MOFs for Ultrahigh Efficiency Pulsed Laser Micropropulsion.

Conventional propellant materials, such as polymers and single metal elements, have long been investigated for their potential in pulsed laser micropropulsion (LMP) technology. However, achieving superior LMP efficiency through physical mixing of these materials remains a significant challenge. This study presents a paradigm shift by introducing porous crystalline polymers, known as metal-organic frameworks (MOFs), as novel propellants in pulsed LMP. MOFs are composed of metal cations and organic ligands that form ordered structures through coordination, eliminating the problem of local hot zones arising from uneven physical mixing encountered in LMP. In direct comparison to conventional polymers and single element targets, MOFs exhibit substantially higher LMP efficiency. By precisely tailoring the metal atom fraction within MOFs, an extraordinary ultrahigh efficiency of 51.15% is achieved in pulsed LMP, surpassing the performance of similar materials previously reported in the literature. This pioneering application of MOFs not only revolutionizes the field of LMP but also opens up new frontiers for MOF utilization in various energy applications.

Optical force brush enabled free-space painting of 4D functional structures.

Femtosecond laser-based technique called two-photon polymerization (TPP) has emerged as a powerful tool for nanofabrication and integrating nanomaterials. However, challenges persist in existing three-dimensional (3D) nanoprinting methods, such as slow layer-by-layer printing and limited material options due to laser-matter interactions. Here, we present an approach to 3D nanoprinting called free-space nanopainting, using an optical force brush (OFB). OFB enables precise spatial writing paths, instantaneous adjustment of linewidths and concentrations, and unrestricted resolution beyond optical limits. OFB allows rapid aggregation and solidification of radicals, resulting in narrower lines at lower polymerization thresholds and enhanced sensitivity to laser energy. This advancement enables high-accuracy free-space painting, analogous to Chinese brush painting on paper. The printing speed is increased substantially compared to layer-by-layer methods, from 100 to 1000 times faster. We successfully printed various bionic muscle models derived from 4D nanostructures with tunable mechanical properties, responsive to electrical signals, and excellent biocompatibility.

High sensitivity and wide range flexible piezoresistive sensor based on petal-shaped MOF-derived NiCo-NPC.

Due to the advantages of high porosity, excellent conductivity, and tunable morphology, carbonized metal-organic framework (C-MOF) is expected to become an ideal material for constructing high-performance flexible pressure sensor. Herein, to achieving the suitable morphology of C-MOF for piezoresistive sensors, a rapid thermal process (RTP) was used for carbonization of NiCo-MOF, and the petal-shaped NiCo alloy nanoparticles/nanoporous carbon composites (NiCo-NPCs) were obtained. Compared with NiCo-NPCs carbonized by common thermal process (CTP), NiCo-NPCs carbonized by RTP exhibit a modified morphology with smaller particle size and larger most frequent pore diameter. Due to the modified morphology, the piezoresistive sensor with RTP-carbonized NiCo-NPCs has a high sensitivity of 62.13 kPa-1at 0-3 kPa, which is 3.46 times higher than that of the sensor with CTP-carbonized NiCo-NPCs. Meanwhile, the sensor shows an ultra-wide range of 1000 kPa, excellent cycle stability (>4000 cycles), and fast response/recovery time of 25/44 ms. Furthermore, the application of the sensor in dynamic loading test, airflow monitoring, voice recognition, and gesture detection demonstrates its great application prospects. In short, this work investigates the application of carbonized NiCo-MOFs in flexible pressure sensors, and provides a new strategy to improve the performance of piezoresistive sensors with porous carbon derived from MOFs.

Oriented Perovskite Film from Laser Recrystallization in Magnetic Field.

The orientation of crystals on the substrate and the presence of defects are critical factors in electro-optic performance. However, technical approaches to guide the orientational crystallization of electro-optical thin films remain challenging. Here, a novel physical method called magnetic-field-assisted pulse laser annealing (MAPLA) for controlling the orientation of perovskite crystals on substrates is reported. By inducing laser recrystallization of perovskite crystals under a magnetic field and with magnetic nanoparticles, the optical and magnetic fields are found to guide the orientational gathering of perovskite units into nanoclusters, resulting in perovskite crystals with preferred lattice orientation in (110) and (220) perpendicular to the substrate. The perovskite crystals obtained by MAPLA exhibit significantly larger grain size and fewer defects compared to those from pulsed laser annealing (PLA) and traditional thermal annealing, resulting in improved carrier lifetime and mobility. Furthermore, MAPLA demonstrates enhanced device performance, increasing responsivity and detectivity by two times, and photocurrent by nearly three orders compared with PLA. The introduction of Fe2 O3 nanoparticles during MAPLA not only improves crystal size and orientation but also significantly enhances long-term stability by preventing Pb2+ reduction. The MAPLA method has great potential for fabricating many electro-optical thin films with desired device properties and stability.

Nanosecond Laser Confined Bismuth Moiety with Tunable Structures on Graphene for Carbon Dioxide Reduction.

Substrate-supported catalysts with atomically dispersed metal centers are promising for driving the carbon dioxide reduction reaction (CO2RR) to produce value-added chemicals; however, regulating the size of exposed catalysts and optimizing their coordination chemistry remain challenging. In this study, we have devised a simple and versatile high-energy pulsed laser method for the enrichment of a Bi "single atom" (SA) with a controlled first coordination sphere on a time scale of nanoseconds. We identify the mechanistic bifurcation routes over a Bi SA that selectively produce either formate or syngas when bound to C or N atoms, respectively. In particular, C-stabilized Bi (Bi-C) exhibits a maximum formate partial current density of -29.3 mA cm-2 alongside a TOF value of 2.64 s-1 at -1.05 V vs RHE, representing one of the best SA-based candidates for CO2-to-formate conversion. Our results demonstrate that the switchable selectivity arises from the different coupling states and metal-support interactions between the central Bi atom and adjacent atoms, which modify the hybridizations between the Bi center and *OCHO/*COOH intermediates, alter the energy barriers of the rate-determining steps, and ultimately trigger the branched reaction pathways after CO2 adsorption. This work demonstrates a practical and universal ultrafast laser approach to a wide range of metal-substrate materials for tailoring the fine structures and catalytic properties of the supported catalysts and provides atomic-level insights into the mechanisms of the CO2RR on ligand-modified Bi SAs, with potential applications in various fields.

Manipulating exchange bias in 2D magnetic heterojunction for high-performance robust memory applications.

The exchange bias (EB) effect plays an undisputed role in the development of highly sensitive, robust, and high-density spintronic devices in magnetic data storage. However, the weak EB field, low blocking temperature, as well as the lack of modulation methods, seriously limit the application of EB in van der Waals (vdW) spintronic devices. Here, we utilized pressure engineering to tune the vdW spacing of the two-dimensional (2D) FePSe3/Fe3GeTe2 heterostructures. The EB field (HEB, from 29.2 mT to 111.2 mT) and blocking temperature (Tb, from 20 K to 110 K) are significantly enhanced, and a highly sensitive and robust spin valve is demonstrated. Interestingly, this enhancement of the EB effect was extended to exposed Fe3GeTe2, due to the single-domain nature of Fe3GeTe2. Our findings provide opportunities for the producing, exploring, and tuning of magnetic vdW heterostructures with strong interlayer coupling, thereby enabling customized 2D spintronic devices in the future.

Epidermal Patch with Biomimetic Multistructural Microfluidic Channels for Timeliness Monitoring of Sweat.

Wearable sweat sensors have been developed rapidly in recent years due to the great potential in health monitoring. Developing a convenient manufacturing process and a novel structure to realize timeliness and continuous monitoring of sweat is crucial for the practical application of sweat sensors. Herein, inspired by the striped grooves and granular structures of bamboo leaves, we realized an epidermal patch with biomimetic multilevel structural microfluidic channels for timeliness monitoring of sweat via 3D printing and femtosecond laser processing. The striped grooves and ridges are alternately arranged at the bottom of the microfluidic channels, and the surface of the ridges has rough granular structures. The striped grooves improve the capillary effect in the microchannels by dividing the microchannels, and the granular structures enhance the slip effect of sweat by increasing surface hydrophobicity. The experimental results show that compared with the conventional microfluidic channels, the water collecting rate of the biomimetic microchannels increased by about 60%, which is consistent with the theoretical analysis. The superior sweat-collecting efficiency in the epidermal patch with the biomimetic multistructure enables sensitive, continuous, and stable monitoring of sweat physiological signals. Besides, this work provides new design and manufacturing approaches for other microfluidic applications.

Armored Nanocones Engraved by Selective Laser Doping Enhanced Plasma Etching for Robust Supertransmissivity.

Optical antireflection surfaces equipped with subwavelength nanocone arrays are commonly used to reach broadband supertransmissivity but are limited by the lack of wear resistance. We design and manufacture a structured surface with robust antireflection structures (R-ARS) composed of substrate-engraved nanocone arrays with micro-grid-shaped walls as protective armor. An ultrafast laser beam is used to selectively ablate and dope the metal from the deposited film into the subsurface of optical substrates to strengthen self-assembled nanoparticles formed during plasma etching as masks for nanocones. The untreated microscale metal grids serve as etching masks for the remaining protective armor. The geometrical features of nanocones and spatial distribution of protective armor with a proper duty cycle are theoretically optimized for improvement in both transmissivity and mechanical robustness. We demonstrate armored dense engraved nanocone arrays (with tip diameters of ∼50 nm and heights of ∼0.8 µm) on visible fused silica and infrared semi-insulating SiC with protective micro-square-grid armor. The average transmittances are improved from 93% to over 97% (on 0.4-1.2 µm) for double-face-structured fused silica, and from 60 to 65% (on 3-5 µm) for single-face-structured SiC, with few reductions of fused silica after 150 cycles of severe abrasion (under a pressure of 5.34 MPa) proving the excellent mechanical robust performance of R-ARS.

In vitro breast cancer models for studying mechanisms of resistance to endocrine therapy.

The development of endocrine resistance is a common reason for the failure of endocrine therapies in hormone receptor-positive breast cancer. This review provides an overview of the different types of in vitro models that have been developed as tools for studying endocrine resistance. In vitro models include cell lines that have been rendered endocrine-resistant by ex vivo treatment; cell lines with de novo resistance mechanisms, including genetic alterations; three-dimensional (3D) spheroid, co-culture, and mammosphere techniques; and patient-derived organoid models. In each case, the key discoveries, different analysis strategies that are suitable, and strengths and weaknesses are discussed. Certain recently developed methodologies that can be used to further characterize the biological changes involved in endocrine resistance are then emphasized, along with a commentary on the types of research outcomes that using these techniques can support. Finally, a discussion anticipates how these recent developments will shape future trends in the field. We hope this overview will serve as a useful resource for investigators that are interested in understanding and testing hypotheses related to mechanisms of endocrine therapy resistance.

High-Efficiency Copper Removal by Nitrogen Plasma-Assisted Picosecond Laser Processing.

Copper (Cu) removal efficiency is a key parameter in the processing of Cu-based electronic devices. Herein, a nitrogen plasma-assisted picosecond (ps) laser process for Cu removal is presented. Based on the cleaning and activation effect of nitrogen plasma on the surface of Cu film in ps-laser ablation, the removal efficiency can be significantly improved. Theoretically, the interaction mechanism between Cu and the ps-laser under the action of the plasma flow field is investigated by the dual temperature model (TTM) and finite element analysis (FEA). Meanwhile, the experimental results show that the angle of the plasma flow significantly affects the laser ablation of Cu. Small-angle plasma helps to improve the ps-laser processing precision of Cu, while large-angle plasma can effectively improve the ps-laser processing efficiency of Cu. Under the laser fluence of 2.69 J/cm2, the removal depth of the Cu film by a 30° plasma-assisted ps-laser is 148% higher than that by the non-plasma-assisted ps-laser, which indicates the application potential of nitrogen plasma in improving the laser ablation process.

2+δ-Dimensional Materials via Atomistic Z-Welding.

Pivotal to functional van der Waals stacked flexible electronic/excitonic/spintronic/thermoelectric chips is the synergy amongst constituent layers. However; the current techniques viz. sequential chemical vapor deposition, micromechanical/wet-chemical transfer are mostly limited due to diffused interfaces, and metallic remnants/bubbles at the interface. Inter-layer-coupled 2+δ-dimensional materials, as a new class of materials can be significantly suitable for out-of-plane carrier transport and hence prompt response in prospective devices. Here, the discovery of the use of exotic electric field ≈106  V cm- 1 (at microwave hot-spot) and 2 thermomechanical conditions i.e. pressure ≈1 MPa, T ≈ 200 °C (during solvothermal reaction) to realize 2+δ-dimensional materials is reported. It is found that Pz Pz chemical bonds form between the component layers, e.g., CB and CN in G-BN, MoN and MoB in MoS2 -BN hybrid systems as revealed by X-ray photoelectron spectroscopy. New vibrational peaks in Raman spectra (BC ≈1320 cm-1 for the G-BN system and MoB ≈365 cm-1 for the MoS2 -BN system) are recorded. Tunable mid-gap formation, along with diodic behavior (knee voltage ≈0.7 V, breakdown voltage ≈1.8 V) in the reduced graphene oxide-reduced BN oxide (RGO-RBNO) hybrid system is also observed. Band-gap tuning in MoS2 -BN system is observed. Simulations reveal stacking-dependent interfacial charge/potential drops, hinting at the feasibility of next-generation functional devices/sensors.

MOF-Like 3D Graphene-Based Catalytic Membrane Fabricated by One-Step Laser Scribing for Robust Water Purification and Green Energy Production.

Increasing both clean water and green energy demands for survival and development are the grand challenges of our age. Here, we successfully fabricate a novel multifunctional 3D graphene-based catalytic membrane (3D-GCM) with active metal nanoparticles (AMNs) loading for simultaneously obtaining the water purification and clean energy generation, via a "green" one-step laser scribing technology. The as-prepared 3D-GCM shows high porosity and uniform distribution with AMNs, which exhibits high permeated fluxes (over 100 L m-2 h-1) and versatile super-adsorption capacities for the removal of tricky organic pollutants from wastewater under ultra-low pressure-driving (0.1 bar). After adsorption saturating, the AMNs in 3D-GCM actuates the advanced oxidization process to self-clean the fouled membrane via the catalysis, and restores the adsorption capacity well for the next time membrane separation. Most importantly, the 3D-GCM with the welding of laser scribing overcomes the lateral shear force damaging during the long-term separation. Moreover, the 3D-GCM could emit plentiful of hot electrons from AMNs under light irradiation, realizing the membrane catalytic hydrolysis reactions for hydrogen energy generation. This "green" precision manufacturing with laser scribing technology provides a feasible technology to fabricate high-efficient and robust 3D-GCM microreactor in the tricky wastewater purification and sustainable clean energy production as well.

Mesoporous LDH Metastructure from Multiscale Assembly of Defective Nanodomains by Laser Shock for Oxygen Evolution Reaction.

Laser is a powerful tool for the synthesis of nanomaterials. The intensive laser pulses delivered to materials within nanoseconds allow the formation of novel structures that are inaccessible for conventional methods. Layered double hydroxide (LDH) nanostructures with high porosity, suitable dopants, and rich defects are desirable for catalysts, however, tremendously difficult in a one-pot synthesis. Here it is found that confined laser shock in solvent leads to the formation of nanoreactors which guide the assembly of multiscale LDH building units, larger nanosheets as frame and smaller nanodomains as building blocks. These nanodomains have rich vacancy defects and are interlocked in a high packed density of 1013  cm-2 , leaving rich mesopores across the nanosheets and coral-like morphology. Like the natural coral reef that has multiscale structure to accommodate different marine organisms, the coral-like LDH metastructure provides large surface area and rich active sites for the interaction with guest molecules. Benefiting from the multiscale porous structure and rational dopant, this LDH catalyst exhibits a low overpotential of 220 mV at 10 mA cm-2 for oxygen evolution reaction (OER), standing as one of the best LDH catalysts to date.

Nanoalloy libraries from laser-induced thermionic emission reduction.

Nanoalloys, especially high-entropy nanoalloys (HENAs) that contain equal stoichiometric metallic elements in each nanoparticle, are widely used in vast applications. Currently, the synthesis of HENAs is challenged by slow reaction kinetics that leads to phase segregation, sophisticated pretreatment of precursors, and inert conditions that preclude scalable fabrication of HENAs. Here, we report direct conversion of metal salts to ultrafine HENAs on carbonaceous support by nanosecond pulsed laser under atmospheric conditions. Because of the unique laser-induced thermionic emission and etch on carbon, the reduced metal elements were gathered to ultrafine HENAs and stabilized by defective carbon support. This scalable, facile, and low-cost method overcomes the immiscible issue and can produce various HENAs uniformly with a size of 1 to 3 nanometers and metal elements up to 11 with productivity up to 7 grams per hour. One of the senary HENAs exhibited excellent catalytic performance in oxygen reduction reaction, manifesting great potential in practical applications.

Bionic Optical Leaf for Photoreduction of CO2 from Noble Metal Atom Mediated Graphene Nanobubble Arrays.

The reduction of CO2 to useful chemicals by solar irradiation has been of great interest in recent years to tackle the greenhouse effect. Compared with inorganic metal oxide particles, carbonaceous materials, such as graphene, are excellent in light absorption; however, they lack in activity and selectivity because of the challenge to manipulate the band gap and optimize the electron-hole separation, which drives the photoreduction process. In this work, inspired by the delicate natural plant leaf structure, we fabricated orderly stacked graphene nanobubble arrays with nitrogen dopant for the coordination of noble metal atoms to mimic the natural photoreduction process in plant leaves. This graphene metamaterial not only mimics the optical structure of leaf cells, which scatter and absorb light efficiently, but also drives the CO2 reduction via nitrogen coordinated metal atoms as the chlorophyll does in plants. Our characterizations show that the band gap of nitrogen-doped graphene could be precisely tailored via substitution with different noble metal atoms on the doped site. The noble atoms coordinated on the doped site of graphene metamaterial not only enlarge the light absorption volume but also maximize the utilization of noble metals. The bionic optical leaf metamaterial coordinated with Au atoms exhibits high CO productivity up to 11.14 mmol gcat-1 h-1 and selectivity to 95%, standing as one of the best catalysts among the carbonaceous and metal-based catalysts reported to date. This catalyst also maintained a high performance at low temperatures, manifesting potential applications of this bionic catalyst at polar regions to reduce greenhouse gases.

3D MOF Nanoarchitecture Membrane via Ultrafast Laser Nanoforging.

Metal-organic framework (MOF) crystals are useful in a vast area of applications because of their unique chemical and physical properties. Manufacturing of an integrated MOF membrane with 3D nanoarchitectures on the surface is especially important for their applications. However, as MOF crystals usually exist as powdery crystals, fabrication of their large area, monolithic, and high-resolution patterns is challenging. Here, it is found that isolated MOF nanocrystals could be directly converted to a monolithic MOF film with designed 3D nanoarchitectures/patterns via an ultrafast laser induced nanoforging without binders. During the nanosecond laser shock, the voids among MOF nanocrystals are eliminated due to the surface amorphization effect, which allows the fusing of the MOF nanocrystals on the grain boundaries, leading to the formation of a dense film while preserving the nature of the pristine MOF. The high strain rate by laser enhances formability of MOFs and overcomes their brittleness to generate arbitrary 3D nanoarchitectures with feature sizes down to 100 nm and high productivity up to 80 cm2 min-1 . These 3D MOF nanoarchitectures also exhibit boosted mechanical strength up to 100% compared with their powdery particles. This method is facile and low-cost and could potentially be used in various fields, such as devices, separation, and biochemical applications.

Soap film inspired mechanical metamaterials approaching theoretical bound of stiffness across full density range.

Structural mechanical metamaterials, with their mass-efficient architectures and unprecedented mechanical properties, are in critical demand for high-performance applications. However, finding the optimal 3D geometries towards a particular property, such as reaching the stiffness upper bound, usually demands high volume of calculations or numerical optimizations. Here we generate structured mechanical metamaterials by imitating the natural occupation of periodic volume by inflated soap films. Our strategy of occupying volume between two periodic constant mean curvature (CMC) surfaces generates a series of mechanical metamaterials of varied relative densities ranging from 0 to 1. The mechanically isotropic ISO-CMC structures exhibit bulk moduli over 94% of the theoretical limit. Using finite element models, we reveal the fundamental mechanical behaviors of the structures that lead to ideal performances. These phenomena are found to be in close relation to the curvature-driven design of our metamaterial structures. These structures are compared to other reported mechanical metamaterials, such as closed-cell plate structures and triply periodic minimal surface (TPMS) structures. The unique curvature-driven thickening strategy of our method renders structures that outperform their peers in terms of bulk moduli and relative density coverage. The CMC structures present a new class of easily 3D printable, permeable and stiff mechanical metamaterials. The design methodology also could serve in future development of novel mechanical metamaterials powered by advanced computational tools.

Magnetically Aligned Ultrafine Cobalt Embedded 3D Porous Carbon Metamaterial by One-Step Ultrafast Laser Direct Writing.

Spatial manipulation of nanoparticles (NPs) in a controlled manner is critical for the fabrication of 3D hybrid materials with unique functions. However, traditional fabrication methods such as electron-beam lithography and stereolithography are usually costly and time-consuming, precluding their production on a large scale. Herein, for the first time the ultrafast laser direct writing is combined with external magnetic field (MF) to massively produce graphene-coated ultrafine cobalt nanoparticles supported on 3D porous carbon using metal-organic framework crystals as precursors (5 × 5 cm2 with 10 s). The MF-confined picosecond laser scribing not only reduces the metal ions rapidly but also aligns the NPs in ultrafine and evenly distributed order (from 7.82 ± 2.37 to 3.80 ± 0.84 nm). ≈400% increment of N-Q species within N compositionis also found as the result of the special MF-induced laser plasma plume. (). The importance of MF is further exmined by electrochemical water-splitting tests. Significant overpotential improvements of 90 and 150 mV for oxygen evolution reaction and hydrogen evolution reaction are observed, respectively, owing to the MF-induced alignment of the NPs and controlled elemental compositions. This work provides a general bottom-up approach for the synthesis of metamaterials with high outputs yet a simple setup.

Employing Hybrid Lennard-Jones and Axilrod-Teller Potentials to Parametrize Force Fields for the Simulation of Materials' Properties.

The development of novel materials has challenges besides their synthesis. Materials such as novel MXenes are difficult to probe experimentally due to their reduced size and low stability under ambient conditions. Quantum mechanics and molecular dynamics simulations have been valuable options for material properties determination. However, computational materials scientists may still have difficulty finding specific force field models for their simulations. Force fields are usually hard to parametrize, and their parameters' determination is computationally expensive. We show the Lennard-Jones (2-body interactions) combined with the Axilrod-Teller (3-body interactions) parametrization process' applicability for metals and new classes of materials (MXenes). Because this parametrization process is simple and computationally inexpensive, it allows users to predict materials' behaviors under close-to-ambient conditions in molecular dynamics, independent of pre-existing potential files. Using the process described in this work, we have made the Ti2C parameters set available for the first time in a peer-reviewed work.

Nanoscale-Precision Removal of Copper in Integrated Circuits Based on a Hybrid Process of Plasma Oxidation and Femtosecond Laser Ablation.

Copper (Cu) is the main interconnect conductor for integrated circuits (IC), and its processing quality is very important to device performance. Herein, a hybrid process of plasma oxidation and femtosecond laser (fs-laser) ablation was proposed for the nanoscale precision removal of Cu in integrated circuits. In this hybrid process, the surface layer of Cu was oxidized to the copper oxide by plasma oxidation, and then the fs-laser with a laser fluence lower than the Cu ablation threshold was used to remove the copper oxide without damaging the underlying Cu. Theoretically, the surface temperature evolutions of Cu and copper oxide under the femtosecond laser were studied by the two-temperature model, and it was revealed that the ablation threshold of copper oxide is much lower than that of Cu. The experimental results showed that the ablation threshold of copper oxide is lower than that of Cu, which is consistent with the theoretical analysis. Using the hybrid process, a surface roughness of 3 nm and a removal accuracy of 4 nm were obtained in the process of Cu film processing, which were better than those obtained by fs-laser ablation. This demonstrated that the hybrid process has good application potential in the field of copper micromachining.