A multiscale ion diffusion framework sheds light on the diffusion-stability-hysteresis nexus in metal halide perovskites.

Stability and current-voltage hysteresis stand as major obstacles to the commercialization of metal halide perovskites. Both phenomena have been associated with ion migration, with anecdotal evidence that stable devices yield low hysteresis. However, the underlying mechanisms of the complex stability-hysteresis link remain elusive. Here we present a multiscale diffusion framework that describes vacancy-mediated halide diffusion in polycrystalline metal halide perovskites, differentiating fast grain boundary diffusivity from volume diffusivity that is two to four orders of magnitude slower. Our results reveal an inverse relationship between the activation energies of grain boundary and volume diffusions, such that stable metal halide perovskites exhibiting smaller volume diffusivities are associated with larger grain boundary diffusivities and reduced hysteresis. The elucidation of multiscale halide diffusion in metal halide perovskites reveals complex inner couplings between ion migration in the volume of grains versus grain boundaries, which in turn can predict the stability and hysteresis of metal halide perovskites, providing a clearer path to addressing the outstanding challenges of the field.

Water Quenched and Acceptor-Doped Textured Piezoelectric Ceramics for Off-Resonance and On-Resonance Devices.

Piezoelectric materials should simultaneously possess the soft properties (high piezoelectric coefficient, d33 ; high voltage coefficient, g33 ; high electromechanical coupling factor, k) and hard properties (high mechanical quality factor, Qm ; low dielectric loss, tan δ) along with wide operation temperature (e.g., high rhombohedral-tetragonal phase transition temperature Tr-t ) for covering off-resonance (figure of merit (FOM), d33  × g33 ) and on-resonance (FOM, Qm  × k2 ) applications. However, achieving hard and soft piezoelectric properties simultaneously along with high transition temperature is quite challenging since these properties are inversely related to each other. Here, through a synergistic design strategy of combining composition/phase selection, crystallographic texturing, defect engineering, and water quenching technique, <001> textured 2 mol% MnO2 doped 0.19PIN-0.445PSN-0.365PT ceramics exhibiting giant FOM values of Qm  × k 31 2 $k_{31}^2$ (227-261) along with high d33  × g33 (28-35 × 10-12 m2 N-1 ), low tan δ (0.3-0.39%) and high Tr-t of 140-190 °C, which is far beyond the performance of the state-of-the-art piezoelectric materials, are fabricated. Further, a novel water quenching (WQ) room temperature poling technique, which results in enhanced piezoelectricity of textured MnO2 doped PIN-PSN-PT ceramics, is reported. Based upon the experiments and phase-field modeling, the enhanced piezoelectricity is explained in terms of the quenching-induced rhombohedral phase formation. These findings will have tremendous impact on development of high performance off-resonance and on-resonance piezoelectric devices with high stability.

Invited review: Sensor technologies for real-time monitoring of the rumen environment.

Quantifying digestive and fermentative processes within the rumen environment has been the subject of decades of research; however, our existing research methodologies preclude time-sensitive and spatially explicit investigation of this system. To better understand the temporal and spatial dynamics of the rumen environment, real-time and in situ monitoring of various chemical and physical parameters in the rumen through implantable microsensor technologies is a practical solution. Moreover, such sensors could contribute to the next generation of precision livestock farming, provided sufficient wireless data networking and computing systems are incorporated. In this review, various microsensor technologies applicable to real-time metabolic monitoring for ruminants are introduced, including the detection of parameters for rumen metabolism, such as pH, temperature, histamine concentrations, and volatile fatty acid concentrations. The working mechanisms and requirements of the sensors are summarized with respect to the selected target parameters. Lastly, future challenges and perspectives of this research field are discussed.

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.

Ambient-Air-Stable Lead-Free CsSnI3 Solar Cells with Greater than 7.5% Efficiency.

Black orthorhombic (B-γ) CsSnI3 with reduced biotoxicity and environmental impact and excellent optoelectronic properties is being considered as a promising eco-friendly candidate for high-performing perovskite solar cells (PSCs). A major challenge in a large-scale implementation of CsSnI3 PSCs includes the rapid transformation of Sn2+ to Sn4+ (within a few minutes) under an ambient-air condition. Here, we demonstrate that ambient-air stable B-γ CsSnI3 PSCs can be fabricated by incorporating N,N'-methylenebis(acrylamide) (MBAA) into the perovskite layer and by using poly(3-hexylthiophene) as the hole transporting material. The lone electron pairs of -NH and -CO units of MBAA are designed to form coordination bonding with Sn2+ in the B-γ CsSnI3, resulting in a reduced defect (Sn4+) density and better stability under multiple conditions for the perovskite light absorber. After a modification, the highest power conversion efficiency (PCE) of 7.50% is documented under an ambient-air condition for the unencapsulated CsSnI3-MBAA PSC. Furthermore, the MBAA-modified devices sustain 60.2%, 76.5%, and 58.4% of their initial PCEs after 1440 h of storage in an inert condition, after 120 h of storage in an ambient-air condition, and after 120 h of 1 Sun continuous illumination, respectively.

High-Efficiency Perovskite Solar Cells with Imidazolium-Based Ionic Liquid for Surface Passivation and Charge Transport.

Surface defects have been a key constraint for perovskite photovoltaics. Herein, 1,3-dimethyl-3-imidazolium hexafluorophosphate (DMIMPF6 ) ionic liquid (IL) is adopted to passivate the surface of a formamidinium-cesium lead iodide perovskite (Cs0.08 FA0.92 PbI3 ) and also reduce the energy barrier between the perovskite and hole transport layer. Theoretical simulations and experimental results demonstrate that Pb-cluster and Pb-I antisite defects can be effectively passivated by [DMIM]+ bonding with the Pb2+ ion on the perovskite surface, leading to significantly suppressed non-radiative recombination. As a result, the solar cell efficiency was increased to 23.25 % from 21.09 %. Meanwhile, the DMIMPF6 -treated perovskite device demonstrated long-term stability because the hydrophobic DMIMPF6 layer blocked moisture permeation.

Three-dimensional printing of piezoelectric materials with designed anisotropy and directional response.

Piezoelectric coefficients are constrained by the intrinsic crystal structure of the constituent material. Here we describe design and manufacturing routes to previously inaccessible classes of piezoelectric materials that have arbitrary piezoelectric coefficient tensors. Our scheme is based on the manipulation of electric displacement maps from families of structural cell patterns. We implement our designs by additively manufacturing free-form, perovskite-based piezoelectric nanocomposites with complex three-dimensional architectures. The resulting voltage response of the activated piezoelectric metamaterials at a given mode can be selectively suppressed, reversed or enhanced with applied stress. Additionally, these electromechanical metamaterials achieve high specific piezoelectric constants and tailorable flexibility using only a fraction of their parent materials. This strategy may be applied to create the next generation of intelligent infrastructure, able to perform a variety of structural and functional tasks, including simultaneous impact absorption and monitoring, three-dimensional pressure mapping and directionality detection.

Stable Efficiency Exceeding 20.6% for Inverted Perovskite Solar Cells through Polymer-Optimized PCBM Electron-Transport Layers.

Fullerene derivative, such as [6,6]-phenyl C61 butyric acid methyl ester (PCBM), is widely used as an electron-transport layer (ETL) in inverted perovskite solar cell (PSC). However, its low electron mobility, complexity in achieving quality film formation, and severe nonradiative recombination at perovskite/PCBM interface due to the large electron capture region, lead to lower efficiency for inverted PSCs compared to the normal structures. Herein, we demonstrate an effective and practical strategy to overcome these challenges. Conjugated n-type polymeric materials are mixed together with PCBM to form a homogeneous bulk-mixed (HBM) continuous film with high electron mobility and suitable energy level. HBM film is found to completely cap the perovskite surface to enhance the electron extraction. The critical electron capture radius of the HBM decreases to 12.52 nm from 14.89 nm of PCBM due to the large relative permittivity, resulting in reduced nonradiative recombination at perovskite/HBM interface. The efficiency of inverted PSCs with HBM ETLs exceeds 20.6% with a high fill factor of 0.82. Further, the stability of devices is improved owing to the high hydrophobicity of the HBM ETLs. Under ambient air condition after 45 days, the efficiency of inverted PSCs based on HBM remains 80% of the initial value. This is significantly higher than the control devices which retain only 48% of the initial value under similar aging conditions. We believe these breakthroughs in improving efficiency and stability of inverted PSCs will expedite their transition.

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.

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.

Recent Advances in Flexible Perovskite Solar Cells: Fabrication and Applications.

Flexible perovskite solar cells have attracted widespread research effort because of their potential in portable electronics. The efficiency has exceeded 18 % owing to the high-quality perovskite film achieved by various low-temperature fabrication methods and matching of the interface and electrode materials. This Review focuses on recent progress in flexible perovskite solar cells concerning low-temperature fabrication methods to improve the properties of perovskite films, such as full coverage, uniform morphology, and good crystallinity; demonstrated interface layers used in flexible perovskite solar cells, considering key figures-of-merit such as high transmittance, high carrier mobility, suitable band gap, and easy fabrication via low-temperature methods; flexible transparent electrode materials developed to enhance the mechanical stability of the devices; mechanical and long-term environmental stability; an outlook of flexible perovskite solar cells in portable electronic devices; and perspectives of commercialization for flexible perovskite solar cells based on cost.

Thermoacoustic sound projector: exceeding the fundamental efficiency of carbon nanotubes.

The combination of smooth, continuous sound spectra produced by a sound source having no vibrating parts, a nanoscale thickness of a flexible active layer and the feasibility of creating large, conformal projectors provoke interest in thermoacoustic phenomena. However, at low frequencies, the sound pressure level (SPL) and the sound generation efficiency of an open carbon nanotube sheet (CNTS) is low. In addition, the nanoscale thickness of fragile heating elements, their high sensitivity to the environment and the high surface temperatures practical for thermoacoustic sound generation necessitate protective encapsulation of a freestanding CNTS in inert gases. Encapsulation provides the desired increase of sound pressure towards low frequencies. However, the protective enclosure restricts heat dissipation from the resistively heated CNTS and the interior of the encapsulated device. Here, the heat dissipation issue is addressed by short pulse excitations of the CNTS. An overall increase of energy conversion efficiency by more than four orders (from 10-5 to 0.1) and the SPL of 120 dB re 20 µPa @ 1 m in air and 170 dB re 1 µPa @ 1 m in water were demonstrated. The short pulse excitation provides a stable linear increase of output sound pressure with substantially increased input power density (>2.5 W cm-2). We provide an extensive experimental study of pulse excitations in different thermodynamic regimes for freestanding CNTSs with varying thermal inertias (single-walled and multiwalled with varying diameters and numbers of superimposed sheet layers) in vacuum and in air. The acoustical and geometrical parameters providing further enhancement of energy conversion efficiency are discussed.

Enhanced torsional actuation and stress coupling in Mn-modified 0.93(Na0.5Bi0.5TiO3)-0.07BaTiO3 lead-free piezoceramic system.

This paper is concerned with the development of a piezoelectric d15 shear-induced torsion actuator made of a lead-free piezoceramic material exhibiting giant piezoelectric shear stress coefficient (e15) and piezoelectric transverse shear actuation force comparable to that of lead-based shear-mode piezoceramics. The Mn-modified 0.93(Na0.5Bi0.5TiO3)-0.07BaTiO3 (NBT-BT-Mn) composition exhibited excellent properties as a torsional transducer with piezoelectric shear stress coefficient on the order of 11.6 C m-2. The torsional transducer, consisting of two oppositely polarized NBT-BT-Mn d15 mode piezoceramic shear patches, provided a rate of twist of 0.08 mm m-1 V-1 under quasi-static 150 V drive. The high value of piezoelectric shear d15 coefficient in NBT-BT-Mn sample further demonstrated its potential in practical applications. These results confirm that the lead-free piezoceramics can be as effective as their lead-based counterparts.

Passive energy recapture in jellyfish contributes to propulsive advantage over other metazoans.

Gelatinous zooplankton populations are well known for their ability to take over perturbed ecosystems. The ability of these animals to outcompete and functionally replace fish that exhibit an effective visual predatory mode is counterintuitive because jellyfish are described as inefficient swimmers that must rely on direct contact with prey to feed. We show that jellyfish exhibit a unique mechanism of passive energy recapture, which is exploited to allow them to travel 30% further each swimming cycle, thereby reducing metabolic energy demand by swimming muscles. By accounting for large interspecific differences in net metabolic rates, we demonstrate, contrary to prevailing views, that the jellyfish (Aurelia aurita) is one of the most energetically efficient propulsors on the planet, exhibiting a cost of transport (joules per kilogram per meter) lower than other metazoans. We estimate that reduced metabolic demand by passive energy recapture improves the cost of transport by 48%, allowing jellyfish to achieve the large sizes required for sufficient prey encounters. Pressure calculations, using both computational fluid dynamics and a newly developed method from empirical velocity field measurements, demonstrate that this extra thrust results from positive pressure created by a vortex ring underneath the bell during the refilling phase of swimming. These results demonstrate a physical basis for the ecological success of medusan swimmers despite their simple body plan. Results from this study also have implications for bioinspired design, where low-energy propulsion is required.

Thermal management of thermoacoustic sound projectors using a free-standing carbon nanotube aerogel sheet as a heat source.

Carbon nanotube (CNT) aerogel sheets produce smooth-spectra sound over a wide frequency range (1-10(5) Hz) by means of thermoacoustic (TA) sound generation. Protective encapsulation of CNT sheets in inert gases between rigid vibrating plates provides resonant features for the TA sound projector and attractive performance at needed low frequencies. Energy conversion efficiencies in air of 2% and 10% underwater, which can be enhanced by further increasing the modulation temperature. Using a developed method for accurate temperature measurements for the thin aerogel CNT sheets, heat dissipation processes, failure mechanisms, and associated power densities are investigated for encapsulated multilayered CNT TA heaters and related to the thermal diffusivity distance when sheet layers are separated. Resulting thermal management methods for high applied power are discussed and deployed to construct efficient and tunable underwater sound projector for operation at relatively low frequencies, 10 Hz-10 kHz. The optimal design of these TA projectors for high-power SONAR arrays is discussed.

MagSonic: Hybrid Magnetic-Ultrasonic Wireless Interrogation of Millimeter-Scale Biomedical Implants With Magnetoelectric Transducer.

Wireless interrogation (power and data transfer) of biomedical implants, miniaturized to millimeter (mm) dimensions, is critical for their chronic operation. Achieving simultaneous wireless power and data transfer at deep sites reliably within safety limits for closed-loop sensing/actuation functions of mm-sized implants is challenging. To enable this operation, a hybrid magnetic-ultrasonic interrogation approach (called MagSonic) is realized through a single magnetoelectric (ME) transducer at the implant that can generate and receive both magnetic field and ultrasound. The fabricated mm-sized bar-shaped ME transducer (5.2×2×1.6 mm3) operates at acoustic wave resonance, functioning at sub-MHz frequencies. For the first time, we demonstrate wireless power reception through one modality (magnetic field or ultrasound) and simultaneous uplink data transmission using the other. At 40 mm depth, the MagSonic link could achieve 100 kbps uplink data rate (bit error rate ≤ 10-5) using 190 pJ/bit transmitted energy and 8 mW delivered power in tissue. The robustness of the MagSonic interrogation link against power carrier interference and misalignments is also demonstrated.

Robot motor learning shows emergence of frequency-modulated, robust swimming with an invariant Strouhal number.

Fish locomotion emerges from diverse interactions among deformable structures, surrounding fluids and neuromuscular activations, i.e. fluid-structure interactions (FSI) controlled by fish's motor systems. Previous studies suggested that such motor-controlled FSI may possess embodied traits. However, their implications in motor learning, neuromuscular control, gait generation, and swimming performance remain to be uncovered. Using robot models, we studied the embodied traits in fish-inspired swimming. We developed modular robots with various designs and used central pattern generators (CPGs) to control the torque acting on robot body. We used reinforcement learning to learn CPG parameters for maximizing the swimming speed. The results showed that motor frequency converged faster than other parameters, and the emergent swimming gaits were robust against disruptions applied to motor control. For all robots and frequencies tested, swimming speed was proportional to the mean undulation velocity of body and caudal-fin combined, yielding an invariant, undulation-based Strouhal number. The Strouhal number also revealed two fundamental classes of undulatory swimming in both biological and robotic fishes. The robot actuators were also demonstrated to function as motors, virtual springs and virtual masses. These results provide novel insights in understanding fish-inspired locomotion.

Effects of caudal fin stiffness on optimized forward swimming and turning maneuver in a robotic swimmer.

In animal and robot swimmers of body and caudal fin (BCF) form, hydrodynamic thrust is mainly produced by their caudal fins, the stiffness of which has profound effects on both thrust and efficiency of swimming. Caudal fin stiffness also affects the motor control and resulting swimming gaits that correspond to optimal swimming performance; however, their relationship remains scarcely explored. Here using magnetic, modular, undulatory robots (µBots), we tested the effects of caudal fin stiffness on both forward swimming and turning maneuver. We developed six caudal fins with stiffness of more than three orders of difference. For aµBot equipped with each caudal fin (andµBot absent of caudal fin), we applied reinforcement learning in experiments to optimize the motor control for maximizing forward swimming speed or final heading change. The motor control ofµBot was generated by a central pattern generator for forward swimming or by a series of parameterized square waves for turning maneuver. In forward swimming, the variations in caudal fin stiffness gave rise to three modes of optimized motor frequencies and swimming gaits including no caudal fin (4.6 Hz), stiffness <10-4Pa m4(∼10.6 Hz) and stiffness >10-4Pa m4(∼8.4 Hz). Swimming speed, however, varied independently with the modes of swimming gaits, and reached maximal at stiffness of 0.23 × 10-4Pa m4, with theµBot without caudal fin achieving the lowest speed. In turning maneuver, caudal fin stiffness had considerable effects on the amplitudes of both initial head steering and subsequent recoil, as well as the final heading change. It had relatively minor effect on the turning motor program except for theµBots without caudal fin. Optimized forward swimming and turning maneuver shared an identical caudal fin stiffness and similar patterns of peduncle and caudal fin motion, suggesting simplicity in the form and function relationship inµBot swimming.

Down-selection of biomolecules to assemble "reverse micelle" with perovskites.

Biological molecule-semiconductor interfacing has triggered numerous opportunities in applied physics such as bio-assisted data storage and computation, brain-computer interface, and advanced distributed bio-sensing. The introduction of electronics into biological embodiment is being quickly developed as it has great potential in providing adaptivity and improving functionality. Reciprocally, introducing biomaterials into semiconductors to manifest bio-mimetic functionality is impactful in triggering new enhanced mechanisms. In this study, we utilize the vulnerable perovskite semiconductors as a platform to understand if certain types of biomolecules can regulate the lattice and endow a unique mechanism for stabilizing the metastable perovskite lattice. Three tiers of biomolecules have been systematically tested and the results reveal a fundamental mechanism for the formation of a "reverse-micelle" structure. Systematic exploration of a large set of biomolecules led to the discovery of guiding principle for down-selection of biomolecules which extends the classic emulsion theory to this hybrid systems. Results demonstrate that by introducing biomaterials into semiconductors, natural phenomena typically observed in biological systems can also be incorporated into semiconducting crystals, providing a new perspective to engineer existing synthetic materials.

Underwater Thermoacoustic Generation by a Hierarchical Tetrapodal Carbon Nanotube Network.

Solid-state fabricated carbon nanotube (CNT) sheets have shown promise as thermoacoustic (TA) sound generators, emitting tunable sound waves across a broad frequency spectrum (1-105 Hz) due to their ultralow specific heat capacity. However, their applications as underwater TA sound generators are limited by the reduced mechanical strength of CNT sheets in aqueous environments. In this study, we present a mechanically robust underwater TA device constructed from a three-dimensional (3D) tetrapodal assembly of carbon nanotubes (t-CNTs). These structures feature a high porosity (>99.9%) and a double-hollowed network of well-interconnected CNTs. We systematically explore the impact of different dimensions of t-CNTs and various annealing procedures on sound generation performance. Furnace-annealed t-CNTs, in contrast to directly resistive Joule heating annealing, provide superior, continuous, and homogeneous hydrophobicity across the surface of bulk t-CNTs. As a result, the t-CNTs-based underwater TA device demonstrates stable, smooth, and broad-spectrum sound generation within the frequency range of 1 × 102 to 1 × 104 Hz, along with a weak resonance response. Furthermore, these devices exhibit enhanced and more stable sound generation performance at nonresonance frequencies compared to regular CNT-based devices. This study contributes to advancing the development of underwater TA devices with characteristics such as being nonresonant, high-performing, flexible, elastically compressible, and reliable, enabling operation across a broad frequency range.