Magnet-in-ferroelectric crystals exhibiting photomultiferroicity.

Growing crystallographically incommensurate and dissimilar organic materials is fundamentally intriguing but challenging for the prominent cross-correlation phenomenon enabling unique magnetic, electronic, and optical functionalities. Here, we report the growth of molecular layered magnet-in-ferroelectric crystals, demonstrating photomanipulation of interfacial ferroic coupling. The heterocrystals exhibit striking photomagnetization and magnetoelectricity, resulting in photomultiferroic coupling and complete change of their color while inheriting ferroelectricity and magnetism from the parent phases. Under a light illumination, ferromagnetic resonance shifts of 910 Oe are observed in heterocrystals while showing a magnetization change of 0.015 emu/g. In addition, a noticeable magnetization change (8% of magnetization at a 1,000 Oe external field) in the vicinity of ferro-to-paraelectric transition is observed. The mechanistic electric-field-dependent studies suggest the photoinduced ferroelectric field effect responsible for the tailoring of photo-piezo-magnetism. The crystallographic analyses further evidence the lattice coupling of a magnet-in-ferroelectric heterocrystal system.

Lithiating magneto-ionics in a rechargeable battery.

Magneto-ionics, real-time ionic control of magnetism in solid-state materials, promise ultralow-power memory, computing, and ultralow-field sensor technologies. The real-time ion intercalation is also the key state-of-charge feature in rechargeable batteries. Here, we report that the reversible lithiation/delithiation in molecular magneto-ionic material, the cathode in a rechargeable lithium-ion battery, accurately monitors its real-time state of charge through a dynamic tunability of magnetic ordering. The electrochemical and magnetic studies confirm that the structural vacancy and hydrogen-bonding networks enable reversible lithiation and delithiation in the magnetic cathode. Coupling with microwave-excited spin wave at a low frequency (0.35 GHz) and a magnetic field of 100 Oe, we reveal a fast and reliable built-in magneto-ionic sensor monitoring state of charge in rechargeable batteries. The findings shown herein promise an integration of molecular magneto-ionic cathode and rechargeable batteries for real-time monitoring of state of charge.

Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches.

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields including sensing, photoelectronics, and photonic applications. While significant progress has been made in solid-state NLO switching materials, these materials typically showcase their highest NLO performance near room temperature. However, this performance drastically deteriorates upon heating, primarily due to the phase transition undergone by the materials from noncentrosymmetric to centrosymmetric phase. Here, we introduce a new class of NLO switching materials, solid-state supramolecular compounds 18-Crown-6 ether@Cu2Cl4·4H2O (1·4H2O), exhibiting reversible and stable NLO switching when subjected to near-infrared (NIR) photoexcitation and/or thermal stimuli. The reversible crystal structure in response to external stimuli is attributed to the presence of a weakly coordinated bridging water molecule facilitated by hydrogen bonding/chelation interactions between the metal halide and crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110 °C. In addition, the bridging water molecules within the complex can be released and recaptured in a fully reversible manner, all without requiring excessive energy input. This feature allows for precise control of SHG signal activation and deactivation through structural transformations, resulting in a high-contrast off/on ratio, reaching values in the million-fold range.

A 3D-printed molecular ferroelectric metamaterial.

Molecular ferroelectrics combine electromechanical coupling and electric polarizabilities, offering immense promise in stimuli-dependent metamaterials. Despite such promise, current physical realizations of mechanical metamaterials remain hindered by the lack of rapid-prototyping ferroelectric metamaterial structures. Here, we present a continuous rapid printing strategy for the volumetric deposition of water-soluble molecular ferroelectric metamaterials with precise spatial control in virtually any three-dimensional (3D) geometry by means of an electric-field-assisted additive manufacturing. We demonstrate a scaffold-supported ferroelectric crystalline lattice that enables self-healing and a reprogrammable stiffness for dynamic tuning of mechanical metamaterials with a long lifetime and sustainability. A molecular ferroelectric architecture with resonant inclusions then exhibits adaptive mitigation of incident vibroacoustic dynamic loads via an electrically tunable subwavelength-frequency band gap. The findings shown here pave the way for the versatile additive manufacturing of molecular ferroelectric metamaterials.

High-Endurance Magneto-Electronic Switchable Molecular Electronic Crystal.

Electrically switchable magnetic and electronic properties are promising for quantum sensing and information technology. Here, we report an electrically driven magnetic and electronic phase transition in molecular electronic crystal, potassium-7,7,8,8-tetracyanoquinodimethan, with the magneto-electric switching over 105 cycles at room temperature. Electron spin resonance study reveals the cooperative transition between spin and charge degrees of freedom. In addition, the mechanistic spectroscopy studies suggest the charges in an inhomogeneous conductor-insulator mixed state. The findings shown here suggest electrically controlled ordering in strongly correlated molecular crystal leads to dynamic magneto-electric switching, paving the way for developing molecular-based memory and switching devices.

Printing Air-Stable High-Tc Molecular Magnet with Tunable Magnetic Interaction.

High-Tc molecular magnets have amassed much promise; however, the long-standing obstacle for its practical applications is the inaccessibility of high-temperature molecular magnets showing dynamic and nonvolatile magnetization control. In addition, its functional durability is prone to degradation in oxygen and heat. Here, we introduce a rapid prototyping and stabilizing strategy for high Tc (360 K) molecular magnets with precise spatial control in geometry. The printed molecular magnets are thermally stable up to 400 K and air-stable for over 300 days, a significant improvement in its lifetime and durability. X-ray magnetic circular dichroism and computational modeling reveal the water ligands controlling magnetic exchange interaction of molecular magnets. The molecular magnets also show dynamical and reversible tunability of magnetic exchange interactions, enabling a colossal working temperature window of 86 K (from 258 to 344 K). This study provides a pathway to flexible, lightweight, and durable molecular magnetic devices through additive manufacturing.

Emerged Metallicity in Molecular Ferromagnetic Wires.

Supramolecular engineering bridges molecular assembly with macromolecular charge-transfer salts, promising the design to construct supramolecular architectures that integrate cooperative properties difficult or impossible to find in conventional lattices. Here, we report the crystal engineering design and kinetic growth of one-dimensional supramolecular wires composed of bis(ethylenedithio)tetrathiafulvalene (ET+) cation and polymeric Cu[N(CN)2]2- anion. A bulk ferromagnetic order is discovered for filling up the gap where strong ferromagnetism is missing in such ET molecule-based charge-transfer salts. Metallicity is induced by electric current from the semiconducting wire, which is attributed to strain effect by tuning its close molecular contact. This structural feature is evidenced through the combination of various mechanistic spectroscopic studies. Electric dipole is established from the close molecular contacts and is suggestive to stabilize ferromagnetic spin interaction through anions bridging spin sites. The breakthrough shown here provides a pathway to explore low-dimensional supramolecular materials exhibiting strong electron correlation, metallicity, and ferromagnetism.

Ultrahigh Temperature Copper-Ceramic Flexible Hybrid Electronics.

Advanced high-temperature materials, metals and ceramics, have been widely sought after for printed flexible electronics under extreme conditions. However, the thermal stability and electronic performance of these materials generally diminish under extreme environments. Additionally, printable electronics typically utilize nanoscale materials, which further exacerbate the problems with oxidation and corrosion at those extreme conditions. Here we report superior thermal and electronic stability of printed copper-flexible ceramic electronics by means of integral hybridization and passivation strategies. High electric conductivity (5.6 MS/m) and thermal stability above 400 °C are achieved in the printed graphene-passivated copper platelet features, while thermal management and stability above 1000 °C of printed electronics can be achieved by using either ultrathin alumina or flexible alumina aerogel sheets. The findings shown here provide a pathway toward printed, extreme electronic applications for harsh service conditions.

Flexible Lead-Free X-ray Detector from Metal-Organic Frameworks.

Semiconductive metal-organic frameworks (MOFs) obtained by specific host-guest interactions have attracted a large interest in the last two decades, promising development of next-generation electronic devices. Herein, we designed and presented flexible X-ray detectors using Ni-DABDT (DABDT = 2,5-diamino-1,4-benzenedithiol dihydrochloride) MOFs as the absorbing layer. The π-d coupling interactions of Ni-DABDT throughout the framework implement a conspicuous carrier transportation pathway. The detector that converts X-ray photons directly into carriers manifests an attractive achievement with high detection sensitivity of 98.6 µC Gyair-1 cm-2, with a low detection limit of 7.2 µGyair s-1 for the radiation robustness. This work provides insights for next-generation green and high-performance flexible sensor detectors by utilizing MOF materials with the benefits of a designable structure and tunable property, demonstrating a proof-of-concept in wearable X-ray detectors for radiation monitoring and imaging.

Cross-Linking and Charging Molecular Magnetoelectronics.

Magnetoelectrics are witnessing an ever-growing success toward the voltage-controlled magnetism derived from inorganic materials. However, these inorganic materials have predominantly focused on the ferroelectromagnetism at solid-to-solid interfaces and suffered several drawbacks, including the interface-sensitive coupling mediators, high-power electric field, and limited chemical tunability. Here, we report a promising design strategy to shift the paradigm of next-generation molecular magnetoelectrics, which relies on the integration between molecular magnetism and electric conductivity though an in situ cross-linking strategy. Following this approach, we demonstrate a versatile and efficient synthesis of flexible molecular-based magnetoelectronics by cross-linking of magnetic coordination networks that incorporate conducting chain building blocks. The as-grown compounds feature an improved critical temperature up to 337 K and a room-temperature magnetism control of low-power electric field. It is envisaged that the cross-linking of molecular interfaces is a feasible method to couple and modulate magnetism and electron conducting systems.

Printed copper-nanoplate conductor for electro-magnetic interference.

As one of the conductive ink materials with high electric conductivity, elemental copper (Cu) based nanocrystals promise for printable electronics. Here, single crystalline Cu nanoplates were synthesized using a facile hydrothermal method. Size engineering of Cu nanoplates can be rationalized by using the LaMer model and the versatile Cu conductive ink materials are suitable for different printing technologies. The printed Cu traces show high electric conductivity of 6 MS m-1, exhibiting electro-magnetic interference shielding efficiency value of 75 dB at an average thicknesses of 11µm. Together with flexible alumina ceramic aerogel substrates, it kept 87% conductivity at the environmental temperature of 400 °C, demonstrating the potential of Cu conductive ink for high-temperature printable electronics applications.

Light-induced dilation in nanosheets of charge-transfer complexes.

We report the observation of a sizable photostrictive effect of 5.7% with fast, submillisecond response times, arising from a light-induced lattice dilation of a molecular nanosheet, composed of the molecular charge-transfer compound dibenzotetrathiafulvalene (DBTTF) and C60 An interfacial self-assembly approach is introduced for the thickness-controlled growth of the thin films. From photoabsorption measurements, molecular simulations, and electronic structure calculations, we suggest that photostriction within these films arises from a transformation in the molecular structure of constituent molecules upon photoinduced charge transfer, as well as the accommodation of free charge carriers within the material. Additionally, we find that the photostrictive properties of the nanosheets are thickness-dependent, a phenomenon that we suggest arises from surface-induced conformational disorder in the molecular components of the film. Moreover, because of the molecular structure in the films, which results largely from interactions between the constituent π-systems and the sulfur atoms of DBTTF, the optoelectronic properties are found to be anisotropic. This work enables the fabrication of 2D molecular charge-transfer nanosheets with tunable thicknesses and properties, suitable for a wide range of applications in flexible electronic technologies.

A Hierarchical Mesoporous Insulation Ceramic.

Light-weight ceramic aerogels hold promise for superinsulation. However, its mechanical instability and complex manufacturing hampered its technical applications. In this study, we demonstrate lightweight pore-gradient ceramic aerogel-like foam monoliths (PGAFoams) through one-pot and in situ bubble supported pore gradient formation. The mechanically strong PGAFoams exhibit a low thermal conductivity of 0.036 W m-1 K-1 and a compressive strength of 89.85 MPa. The pore gradient and integral ceramic monolith nature provides such hydrophobic PGAFoams with thermal management, robust soundproof, and fire-resistance performance. Highly machinable PGAFoams can be adapted into a variety of shapes and dimensions to accommodate complex geometry applications. The scalable manufacturing of lightweight PGAFoams opens up building insulation with remarkable thermal management, high mechanical strength, low mass density, superior soundproofing, and fire-retardant performances.

Emerging Magnetic Interactions in van der Waals Heterostructures.

Vertical van der Waals (vdWs) heterostructures based on layered materials are attracting interest as a new class of quantum materials, where interfacial charge-transfer coupling can give rise to fascinating strongly correlated phenomena. Transition metal chalcogenides are a particularly exciting material family, including ferromagnetic semiconductors, multiferroics, and superconductors. Here, we report the growth of an organic-inorganic heterostructure by intercalating molecular electron donating bis(ethylenedithio)tetrathiafulvalene into (Li,Fe)OHFeSe, a layered material in which the superconducting ground state results from the intercalation of hydroxide layer. Molecular intercalation in this heterostructure induces a transformation from a paramagnetic to spin-glass-like state that is sensitive to the stoichiometry of molecular donor and an applied magnetic field. Besides, electron-donating molecules reduce the electrical resistivity in the heterostructure and modify its response to laser illumination. This hybrid heterostructure provides a promising platform to study emerging magnetic and electronic behaviors in strongly correlated layered materials.

An All-Ceramic, Anisotropic, and Flexible Aerogel Insulation Material.

To exploit the high-temperature superinsulation potential of anisotropic thermal management materials, the incorporation of ceramic aerogel into the aligned structural networks is indispensable. However, the long-standing obstacle to exploring ultralight superinsulation ceramic aerogels is the inaccessibility of its mechanical elasticity, stability, and anisotropic thermal insulation. In this study, we report a recoverable, flexible ceramic fiber-aerogel composite with anisotropic lamellar structure, where the interfacial cross-linking between ceramic fiber and aerogel is important in its superinsulation performance. The resulting ultralight aerogel composite exhibits a density of 0.05 g/cm3, large strain recovery (over 50%), and low thermal conductivity (0.0224 W m-1 K-1), while its hydrophobicity is achieved by in situ trichlorosilane coating with the water contact angle of 135°. The hygroscopic tests of such aerogel composites demonstrate a reversible thermal insulation. The mechanical elasticity and stability of the anisotropic composites, with its soundproof performance, shed light on the low-cost superelastic aerogel manufacturing with scalability for energy saving building applications.

Magnetically hard ferrite nanoparticles synthesized through aerogel nanoreactor.

Magnetic ferrite materials have been extensively studied for a range of technological applications, such as magnetic motors, recording media, and millimetre-wave devices. In this context, the nanosized epsilon phase of Fe2O3 (ϵ-Fe2O3) attracts significant attention due to its high coercive field at room temperature. Here, we report the in-situ aerogel nanoreactor growth of magnetic ϵ-Fe2O3 nanoparticles, exhibiting a coercive field (Hc) of 4000 Oe. We show that the control of nanoreactor plays an important role in the growth of ϵ-Fe2O3 nanoparticles. The findings provide a versatile reaction pathway for the growth of magnetically hard ferrite nanoparticles.

Magnetically active transition metal cation-substituted alumina.

Alumina (Al2O3) is one of the most widely used ceramic materials for innumerable applications, due to its unique combination of attractive physical and mechanical properties. These intrinsic properties are dictated by the numerous phases that Al2O3 forms and its related phase transformations. Transition metal (TM) cation dopants (iron (Fe), cobalt (Co), nickel (Ni) and manganese (Mn)), even in sparse amounts, have been shown to significantly affect the phase transformation and microstructural evolution of Al2O3. Small concentrations of TM cation dopants have successfully been incorporated to synthesize magnetically active Al2O3, while reducing the θ to α phase transformation temperature by 150 °C, and maintaining the outstanding mechanical properties. In addition, first-principle calculations based on density-functional theory with hybrid functional (HSE06) and the PBE+U methods have provided a mechanistic understanding of the formation energy and magnetism of the TM-doped α and θ phases of Al2O3. The results reveal a potential route for phase transition regulation and external magnetic field-induced texturing of Al2O3 ceramics.

Strongly Correlated Aromatic Molecular Conductor.

Strongly correlated electronic molecules open the way for strong coupling between charge, spin, and lattice degrees of freedom to enable interdisciplinary fields, such as molecular electronic switches and plasmonics, spintronics, information storage, and superconducting circuits. However, despite exciting computational predictions and promising advantages to prepare flexible geometries, the electron correlation effect in molecules has been elusive. Here, the electron correlation effects of molecular plasmonic films are reported to uncover their coupling of charge, spin, lattice, and orbital for the switchable metal-to-insulator transition under external stimuli, at which the simultaneous transition occurs from the paramagnetic, electrical, and thermal conducting state to the diamagnetic, electrical, and thermal insulating state. In addition, density functional theory calculation and spectroscopic studies are combined to provide the mechanistic understanding of electronic transitions and molecular plasmon resonance observed in molecular conducting films. The self-assembled molecular correlated conductor paves the way for the next generation integrated micro/nanosystems.

Ubiquitous energy conversion of two-dimensional molecular crystals.

Two-dimensional (2D) atomic crystals have triggered significant excitement due to their rich physics as well as potential industrial applications. The possibility of a molecular counterpart with scalable processability and superior performance is intriguing from both fundamental and applied perspectives. Here, we present the freestanding 2D molecular charge-transfer bis(ethylenedithio)tetrathiafulvalene-C60 crystals prepared by a modified Langmuir-Blodgett method, with precisely controlled few-layer thickness and centimeter-scale lateral dimension. The interconversion of intrinsic excited process, the long-range ordering and anisotropic stacking arrangement of the molecular layered crystals generate external stimuli responsive behaviors and anisotropic spin-charge conversion with magnetic energy conversion ability, as well as a superior UV photosensitivity. Moreover, the 2D freestanding crystals demonstrate superior magneto-electrical properties. These results suggest that a new class of 2D atomically thin molecular crystals with novel electronic, optical and magnetic properties have great potential for spintronic, energy and sensor applications.

High current carrying and thermal conductive copper-carbon conductors.

The surging demand for miniaturized compact devices has generated the need for new metal conductors with high current carrying ampacity, electric and thermal conductivity. Herein, we report carbon-metal conductors that exhibit a high breakdown current density (39% higher than copper) and electrical conductivity (e.g. 63% higher than that of copper at 363 K) in a broad temperature range. The mechanistic studies of thermal conductivity through first-principle modeling show that the multilayer graphene percolation networks efficiently decrease the electron-phonon coupling in the copper-graphene composites, even if phonon modes are activated at a high temperature. These results imply that the copper-based composites have the potential to be the next generation metal conductor with high electrical and thermal conductivity, as well as excellent current-carrying ampacity. More importantly, the developed composite can be deployed in the ink form, making it possible to be utilized by the microelectronic fabrication process.