Analysis of the acoustoelectric response of SAW gas sensors using a COM model.

Surface acoustic wave (SAW) gas sensors based on the acoustoelectric effect exhibit wide application prospects for in situ gas detection. However, establishing accurate models for calculating the scattering parameters of SAW gas sensors remains a challenge. Here, we present a coupling of modes (COM) model that includes the acoustoelectric effect and specifically explains the nonmonotonic variation in the center frequency with respect to the sensing film's sheet conductivity. Several sensing parameters of the gas sensors, including the center frequency, insertion loss, and phase, were experimentally compared for accuracy and practicality. Finally, the frequency of the phase extremum (FPE) shift was determined to vary monotonically, and the range of selectable test points was wide, making the FPE an appropriate response parameter for leveraging in SAW gas sensors. The simulation results of the COM model were highly consistent with the experimental results. Our study is proposed to provide theoretical guidance for the future development of gas SAW sensors.

Correction: Exploring the Mpemba effect: a universal ice pressing enables porous ceramics.

Correction for 'Exploring the Mpemba effect: a universal ice pressing enables porous ceramics' by Xiaodan Yang et al., Mater. Horiz., 2024, DOI: https://doi.org/10.1039/d3mh01869e.

Exploring the Mpemba effect: a universal ice pressing enables porous ceramics.

Piezoceramics with global porosity and local compaction are highly desired to exploit the combination of mechanical and electrical properties. However, achieving such a functional combination is challenging because of the lack of techniques for applying uniform pressure inside porous ceramic green parts. Nature provides many examples of generating strong forces inside the macro and micro channels via the state transformation of water. Inspired by these phenomena, we present a technique of "ice and fire", that is, water freezing (ice pressing) and high-temperature sintering (fire), to produce ideal porous piezoceramics. We introduce a new compaction method called the "ice pressing method", which manipulates liquid phase transition for compaction. This method has several advantages, including uniform pressure distribution, a wide pressure range, high effectiveness, and selective freezing. It can generate an ultrahigh pressure of up to 180 MPa on the piezoceramic green skeletons in minutes while retaining their functional pore structures. By exploiting the Mpemba phenomenon, we further accelerate the compaction procedure by 11%. The first ice-pressed and second fire-consolidated lead zirconate titanate (PZT) ceramics are highly densified and exhibit an outstanding piezoelectric response (d33 = 531 pC N-1), comparable to conventional pressed bulk counterparts and 10-20 times higher than those of unpressed materials. The novel ice pressing method breaks the limitation of lacking a compaction technique for porous ceramics. The versatile and effective ice pressing method is a green and low-cost route promoting applications in sensors, acoustics, water filtration, catalyst substrates, and energy harvesting.

(Bi,Sb)2 Se3 Alloy Thin Film for Short-Wavelength Infrared Photodetector and TFT Monolithic-Integrated Matrix Imaging.

Short-wavelength infrared photodetectors play a significant role in various fields such as autonomous driving, military security, and biological medicine. However, state-of-the-art short-wavelength infrared photodetectors, such as InGaAs, require high-temperature fabrication and heterogenous integration with complementary metal-oxide-semiconductor (CMOS) readout circuits (ROIC), resulting in a high cost and low imaging resolution. Herein, for the first time, a low-cost, high-performance, high-stable, and thin-film transistor (TFT) ROIC monolithic-integrated (Bi,Sb)2 Se3 alloy thin-film short-wavelength infrared photodetector is reported. The (Bi,Sb)2 Se3 alloy thin-film short-wavelength infrared photodetectors demonstrate a high external quantum efficiency (EQE) of 21.1% (light intensity of 0.76 µW cm-2 ) and a fast response time (3.24 µs). The highest EQE is about two magnitudes than that of the extrinsic photoconduction of Sb2 Se3 (0.051%). In addition, the unpackaged devices demonstrate high electric and thermal stability (almost no attenuation at 120 °C for 312 h), showing potential for in-vehicle applications that may experient such a high temperature. Finally, both the (Bi,Sb)2 Se3 alloy thin film and n-type CdSe buffer layer are directly deposited on the TFT ROIC (with a 64 × 64-pixel array) with a low-temperature process and the material identification and imaging applications are presented. This work is a significant breakthrough in ROIC monolithic-integrated short-wavelength infrared imaging chips.

Thermoelectric coupling effect in BNT-BZT-xGaN pyroelectric ceramics for low-grade temperature-driven energy harvesting.

Pyroelectric energy harvesting has received increasing attention due to its ability to convert low-grade waste heat into electricity. However, the low output energy density driven by low-grade temperature limits its practical applications. Here, we show a high-performance hybrid BNT-BZT-xGaN thermal energy harvesting system with environmentally friendly lead-free BNT-BZT pyroelectric matrix and high thermal conductivity GaN as dopant. The theoretical analysis of BNT-BZT and BNT-BZT-xGaN with x = 0.1 wt% suggests that the introduction of GaN facilitates the resonance vibration between Ga and Ti, O atoms, which not only contributes to the enhancement of the lattice heat conduction, but also improves the vibration of TiO6 octahedra, resulting in simultaneous improvement of thermal conductivity and pyroelectric coefficient. Therefore, a thermoelectric coupling enhanced energy harvesting density of 80 µJ cm-3 has been achieved in BNT-BZT-xGaN ceramics with x = 0.1 wt% driven by a temperature variation of 2 oC, at the optical load resistance of 600 MΩ.

Mobile energy storage technologies for boosting carbon neutrality.

Carbon neutrality calls for renewable energies, and the efficient use of renewable energies requires energy storage mediums that enable the storage of excess energy and reuse after spatiotemporal reallocation. Compared with traditional energy storage technologies, mobile energy storage technologies have the merits of low cost and high energy conversion efficiency, can be flexibly located, and cover a large range from miniature to large systems and from high energy density to high power density, although most of them still face challenges or technical bottlenecks. In this review, we provide an overview of the opportunities and challenges of these emerging energy storage technologies (including rechargeable batteries, fuel cells, and electrochemical and dielectric capacitors). Innovative materials, strategies, and technologies are highlighted. Finally, the future directions are envisioned. We hope this review will advance the development of mobile energy storage technologies and boost carbon neutrality.

Molecular Ferroelectric Crystals with Superior Pyroelectricity, Plasticity, and Recyclability.

The pyroelectric effect is used in a wide range of applications such as infrared (IR) detection and thermal energy harvesting, which require the pyroelectric materials to simultaneously have a high pyroelectric coefficient and a low dielectric constant for high figures of merit. However, in conventional proper ferroelectrics, the positive correlation between the pyroelectric coefficient and the dielectric constant imposes an insurmountable challenge in upgrading the figures of merit. Here, we explored superior pyroelectricity in [(CH3)4N][FeCl4] (TMA-FC) and [(CH3)4N][FeCl3Br] (TMA-FCB) molecular ferroelectric plastic crystals, which could decouple this positive correlation due to the nature of improper polarization behavior. Therefore, TMA-FC and TMA-FCB derive a high pyroelectric coefficient and a low dielectric constant simultaneously, yielding record-high figures of merit around room temperature. Furthermore, the favorable plasticity enables ferroelectric crystals to attach surfaces with different shapes for device design and integration. More interestingly, the molecular ferroelectrics could be softened and reshaped at elevated temperatures without decay in pyroelectricity, making them recyclable for cost savings and e-waste reduction. Combined with the facile fabrication process, the findings of this work would open avenues for employing molecular ferroelectric plastic crystals in the manufacture of high-performance pyroelectric devices.

Hot Spot Engineering in Hierarchical Plasmonic Nanostructures.

The controllable nanogap structures offer an effective way to obtain strong and tunable localized surface plasmon resonance (LSPR). A novel hierarchical plasmonic nanostructure (HPN) is created by incorporating a rotating coordinate system into colloidal lithography. In this nanostructure, the hot spot density is increased drastically by the long-range ordered morphology with discrete metal islands filled in the structural units. Based on the Volmer-Weber growth theory, the precise HPN growth model is established, which guides the hot spot engineering for improved LSPR tunability and strong field enhancement. The hot spot engineering strategy is examined by the application of HPNs as the surface-enhanced Raman spectroscopy (SERS) substrate. It is universally suitable for various SERS characterization excited at different wavelengths. Based on the HPN and hot spot engineering strategy, single-molecule level detection and long-range mapping can be realized simultaneously. In that sense, it offers a great platform and guides the future design for various LSPR applications like surface-enhanced spectra, biosensing, and photocatalysis.

Substantially Enhanced Electrocaloric Effect in Ba(Zr0.2Ti0.8)O3 Lead-Free Ferroelectric Ceramics via Lattice Stress Engineering.

As an alternative to conventional vapor-compression refrigeration, cooling devices based on electrocaloric (EC) materials are environmentally friendly and highly efficient, which are promising in realizing solid-state cooling. Lead-free ferroelectric ceramics with competitive EC performance are urgently desirable for EC cooling devices. In the past few decades, constructing phase coexistence and high polarizability have been two crucial factors in optimizing the EC performance. Different from the external stress generated through heavy equipment and inner interface stress caused by complex interface structures, the internal lattice stress induced by ion substitution engineering is a relatively simple and efficient means to tune the phase structure and polarizability. In this work, we introduce low-radius Li+ into BaZr0.2Ti0.8O3 (BZT) to form a particular A-site substituted cell structure, leading to a change of the internal lattice stress. With the increase of lattice stress, the fraction of the rhombohedral phase in the rhombohedral-cubic (R-C) coexisting system and ferroelectricity are all pronouncedly enhanced for the Li2CO3-doped sample, resulting in the significant enhancement of saturated polarization (Ps) as well as EC performance [e.g., adiabatic temperature change (ΔT) and isothermal entropy change (ΔS)]. Under the same conditions (i.e., 333 K and 70 kV cm-1), the ΔT of 5.7 mol % Li2CO3-doped BZT is 1.37 K, which is larger than that of the pure BZT ceramics (0.61 K). Consequently, in cooperation with the great improvement of electric field breakdown strength (Eb) from 70 to 150 kV cm-1, 5.7 mol % Li2CO3-doped BZT achieved a large ΔT of 2.26 K at a temperature of 333 K, which is a competitive performance in the field of electrocaloric effect (ECE). This work provides a simple but effective approach to designing high-performance electrocaloric materials for next-generation refrigeration.

Highly Sensitive Chemiresistive H2S Detection at Subzero Temperature over the Sb-Doped SnO2@g-C3N4 Heterojunctions under UV Illumination.

NASA has detected H2S in the persistently shadowed region of the lunar South Pole through NIR and UV/vis spectroscopy remotely, but in situ detection is generally considered to be more accurate and convincing. However, subzero temperatures in space drastically reduce chemisorbed oxygen ions for gas sensing reactions, making gas sensing at subzero temperature something that has rarely been attempted. Herein, we report an in situ semiconductor H2S gas sensor assisted by UV illumination at subzero temperature. We constructed a g-C3N4 network to wrap the porous Sb doped SnO2 microspheres to form type II heterojunctions, which facilitate the separation and transport of photoinduced charge carriers under UV irradiation. This UV-driven technique affords the gas sensor a fast response time of 14 s and a response value of 20.1 toward 2 ppm H2S at -20 °C, realizing the sensitive response of the semiconductor gas sensor at subzero temperature for the first time. Both the experimental observations and theoretical calculation results provide evidence that UV irradiation and the formation of type II heterojunctions together promote the performance at subzero temperature. This work fills the gap of semiconductor gas sensors working at subzero temperature and suggests a feasible method for deep space gas detection.

Enhanced Energy Storage Performance by A-B Site Ambipolar Co-Doping in Antiferroelectrics.

Antiferroelectric materials are promising to be used for power capacitive devices. To improve the energy storage performance, solid-solution and defect engineering are widely used to suppress the long-range order by introducing local heterogeneities. However, both methods generally deteriorate either the maximum polarization or breakdown electric field due to damaged intrinsic polarization or increased leakage. Here, we show that forming defect-dipole clusters by A-B site acceptor-donor co-doping in antiferroelectrics can comprehensively enhance the energy storage performance. We took the La-Mn co-doped (Pb0.9Ba0.04La0.04)(Zr0.65Sn0.3Ti0.05)O3 (PBLZST) as an example. For co-doping with unequal amounts, high dielectric loss, impurity phase, and decreased polarization were observed. By contrast, La and Mn in an equal amount of co-doping can significantly improve the overall energy storage performance. An over 48% increasement in both the maximum polarization (62.7 µC/cm2) and breakdown electric field (242.6 kV/cm) was obtained in 1 mol % La and 1 mol % Mn equally co-doped PBLZST, followed by a nearly two-time enhancement in Wrec (6.52 J/cm3) compared with that of the pure matrix. Moreover, a high energy storage efficiency of 86.3% with an enhanced temperature stability over a wide temperature range can be achieved. The defect-dipole clusters associated with charge-compensated co-doping are suggested to contribute to an enhanced dielectric permittivity, linear polarization behavior, and maximum polarization strength compared with that of the unequal co-doping cases. The defect-dipole clusters are suggested to couple with the host, leading to a high energy storage performance. The proposed strategy is believed to be applicable to modify the energy storage behavior of antiferroelectrics.

Glass-Ceramic Capacitors with Simultaneously High Power and Energy Densities under Practical Charge-Discharge Conditions.

Developing dielectric capacitors with both a high power density and a high energy density for application in power electronics has been a long-standing challenge. Glass-ceramics offer the potential of retaining the high relative permittivity of ceramics and at the same time of exhibiting the high dielectric breakdown strength and fast charge/discharge rate of glasses, thus producing concurrently high power and energy densities in a single material. In this work, glass-ceramics are fabricated to achieve simultaneously high power and energy densities, high efficiency, and thermal stability by tuning the glass crystallization process via a suitable nucleating agent and a high oxygen partial pressure. Under the same practical charge-discharge test conditions, the as-prepared glass-ceramics combine the high energy density of ceramics and ultrafast discharge rate of glasses, producing the highest power density among glass- and ceramic-based dielectric materials. This work demonstrates the significant potential of achieving both high power and energy densities in glass-ceramics by optimizing the glass crystallization process.

Giant Room-Temperature Electrocaloric Effect of Polymer-Ceramic Composites with Orientated BaSrTiO3 Nanofibers.

Cooling based on the electrocaloric effect (ECE) is a promising solution to environmental and energy efficiency problems of vapor-compression refrigeration. Ferroelectric polymer-ceramics nanocomposites, integrating high electric breakdown of organic ferroelectrics and large EC strength of ceramics, are attractive EC materials. Here, we tuned the orientation of Ba0.67Sr0.33TiO3 nanofibers (BST nfs) in the P(VDF-TrFE-CFE) polymer. When the nfs were aligned parallel to the field, a ΔT of 11.3 K with an EC strength of 0.16 K·m/MV was achieved in the blends. The EC strength not only surpasses advanced nanocomposites but also is comparable to ferroelectric ceramics. The simulation indicates that a significantly higher electric field is concentrated in polymer regions around the ends of the orientated nfs, contributing to easier flipping of polymer chains for large ECE. This work provides a new method to obtain large ECE in composites for next-generation refrigeration.

Response to Comment on "Improper molecular ferroelectrics with simultaneous ultrahigh pyroelectricity and figures of merit".

Szafranski and Katrusiak stated that [Hdabco]ClO4 and [Hdabco]BF4 are proper ferroelectrics and exhibit much smaller pyroelectric coefficients than our results. We disagree with the arguments and provide a detailed answer highlighting misunderstandings in their interpretation.

A Biodegradable and Recyclable Piezoelectric Sensor Based on a Molecular Ferroelectric Embedded in a Bacterial Cellulose Hydrogel.

Currently, various electronic devices make our life more and more safe, healthy, and comfortable, but at the same time, they produce a large amount of nondegradable and nonrecyclable electronic waste that threatens our environment. In this work, we explore an environmentally friendly and flexible mechanical sensor that is biodegradable and recyclable. The sensor consists of a bacterial cellulose (BC) hydrogel as the matrix and imidazolium perchlorate (ImClO4) molecular ferroelectric as the functional element, the hybrid of which possesses a high sensitivity of 4 mV kPa-1 and a wide operational range from 0.2 to 31.25 kPa, outperforming those of most devices based on conventional functional biomaterials. Moreover, the BC hydrogel can be fully degraded into glucose and oligosaccharides, while ImClO4 can be recyclable and reused for the same devices, leaving no environmentally hazardous electronic waste.

How Far Can We Push the Rigid Oligomers/Polymers toward Ferroelectric Nematic Liquid Crystals?

The emerging ferroelectric nematic (NF) liquid crystal is a novel 3D-ordered liquid exhibiting macroscopic electric polarization. The combination of the ultrahigh dielectric constant, strong nonlinear optical signal, and high sensitivity to the electric field makes NF materials promising for the development of advanced liquid crystal electroopic devices. Previously, all studies focused on the rod-shaped small molecules with limited length (l) range and dipole moment (µ) values. Here, through the precision synthesis, we extend the aromatic rod-shaped mesogen to oligomer/polymer (repeat unit up to 12 with monodisperse molecular-weight dispersion) and increase the µ value over 30 Debye (D). The NF phase has a widespread existence far beyond our expectation and could be observed in all the oligomer/polymer length range. Notably, the NF phase experiences a nontrivial evolution pathway with the traditional apolar nematic phase completely suppressed, i.e., the NF phase nucleates directly from the isotropic liquid phase. The discovery of thte ferroelectric packing of oligomer/polymer rods not only offers the concept of extending the NF state to oligomers/polymers but also provides some previously overlooked insights in oxybenzoate-based liquid crystal polymer materials.

A gravity-driven sintering method to fabricate geometrically complex compact piezoceramics.

Highly compact and geometrically complex piezoceramics are required by a variety of electromechanical devices owing to their outstanding piezoelectricity, mechanical stability and extended application scenarios. 3D printing is currently the mainstream technology for fabricating geometrically complex piezoceramic components. However, it is hard to print piezoceramics in a curve shape while also keeping its compactness due to restrictions on the ceramic loading and the viscosity of feedstocks. Here, we report a gravity-driven sintering (GDS) process to directly fabricate curved and compact piezoceramics by exploiting gravitational force and high-temperature viscous behavior of sintering ceramic specimens. The sintered lead zirconate titanate (PZT) ceramics possess curve geometries that can be facilely tuned via the initial mechanical boundary design, and exhibit high piezoelectric properties comparable to those of conventional-sintered compact PZT (d33 = 595 pC/N). In contrast to 3D printing technology, our GDS process is suitable for scale-up production and low-cost production of piezoceramics with diverse curved surfaces. Our GDS strategy is an universal and facile route to fabricate curved piezoceramics and other functional ceramics with no compromise of their functionalities.

Plasmonic metamaterial absorbers with strong coupling effects for small pixel infrared detectors.

Here we report a metal-insulator-metal (MIM) based infrared plasmonic metamaterial absorber consisting of deep subwavelength meander line nanoantennas. High absorption composed of two-hybrid modes from 11 µm to 14 µm is experimentally demonstrated with a pixel pitch of 1.47 µm corresponding to a compression ratio of 8.57. The physical mechanisms responsible for novelty spectral absorption, including the strong coupling between the plasmon resonances and the phonon vibrations, material loss from the dielectric spacer, localized surface plasmon resonance (LSPR), and Berreman mode excited by oblique incidence, have been systematically analyzed by finite-difference time-domain (FDTD) method, Fabry-Perot resonance model and two-coupled damped oscillator model. At oblique incidence, a spectral splitting related to the strong coupling between LSPR mode and Berreman mode is also observed. The distribution of local electromagnetic fields and ohmic loss are numerically investigated. Moreover, we evaluate the absorption performances with finite-sized arrays. We also show that the absorber can maintain its absorption with a 2 × 2 nanoantenna array. Such a miniaturized absorber can adapt to infrared focal plane arrays with a pixel size smaller than 5 µm, and thermal analysis is also performed. Our approach provides an effective way to minimize the antenna footprint without undermining the absorber performances, paving the way towards its integration with small pixels of infrared focal plane arrays for enhanced performances and expanded functionalities.

Molecular Ferroelectric-Based Flexible Sensors Exhibiting Supersensitivity and Multimodal Capability for Detection.

Although excellent dielectric, piezoelectric, and pyroelectric properties matched with or even surpassing those of ferroelectric ceramics have been recently discovered in molecular ferroelectrics, their successful applications in devices are scarce. The fracture proneness of molecular ferroelectrics under mechanical loading precludes their applications as flexible sensors in bulk crystalline form. Here, self-powered flexible mechanical sensors prepared from the facile deposition of molecular ferroelectric [C(NH2 )3 ]ClO4 onto a porous polyurethane (PU) matrix are reported. [C(NH2 )3 ]ClO4 -PU is capable of detecting pressure of 3 Pa and strain of 1% that are hardly accessible by the state-of-the-art piezoelectric, triboelectric, and piezoresistive sensors, and presents the ability of sensing multimodal mechanical forces including compression, stretching, bending, shearing, and twisting with high cyclic stability. This scaling analysis corroborated with computational modeling provides detailed insights into the electro-mechanical coupling and establishes rules of engineering design and optimization for the hybrid sponges. Demonstrative applications of the [C(NH2 )3 ]ClO4 -PU array suggest potential uses in interactive electronics and robotic systems.

Template-Free Construction of Tin Oxide Porous Hollow Microspheres for Room-Temperature Gas Sensors.

Porous hollow microsphere (PHM) materials represent ideal building blocks for realizing diverse functional applications such as catalysis, energy storage, drug delivery, and chemical sensing. This has stimulated intense efforts to construct metal oxide PHMs for achieving highly sensitive and low-power-consumption semiconductor gas sensors. Conventional methods for constructing PHMs rely on delicate reprogramming of templates and may suffer from the structural collapse issue during the removal of templates. Here, we propose a template-free method for the construction of tin oxide (SnO2) PHMs via the competition between the solvent evaporation rate and the phase separation dynamics of colloidal SnO2 quantum wires. The SnO2 PHMs (typically 3 ± 0.5 µm diameter and approximately 200 nm shell thickness) exhibit desirable structural stability with desirable processing compatibility with various substrates. This enables the realization of NO2 gas sensors having a superior response and recovery process at room temperature. The superior NO2-sensing characteristic is attributed to the effective gas adsorption competition on solid surfaces benefiting from efficient diffusion channels, enhancing the interaction of metal oxide solids with gas molecules in terms of the receptor function, transducer function, and utility factor. In addition, the one-step deposition of SnO2 PHMs directly onto device substrates simplifies the fabrication conditions for semiconductor gas sensors. The desirable structural stability of PHMs combined with the functional diversity of metal oxides may open new opportunities for the design of functional materials and devices.