A universal all-solid synthesis for high throughput production of halide perovskite.

Halide perovskites show ubiquitous presences in growing fields at both fundamental and applied levels. Discovery, investigation, and application of innovative perovskites are heavily dependent on the synthetic methodology in terms of time-/yield-/effort-/energy- efficiency. Conventional wet chemistry method provides the easiness for growing thin film samples, but represents as an inefficient way for bulk crystal synthesis. To overcome these, here we report a universal solid state-based route for synthesizing high-quality perovskites, by means of simultaneously applying both electric and mechanical stress fields during the synthesis, i.e., the electrical and mechanical field-assisted sintering technique. We employ various perovskite compositions and arbitrary geometric designs for demonstration in this report, and establish such synthetic route with uniqueness of ultrahigh yield, fast processing and solvent-free nature, along with bulk products of exceptional quality approaching to single crystals. We exemplify the applications of the as-synthesized perovskites in photodetection and thermoelectric as well as other potentials to open extra chapters for future technical development.

Bio-inspired strategies for next-generation perovskite solar mobile power sources.

Smart electronic devices are becoming ubiquitous due to many appealing attributes including portability, long operational time, rechargeability and compatibility with the user-desired form factor. Integration of mobile power sources (MPS) based on photovoltaic technologies with smart electronics will continue to drive improved sustainability and independence. With high efficiency, low cost, flexibility and lightweight features, halide perovskite photovoltaics have become promising candidates for MPS. Realization of these photovoltaic MPS (PV-MPS) with unconventionally extraordinary attributes requires new 'out-of-box' designs. Natural materials have provided promising designing solutions to engineer properties under a broad range of boundary conditions, ranging from molecules, proteins, cells, tissues, apparatus to systems in animals, plants, and humans optimized through billions of years of evolution. Applying bio-inspired strategies in PV-MPS could be biomolecular modification on crystallization at the atomic/meso-scale, bio-structural duplication at the device/system level and bio-mimicking at the functional level to render efficient charge delivery, energy transport/utilization, as well as stronger resistance against environmental stimuli (e.g., self-healing and self-cleaning). In this review, we discuss the bio-inspired/-mimetic structures, experimental models, and working principles, with the goal of revealing physics and bio-microstructures relevant for PV-MPS. Here the emphasis is on identifying the strategies and material designs towards improvement of the performance of emerging halide perovskite PVs and strategizing their bridge to future MPS.

Electrocaloric Performance of Multilayer Ceramic Chips: Effect of Geometric Structure Induced Internal Stress.

Driven by an ever-growing demand for environmentally benign cooling systems, the past decade has witnessed the booming development in the field of electrocaloric (EC) cooling technology, which is considered as a promising solid-state cooling approach. Multilayer ceramic chip capacitors (MLCCs) represent the optimum structure for EC cooling elements because of large breakdown strengths, low driving voltages, and high macroscopic volumes of active EC materials. However, fundamental relationships between the geometric parameters of MLCCs and the EC coefficient are less understood. In this study, 0.92Pb(Mg1/3Nb2/3)O3-0.08PbTiO3 (PMN-PT) MLCCs with controlled configurations, such as active/inactive layer thickness, number of layers, and active volume ratio, were fabricated, and their EC performance was evaluated. The electric properties of the MLCCs are confirmed to be closely related to the geometric structure, which influences not only the heat flow but also the internal stress, resulting in the variability of EC performance and reliability/breakdown strength. The internal stress arises due to the residual thermal stress originating from the densification-related shrinkage, thermal expansion mismatch during the sintering, and clamping stress arising from the inactive area due to the large strain from the active area under a high electric field. The geometric structure-based stress distribution and the magnitude of stress on the active layers in MLCCs were determined by finite element modeling (FEM) and correlated with the experimental EC coefficients. The results reveal that a low inactive volume percentage is beneficial toward increasing the breakdown field and enhancement of EC performance because of reduced clamping stress on active EC material.

A New Method for Evaluation of the Complex Material Coefficients of Piezoelectric Ceramics in the Radial Vibration Modes.

The determination of complex elastic, piezoelectric, and dielectric coefficients of piezoelectric ceramics is important for precision engineering devices. Here, a novel method for determining the optimal material coefficients is presented. This method minimizes the average relative error in the values of conductance, susceptance, resistance, and reactance obtained from the 1-D model in the IEEE Standard (ANSI/IEEE Std 176-1987) and the experimental measurements of the first and second radial modes. Poisson's ratio is assumed to be a complex number in addition to the elastic, piezoelectric, and dielectric coefficients in the present method. The global minimum of the average relative error is found by searching the minimum among all local minima of the average relative error, which are obtained with the Levenberg-Marquardt modification of Newton's method from randomly chosen initial conditions. The optimal material coefficients of an APC 850 disk and an APC 855 disk are calculated with this method. The uncertainties in the optimal material coefficients are evaluated by calculating the minimum average relative error when the real or imaginary part of each coefficient is prescribed.

Universal Multienergy Harvester Architecture.

The energy available in the ambient vibrations, magnetic fields, and sunlight can be simultaneously or independently harvested using universal architecture. The universal harvester design is shown to effectively convert ambient magnetic fields, vibration, and light into electricity. The architecture is composed of a perovskite solar cell integrated onto a magnetoelectric composite cantilever beam. The efficiency of the large-area perovskite solar cell is shown to reach 15.74% (cell area is >1100% larger than traditional perovskite solar cells) by selecting glass/indium tin oxide (ITO) as the cathode that reduces the charge recombination. The magnetoelectric composite beam is designed to include the effect of the mass and volume of the solar cell on power generation. Results demonstrate that universal energy harvester can simultaneously capture vibration, magnetic fields, and solar irradiation to provide an ultrahigh-power density of 18.6 mW/cm3. The total power generated by the multienergy harvester, including vibration, magnetic field, and solar stimuli, is 23.52 mW from a total surface area of 9.6 cm2 and a total volume of 1.26 cm3. These results will have a tremendous impact on the design of the power sources for Internet of Things sensors and wireless devices.

Laser-sculptured ultrathin transition metal carbide layers for energy storage and energy harvesting applications.

Ultrathin transition metal carbides with high capacity, high surface area, and high conductivity are a promising family of materials for applications from energy storage to catalysis. However, large-scale, cost-effective, and precursor-free methods to prepare ultrathin carbides are lacking. Here, we demonstrate a direct pattern method to manufacture ultrathin carbides (MoCx, WCx, and CoCx) on versatile substrates using a CO2 laser. The laser-sculptured polycrystalline carbides (macroporous, ~10-20 nm wall thickness, ~10 nm crystallinity) show high energy storage capability, hierarchical porous structure, and higher thermal resilience than MXenes and other laser-ablated carbon materials. A flexible supercapacitor made of MoCx demonstrates a wide temperature range (-50 to 300 °C). Furthermore, the sculptured microstructures endow the carbide network with enhanced visible light absorption, providing high solar energy harvesting efficiency (~72 %) for steam generation. The laser-based, scalable, resilient, and low-cost manufacturing process presents an approach for construction of carbides and their subsequent applications.

Ultra-high performance wearable thermoelectric coolers with less materials.

Thermoelectric coolers are attracting significant attention for replacing age-old cooling and refrigeration devices. Localized cooling by wearable thermoelectric coolers will decrease the usage of traditional systems, thereby reducing global warming and providing savings on energy costs. Since human skin as well as ambient air is a poor conductor of heat, wearable thermoelectric coolers operate under huge thermally resistive environment. The external thermal resistances greatly influence thermoelectric material behavior, device design, and device performance, which presents a fundamental challenge in achieving high efficiency for on-body applications. Here, we examine the combined effect of heat source/sink thermal resistances and thermoelectric material properties on thermoelectric cooler performance. Efficient thermoelectric coolers demonstrated here can cool the human skin up to 8.2 °C below the ambient temperature (170% higher cooling than commercial modules). Cost-benefit analysis shows that cooling over material volume for our optimized thermoelectric cooler is 500% higher than that of the commercial modules.

Ultrahigh Durability Perovskite Solar Cells.

Unprecedented conversion efficiency has been demonstrated for perovskite solar cells (PSCs), however, their stability and reliability continue to be challenge. Here, an effective and practical method is demonstrated to overcome the device stability issues in PSCs. A CF4 plasma treatment method is developed that results in the formation of a robust C-F x layer covering the PSC device, thereby, imparting protection during the operation of solar cell. PSCs exposed to fluorination process showed excellent stability against water, light, and oxygen, displaying relatively no noticeable degradation after being dipped into water for considerable time period. The fluorination process did not have any impact on the morphology and electrical property of the top Spiro-OMeTAD layer, resulting in a conversion efficiency of 18.7%, which is identical to that of the pristine PSC. Under the continuous Xe lamp (AM 1.5G, 1 sun) illumination in ambient air for 100 h, the fluorinated PSCs demonstrated 70% of initial conversion efficiency, which is 4000% higher than that of the pristine PSC devices. We believe this breakthrough will have significant impact on the transition of PSCs into real world applications.

Colossal tunability in high frequency magnetoelectric voltage tunable inductors.

The electrical modulation of magnetization through the magnetoelectric effect provides a great opportunity for developing a new generation of tunable electrical components. Magnetoelectric voltage tunable inductors (VTIs) are designed to maximize the electric field control of permeability. In order to meet the need for power electronics, VTIs operating at high frequency with large tunability and low loss are required. Here we demonstrate magnetoelectric VTIs that exhibit remarkable high inductance tunability of over 750% up to 10 MHz, completely covering the frequency range of state-of-the-art power electronics. This breakthrough is achieved based on a concept of magnetocrystalline anisotropy (MCA) cancellation, predicted in a solid solution of nickel ferrite and cobalt ferrite through first-principles calculations. Phase field model simulations are employed to observe the domain-level strain-mediated coupling between magnetization and polarization. The model reveals small MCA facilitates the magnetic domain rotation, resulting in larger permeability sensitivity and inductance tunability.

Self-Assembly of Large-Area 2D Polycrystalline Transition Metal Carbides for Hydrogen Electrocatalysis.

Low-dimensional (0/1/2 dimension) transition metal carbides (TMCs) possess intriguing electrical, mechanical, and electrochemical properties, and they serve as convenient supports for transition metal catalysts. Large-area single-crystalline 2D TMC sheets are generally prepared by exfoliating MXene sheets from MAX phases. Here, a versatile bottom-up method is reported for preparing ultrathin TMC sheets (≈10 nm in thickness and >100 µm in lateral size) with metal nanoparticle decoration. A gelatin hydrogel is employed as a scaffold to coordinate metal ions (Mo5+ , W6+ , Co2+ ), resulting in ultrathin-film morphologies of diverse TMC sheets. Carbonization of the scaffold at 600 °C presents a facile route to the corresponding MoCx , WCx , CoCx , and to metal-rich hybrids (Mo2- x Wx C and W/Mo2 C-Co). Among these materials, the Mo2 C-Co hybrid provides excellent hydrogen evolution reaction (HER) efficiency (Tafel slope of 39 mV dec-1 and 48 mVj = 10 mA cm-2 in overpotential in 0.5 m H2 SO4 ). Such performance makes Mo2 C-Co a viable noble-metal-free catalyst for the HER, and is competitive with the standard platinum on carbon support. This template-assisted, self-assembling, scalable, and low-cost manufacturing process presents a new tactic to construct low-dimensional TMCs with applications in various clean-energy-related fields.

Laser-Induced Molybdenum Carbide-Graphene Composites for 3D Foldable Paper Electronics.

Versatile and low-cost manufacturing processes/materials are essential for the development of paper electronics. Here, a direct-write laser patterning process is developed to make conductive molybdenum carbide-graphene (MCG) composites directly on paper substrates. The hierarchically porous MCG structures are converted from fibrous paper soaked with the gelatin-mediated inks containing molybdenum ions. The resulting Mo3 C2 and graphene composites are mechanically stable and electrochemically active for various potential applications, such as electrochemical ion detectors and gas sensors, energy harvesters, and supercapacitors. Experimentally, the electrical conductivity of the composite is resilient to mechanical deformation with less than 5% degradation after 750 cycles of 180° repeated folding tests. As such, the direct laser conversion of MCGs on papers can be applicable for paper-based electronics, including the 3D origami folding structures.

Magnetic Field Sensing by Exploiting Giant Nonstrain-Mediated Magnetodielectric Response in Epitaxial Composites.

Heteroepitaxial magnetoelectric (ME) composites are promising for the development of a new generation of multifunctional devices, such as sensors, tunable electronics, and energy harvesters. However, challenge remains in realizing practical epitaxial composite materials, mainly due to the interfacial lattice misfit strain between magnetostrictive and piezoelectric phases and strong substrate clamping that reduces the strain-mediated ME coupling. Here, we demonstrate a nonstrain-mediated ME coupling in PbZr0.52Ti0.48O3 (PZT)/La0.67Sr0.33MnO3 (LSMO) heteroepitaxial composites that resolves these challenges, thereby, providing a giant magnetodielectric (MD) response of ∼27% at 310 K. The factors driving the magnitude of the MD response were found to be the magnetoresistance-coupled dielectric dispersion and piezoelectric strain-mediated modulation of magnetic moment. Building upon this giant MD response, we demonstrate a magnetic field sensor architecture exhibiting a high sensitivity of 54.7 pF/T and desirable linearity with respect to the applied external magnetic field. The demonstrated technique provides a new mechanism for detecting magnetic fields based upon the MD effect.

Self-Powered Temperature-Mapping Sensors Based on Thermo-Magneto-Electric Generator.

We demonstrate a thermo-magneto-electric generator (TMEG) based on second-order phase transition of soft magnetic materials that provides a promising pathway for scavenging low-grade heat. It takes advantage of the cyclic magnetic forces of attraction and repulsion arising through ferromagnetic-to-paramagnetic phase transition to create mechanical vibrations that are converted into electricity through piezoelectric benders. To enhance the mechanical vibration frequency and thereby the output power of the TMEG, we utilize the nonlinear behavior of piezoelectric cantilevers and enhanced thermal transport through silver (Ag) nanoparticles (NPs) applied on the surface of a soft magnet. This results in large enhancement of the oscillation frequency reaching up to 9 Hz (300% higher compared with that of the prior literature). Optimization of the piezoelectric beam and Ag NP distribution resulted in the realization of nonlinear TMEGs that can generate a high output power of 80 µW across the load resistance of 0.91 MΩ, which is 2200% higher compared with that of the linear TMEG. Using a nonlinear TMEG, we fabricated and evaluated self-powered temperature-mapping sensors for monitoring the thermal variations across the surface. Combined, our results demonstrate that nonlinear TMEGs can provide additional functionality including temperature monitoring, thermal mapping, and powering sensor nodes.

Kirigami-inspired, highly stretchable micro-supercapacitor patches fabricated by laser conversion and cutting.

The recent developments in material sciences and rational structural designs have advanced the field of compliant and deformable electronics systems. However, many of these systems are limited in either overall stretchability or areal coverage of functional components. Here, we design a construct inspired by Kirigami for highly deformable micro-supercapacitor patches with high areal coverages of electrode and electrolyte materials. These patches can be fabricated in simple and efficient steps by laser-assisted graphitic conversion and cutting. Because the Kirigami cuts significantly increase structural compliance, segments in the patches can buckle, rotate, bend and twist to accommodate large overall deformations with only a small strain (<3%) in active electrode areas. Electrochemical testing results have proved that electrical and electrochemical performances are preserved under large deformation, with less than 2% change in capacitance when the patch is elongated to 382.5% of its initial length. The high design flexibility can enable various types of electrical connections among an array of supercapacitors residing in one patch, by using different Kirigami designs.

Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors.

While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS2 ) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g-1 in an Li-rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg-1 -the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg-1 with stable operation over 10 000 cycles. A flexible solid-state supercapacitor prepared by transferring the TiS2 -VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min.

Optimization of segmented thermoelectric generator using Taguchi and ANOVA techniques.

Recent studies have demonstrated that segmented thermoelectric generators (TEGs) can operate over large thermal gradient and thus provide better performance (reported efficiency up to 11%) as compared to traditional TEGs, comprising of single thermoelectric (TE) material. However, segmented TEGs are still in early stages of development due to the inherent complexity in their design optimization and manufacturability. In this study, we demonstrate physics based numerical techniques along with Analysis of variance (ANOVA) and Taguchi optimization method for optimizing the performance of segmented TEGs. We have considered comprehensive set of design parameters, such as geometrical dimensions of p-n legs, height of segmentation, hot-side temperature, and load resistance, in order to optimize output power and efficiency of segmented TEGs. Using the state-of-the-art TE material properties and appropriate statistical tools, we provide near-optimum TEG configuration with only 25 experiments as compared to 3125 experiments needed by the conventional optimization methods. The effect of environmental factors on the optimization of segmented TEGs is also studied. Taguchi results are validated against the results obtained using traditional full factorial optimization technique and a TEG configuration for simultaneous optimization of power and efficiency is obtained.

Correlation between tunability and anisotropy in magnetoelectric voltage tunable inductor (VTI).

Electric field modulation of magnetic properties via magnetoelectric coupling in composite materials is of fundamental and technological importance for realizing tunable energy efficient electronics. Here we provide foundational analysis on magnetoelectric voltage tunable inductor (VTI) that exhibits extremely large inductance tunability of up to 1150% under moderate electric fields. This field dependence of inductance arises from the change of permeability, which correlates with the stress dependence of magnetic anisotropy. Through combination of analytical models that were validated by experimental results, comprehensive understanding of various anisotropies on the tunability of VTI is provided. Results indicate that inclusion of magnetic materials with low magnetocrystalline anisotropy is one of the most effective ways to achieve high VTI tunability. This study opens pathway towards design of tunable circuit components that exhibit field-dependent electronic behavior.

Wearable woven supercapacitor fabrics with high energy density and load-bearing capability.

Flexible power sources with load bearing capability are attractive for modern wearable electronics. Here, free-standing supercapacitor fabrics that can store high electrical energy and sustain large mechanical loads are directly woven to be compatible with flexible systems. The prototype with reduced package weight/volume provides an impressive energy density of 2.58 mWh g-1 or 3.6 mWh cm-3, high tensile strength of over 1000 MPa, and bearable pressure of over 100 MPa. The nanoporous thread electrodes are prepared by the activation of commercial carbon fibers to have three-orders of magnitude increase in the specific surface area and 86% retention of the original strength. The novel device configuration woven by solid electrolyte-coated threads shows excellent flexibility and stability during repeated mechanical bending tests. A supercapacitor watchstrap is used to power a liquid crystal display as an example of load-bearing power sources with various form-factor designs for wearable electronics.

Ultrathin Coaxial Fiber Supercapacitors Achieving High Energy and Power Densities.

Fiber-based supercapacitors have attracted significant interests because of their potential applications in wearable electronics. Although much progress has been made in recent years, the energy and power densities, mechanical strength, and flexibility of such devices are still in need of improvement for practical applications. Here, we demonstrate an ultrathin microcoaxial fiber supercapacitor (µCFSC) with high energy and power densities (2.7 mW h/cm3 and 13 W/cm3), as well as excellent mechanical properties. The prototype with the smallest reported overall diameter (∼13 µm) is fabricated by successive coating of functional layers onto a single micro-carbon-fiber via a scalable process. Combining the simulation results via the electrochemical model, we attribute the high performance to the well-controlled thin coatings that make full use of the electrode materials and minimize the ion transport path between electrodes. Moreover, the µCFSC features high bending flexibility and large tensile strength (more than 1 GPa), which make it promising as a building block for various flexible energy storage applications.

Lead-free epitaxial ferroelectric material integration on semiconducting (100) Nb-doped SrTiO3 for low-power non-volatile memory and efficient ultraviolet ray detection.

We report lead-free ferroelectric based resistive switching non-volatile memory (NVM) devices with epitaxial (1-x)BaTiO3-xBiFeO3 (x = 0.725) (BT-BFO) film integrated on semiconducting (100) Nb (0.7%) doped SrTiO3 (Nb:STO) substrates. The piezoelectric force microscopy (PFM) measurement at room temperature demonstrated ferroelectricity in the BT-BFO thin film. PFM results also reveal the repeatable polarization inversion by poling, manifesting its potential for read-write operation in NVM devices. The electroforming-free and ferroelectric polarization coupled electrical behaviour demonstrated excellent resistive switching with high retention time, cyclic endurance, and low set/reset voltages. X-ray photoelectron spectroscopy was utilized to determine the band alignment at the BT-BFO and Nb:STO heterojunction, and it exhibited staggered band alignment. This heterojunction is found to behave as an efficient ultraviolet photo-detector with low rise and fall time. The architecture also demonstrates half-wave rectification under low and high input signal frequencies, where the output distortion is minimal. The results provide avenue for an electrical switch that can regulate the pixels in low or high frequency images. Combined this work paves the pathway towards designing future generation low-power ferroelectric based microelectronic devices by merging both electrical and photovoltaic properties of BT-BFO materials.