechanisms in Aged Kesterite Solar Cells.

For successful long-term deployment and operation of kesterites Cu2ZnSn(S x Se1-x )4 (CZTSSe) as light-absorber materials for photovoltaics, device stability and recovery in kesterite solar cells are investigated. A low-temperature heat treatment is applied to overcome the poor charge extraction that developed in the natural aging process. It is suggested that defect states at aged CZTSSe/CdS heterojunctions were reduced, while apparent doping density in the CZTSSe absorber increased due to Cd/Zn interdiffusion at the heterojunction during the annealing process. In situ annealing experiments in a transmission electron microscope were used to investigate the elemental diffusion at the CZTSSe/CdS heterojunction. This study reveals the critical role of heat treatment to enhance the absorber/Mo back contact, improve the quality of the absorber/buffer heterojunction, and recover the device performance in aged kesterite thin-film solar cells.

Operando Direct Observation of Filament Formation in Resistive Switching Devices Enabled by a Topological Transformation Molecule.

Conductive filaments (CFs) play a critical role in the mechanism of resistive random-access memory (ReRAM) devices. However, in situ detection and visualization of the precise location of CFs are still key challenges. We demonstrate for the first time the use of a π-conjugated molecule which can transform between its twisted and planar states upon localized Joule heating generated within filament regions, thus reflecting the locations of the underlying CFs. Customized patterns of CFs were induced and observed by the π-conjugated molecule layer, which confirmed the hypothesis. Additionally, statistical studies on filaments distribution were conducted to study the effect of device sizes and bottom electrode heights, which serves to enhance the understanding of switching behavior and their variability at device level. Therefore, this approach has great potential in aiding the development of ReRAM technology.

High-k, Ultrastretchable Self-Enclosed Ionic Liquid-Elastomer Composites for Soft Robotics and Flexible Electronics.

Soft robotics focuses on mimicking natural systems to produce dexterous motion. Dielectric elastomer actuators (DEAs) are an attractive option due to their large strains, high efficiencies, lightweight design, and integrability, but require high electric fields. Conventional approaches to improve DEA performance by incorporating solid fillers in the polymer matrices can increase the dielectric constant but to the detriment of mechanical properties. In the present work, we draw inspiration from soft and deformable human skin, enabled by its unique structure, which consists of a fluid-filled membrane, to create self-enclosed liquid filler (SELF)-polymer composites by mixing an ionic liquid into the elastomeric matrix. Unlike hydrogels and ionogels, the SELF-polymer composites are made from immiscible liquid fillers, selected based on interfacial interaction with the elastomer matrix, and exist as dispersed globular phases. This combination of structure and filler selection unlocks synergetic improvements in electromechanical properties-doubling of dielectric constant, 100 times decrease in Young's modulus, and ∼5 times increase in stretchability. These composites show superior thermal stability to volatile losses, combined with excellent transparency. These ultrasoft high-k composites enable a significant improvement in the actuation performance of DEAs-longitudinal strain (5 times) and areal strain (8 times)-at low applied nominal electric fields (4 V/µm). They also enable high-sensitivity capacitive pressure sensors without the need of miniaturization and microstructuring. This class of self-enclosed ionic liquid polymer composites could impact the areas of soft robotics, shape morphing, flexible electronics, and optoelectronics.

Directed Assembly of Liquid Metal-Elastomer Conductors for Stretchable and Self-Healing Electronics.

Growing interest in soft robotics, stretchable electronics, and electronic skins has created demand for soft, compliant, and stretchable electrodes and interconnects. Here, dielectrophoresis (DEP) is used to assemble, align, and sinter eutectic gallium indium (EGaIn) microdroplets in uncured poly(dimethylsiloxane) (PDMS) to form electrically conducting microwires. There are several noteworthy aspects of this approach. 1) Generally, EGaIn droplets in silicone at loadings approaching 90 wt% remain insulating and form a conductive network only when subjected to sintering. Here, DEP facilitates assembly of EGaIn droplets into conductive microwires at loadings as low as 10 wt%. 2) DEP is done in silicone for the first time, enabling the microwires to be cured in a stretchable matrix. 3) Liquid EGaIn droplets sinter during DEP to form a stretchable metallic microwire that retains its shape after curing the silicone. 4) Use of liquid metal eliminates the issue of compliance mismatch observed in soft polymers with solid fillers. 5) The silicone-EGaIn "ink" can be assembled by DEP within the crevices of severely damaged wires to create stretchable interconnects that heal the damage mechanically and electrically. The DEP process of this unique set of materials is characterized and the interesting attributes enabled by such liquid microwires are demonstrated.

Glass formation of a DMSO-water mixture probed with a photosynthetic pigment.

Despite their extensive industrial usage, glass-forming liquids are not fully understood, and methods to investigate their dynamical heterogeneity are sought after. Here we show how the appearance of a second component in the visible absorption spectrum of a photosynthetic pigment upon cooling can be used to probe the glass transition of a dimethylsulfoxide-water mixture. The changes in the relative ratio of the two components with respect to temperature follow a sigmoid curve, and we show that the second component arises due to protonation of the pigment at low temperatures. Furthermore, from visible transient absorption spectra we show that, unlike the first component, the dynamics of the second component slows down significantly at lower temperatures, suggesting that there are two distinct environments with fast and slow fluctuations. Our results therefore enable a new method to characterize the dynamical heterogeneity of glass-forming liquids.

Neural network approach for non-invasive detection of hyperglycemia using electrocardiographic signals.

Hyperglycemia or high blood glucose (sugar) level is a common dangerous complication among patients with Type 1 diabetes mellitus (T1DM). Hyperglycemia can cause serious health problems if left untreated such as heart disease, stroke, vision and nerve problems. Based on the electrocardiographic (ECG) parameters, we have identified hyperglycemic and normoglycemic states in T1DM patients. In this study, a classification unit is introduced with the approach of feed forward multi-layer neural network to detect the presences of hyperglycemic/normoglycemic episodes using ECG parameters as inputs. A practical experiment using the real T1DM patients' data sets collected from Department of Health, Government of Western Australia is studied. Experimental results show that proposed ECG parameters contributed significantly to the good performance of hyperglycemia detections in term of sensitivity, specificity and geometric mean (70.59%, 65.38%, and 67.94%, respectively). From these results, it is proved that hyperglycemic events in T1DM can be detected non-invasively and effectively by using ECG signals and ANN approach.

Identification of hypoglycemia and hyperglycemia in type 1 diabetic patients using ECG parameters.

Hypoglycemia and Hyperglycemia are both serious diseases related to diabetes mellitus. Among Type 1 Diabetic patients, there are who experience both hypoglycemic and hyperglycemic events. The aim of this study was to identify of hypoglycemia and hyperglycemia based on ECG changes in this population. An ECG Acquisition and Analysis System based on LabVIEW software has been developed for collecting ECG signals and extracting features with abnormal changes. ECG parameters included Heart rate (HR), corrected QT interval (QTeC), PR interval, corrected RT interval (RTC) and corrected TpTe interval (TpTe(C)). Blood glucose levels were used to classify glycemic states in subjects as hypoglycemic state (≤ 60 mml/l, Hypo), as normoglycemic state (80 to 110 mmol/l, Normo), and as hyperglycemic state 150 mml/l, Hyper). The results indicated that hypoglycemic and hyperglycemic states produce significant inverse changes on those ECG parameters.