Exploring a Stable and Dense 3D Lead Chloride Hybrid with Emission of Self-Trapped Excitons toward X-Ray Scintillation

The exceptional photophysical properties of 3D organic–inorganic lead halide hybrids (OILHs) endow their significant potential for usage in optoelectronics, which has sparked intense research on novel 3D OILHs and associated applications. However, constructing new 3D OILHs based on large organic cations suffers from tough challenges due to the limitation of the Goldschmidt tolerance factor rule, let alone further explorations of their practical applications. Herein, a brand-new 3D lead chloride hybrid, (1MPZ)Pb₄Cl₁₀·H₂O ( 1 , 1MPZ = 1-methylpiperazine) is reported, featuring a dense 3D lead chloride framework made of the corner-, edge-, and face-shared lead chloride polyhedra. 1 presents a broadband white light emission with a large Stokes shift and a nanosecond photoluminescence lifetime, which originates from radiative recombination of self-trapped excitons (STEs) induced by the highly distorted structure. Such a reabsorption-free and fast-decayed STEs emission coupling with the dense 3D architecture further enables 1 with effective X-ray scintillation with good sensitivity. Impressively, 1 also shows superior environmental and radiation stability. This study provides a new 3D OILH with appealing luminescence, not only expanding the 3D OILH family but also inspiring the exploitation of their optoelectronic applications.     

Covalent Adaptable Microstructures via Combining Two-Photon Laser Printing and Alkoxyamine Chemistry: Toward Living 3D Microstructures

Manufacturing programmable materials, whose mechanical properties can be adapted on demand, is highly desired for their application in areas ranging from robotics, to biomedicine, or microfluidics. Herein, the inclusion of dynamic and living bonds, such as alkoxyamines, in a printable formulation suitable for two-photon 3D laser printing is exploited. On one hand, taking advantage of the dynamic covalent character of alkoxyamines, the nitroxide exchange reaction is investigated. As a consequence, a reduction of the Young´s Modulus by 50%, is measured by nanoindentation. On the other hand, due to its “living” characteristic, the chain extension becomes possible via nitroxide mediated polymerization. In particular, living nitroxide mediated polymerization of styrene results not only in a dramatic increase of the volume (≈8 times) of the 3D printed microstructure but also an increase of the Young's Modulus by two orders of magnitude (from 14 MPa to 2.7 GPa), while maintaining the shape including fine structural details. Thus, the approach introduces a new dimension by enabling to create microstructures with dynamically tunable size and mechanical properties.     

3D Printing Thermally Stable High-Performance Polymers Based on a Dual Curing Mechanism

High-performance polymers are an important class of materials that are used in challenging conditions, such as in aerospace applications. Until now, 3D printing based on stereolithography processes can not be performed due to a lack of suitable materials. There is report on new materials and printing compositions that enable 3D printing of objects having extremely high thermal resistance, with Tg of 283 °C and excellent mechanical properties. The printing is performed by a low-cost Digital Light Processing printer, and the formulation is based on a dual-cure mechanism, photo, and thermal process. The main components are a molecule that has both epoxy and acrylate groups, alkylated melamine that enables a high degree of crosslinking, and a soluble precursor of silica. The resulting objects are made of hybrid materials, in which the silicon is present in the polymeric backbone and partly as silica enforcement particles.     

High-rate Decoupled Water Electrolysis System Integrated with α-MoO3 as a Redox Mediator with Fast Anhydrous Proton Kinetics

Hydrogen is a promising alternative to fossil fuels that can reduce greenhouse gas emissions. Decoupled water electrolysis system using a reversible proton storage redox mediator, where the oxygen evolution reaction and hydrogen evolution reaction are separated in time and space, is an effective approach to producing hydrogen gas with high purity, high flexibility, and low cost. To realize fast hydrogen production in such a system, a redox mediator capable of releasing protons rapidly is required. Herein, α-MoO₃, with an ultrafast proton transfer property that can be explained by a dense hydrogen bond network in the lattice oxygen arrays of HxMoO₃, is examined as a high-rate redox mediator for fast hydrogen production in acidic electrolytes. The α-MoO₃ redox mediator shows both a large capacity of 204 mAh g⁻¹ and fast hydrogen production at a current rate of 10 A cm⁻²(≈153 A g⁻¹), outperforming most of the previously reported solid-state redox mediators.     

A Phase Engineering Strategy of Perovskite-Type ZnSnO3:Nd for Boosting the Sonodynamic Therapy Performance

The sensitization performance of sonosensitizers plays a key role in the sonodynamic therapy (SDT) effect. Herein, ZnSnO₃:Nd nanoparticles with R3c phase/amorphous heterogeneous structure are developed by phase engineering strategy and applied as an ideal sonosensitizer. In the crystalline perovskite-type ZnSnO₃:Nd, the substitution of the Zn²⁺ with Nd³⁺ causes the O 2p non-bonded state to move toward the Fermi level, which optimizes the band structure for ultrasound sensitization by reducing bandgap. Meanwhile, the unequal charge substitution can also form electron traps and oxygen vacancies to shorten the electron migration distance, which accelerates the electron–hole separation and inhibits carrier recombination, thus improving the acoustic sensitivity. Moreover, the dangling bonds exposed on the surface of amorphous ZnSnO₃:Nd provide more active sites, and the localized states of the amorphous phase may also promote carrier separation, resulting in synergistic SDT effect. In particular, the Zn²⁺ released from ZnSnO₃:Nd in the acidic tumor microenvironment (TME) reduces the adenosine triphosphate production by inhibiting the electron transport chain , which promotes the tumor cell apoptosis through destroying the redox balance of TME. Combining the inherent second near infrared and computed tomography imaging capabilities, this ZnSnO₃:Nd nanoplatform shows a promising perspective in clinic SDT field.     

Formation Theory and Printability of Photocurable Hydrogel for 3D Bioprinting

Bio-ink has gradually transited from ionic-crosslinking to photocrosslinking due to photocurable bio-hydrogel having good formability and biocompatibility. It is very important to understand and quantify the crosslinking process of photocurable hydrogels, otherwise, bioprinting cannot be standardized and scalable. However, there are few studies on hydrogel formation process and its photocrosslinking behavior which cannot be accurately predicted. Herein, the photoinitiated radical polymerized bio-hydrogels are taken as an example to establish the formation theory. Three typical crosslinking reactions are first distinguished. It is further proposed that not all double-bonds consumed during crosslinking contributeequally to polymerization. Then the concept of effective double-bond conversion (EDBC) is elicited. Deriving from EDBC, several important formation indices are defined. According to theory, it is predicted that slow crosslinking can improve the crosslinking degree. Furthermore, based on the slow crosslinking effect, a new strategy of projection-based 3D printing (PBP) is proposed, which significantly improved printing quality and efficiency. Overall, this work will fill the gap in hydrogel's formation theory, making it possible to accurately quantify the formation process.     

Enabling On-Demand Conformal Zn-Ion Batteries on Non-Developable Surfaces

Conventional power sources encounter difficulties in achieving structural unitization with complex-shaped electronic devices because of their fixed form factors. Here, it is realized that an on-demand conformal Zn-ion battery (ZIB) on non-developable surfaces uses direct ink writing (DIW)-based nonplanar 3D printing. First, ZIB component (manganese oxide-based cathode, Zn powder-based anode, and UV-curable gel composite electrolyte) inks are designed to regulate their colloidal interactions to fulfill the rheological requirements of nonplanar 3D printing, and establish bi-percolating ion/electron conduction pathways, thereby enabling geometrical synchronization with non-developable surfaces, and ensuring reliable electrochemical performance. The ZIB component inks are conformally printed on arbitrary curvilinear substrates to produce embodied ZIBs that can be seamlessly integrated with complicated 3D objects (including human ears). The conformal ZIB exhibits a high fill factor (i.e., areal coverage of cells on underlying substrates, ≈100%) that ensures high volumetric energy density (50.5 mWh cm_cell⁻³), which exceeds those of previously-reported shape-adaptable power sources.     

Ultra-Stable and Sensitive Ultraviolet Photodetectors Based on Monocrystalline Perovskite Thin Films

The detection of ultraviolet (UV) radiation with effective performance and robust stability is essential to practical applications. Metal halide single-crystal perovskites (ABX₃) are promising next-generation materials for UV detection. The device performance of all-inorganic CsPbCl₃ photodetectors (PDs) is still limited by inner imperfection of crystals grown in solution. Here wafer-scale single-crystal CsPbCl₃ thin films are successfully grown by vapor-phase epitaxy method, and the as-constructed PDs under UV light illumination exhibit an ultralow dark current of 7.18 pA, ultrahigh ON/OFF ratio of ≈5.22 × 10⁵, competitive responsivity of 32.8 A W⁻¹, external quantum efficiency of 10867% and specific detectivity of 4.22 × 10¹² Jones. More importantly, they feature superb long-term stability toward moisture and oxygen within twenty-one months, good temperature tolerances at low and high temperatures. The ability of the photodetector arrays for excellent UV light imaging is further demonstrated.     

3D Printable One-Part Carbon Nanotube-Elastomer Ink for Health Monitoring Applications

3D printing of conductive elastomers is a promising route to personalized health monitoring applications due to its flexibility and biocompatibility. Here, a one-part, highly conductive, flexible, stretchable, 3D printable carbon nanotube (CNT)-silicone composite is developed and thoroughly characterized. The one-part nature of the inks: i) enables printing without prior mixing and cures under ambient conditions; ii) allows direct dispensing at ≈100 µm resolution printability on nonpolar and polar substrates; iii) forms both self-supporting and high-aspect-ratio structures, key aspects in additive biomanufacturing that eliminate the need for sacrificial layers; and iv) lends efficient, reproducible, and highly sensitive responses to various tensile and compressive stimuli. The high electrical and thermal conductivity of the CNT-silicone composite is further extended to facilitate use as a flexible and stretchable heating element, with applications in body temperature regulation, water distillation, and dual temperature sensing and Joule heating. Overall, the facile fabrication of this composite points to excellent synergy with direct ink writing and can be used to prepare patient-specific wearable electronics for motion detection and cardiac and respiratory monitoring devices and toward advanced personal health tracking and bionic skin applications.     

Room-Temperature-Processable Highly Reliable Resistive Switching Memory with Reconfigurability for Neuromorphic Computing and Ultrasonic Tissue Classification

Reversible metal-filamentary mechanism has been widely investigated to design an analog resistive switching memory (RSM) for neuromorphic hardware-implementation. However, uncontrollable filament-formation, inducing its reliability issues, has been a fundamental challenge. Here, an analog RSM with 3D ion transport channels that can provide unprecedentedly high reliability and robustness is demonstrated. This architecture is realized by a laser-assisted photo-thermochemical process, compatible with the back-end-of-line process and even applicable to a flexible format. These superior characteristics also lead to the proposal of a practical adaptive learning rule for hardware neural networks that can significantly simplify the voltage pulse application methodology even with high computing accuracy. A neural network, which can perform the biological tissue classification task using the ultrasound signals, is designed, and the simulation results confirm that this practical adaptive learning rule is efficient enough to classify these weak and complicated signals with high accuracy (97%). Furthermore, the proposed RSM can work as a diffusive-memristor at the opposite voltage polarity, exhibiting extremely stable threshold switching characteristics. In this mode, several crucial operations in biological nervous systems, such as Ca²⁺ dynamics and nonlinear integrate-and-fire functions of neurons, are successfully emulated. This reconfigurability is also exceedingly beneficial for decreasing the complexity of systems—requiring both drift- and diffusive-memristors.