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.

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.

Ultrafast Laser Manufacture of Stable, Efficient Ultrafine Noble Metal Catalysts Mediated with MOF Derived High Density Defective Metal Oxides.

Supported metal nanoparticles (MNPs) undergo severe aggregation, especially when the interaction between MNPs and their supports are limited and weak where their performance deteriorates dramatically. This becomes more severe when catalysts are operated under high temperature. Here, it is reported that MNPs including Pt, Au, Rh, and Ru, with sub-2 nm size can be stabilized on densely packed defective CeO2 nanoparticles with sub-5 nm size via strong coupling by direct laser conversion of corresponding metal ions encapsulated cerous metal-organic frameworks (Ce-MOFs). Ce-MOF serves as an ideal dispersion precursor to uniformly encapsulate noble metal ions in their orderly arranged pores. Ultrafast laser vaporization and cooling forms uniform, ultrasmall, well-mixed, and exceptionally dense nanoparticles of metal and metal oxide concurrently. The laser-induced ultrafast reaction (within tens of nanoseconds) facilitates the precipitation of CeO2 nanoparticles with abundant surficial defects. Due to the well-mixed ultrasmall Pt and CeO2 components with strong coupling, this catalyst exhibits exceptionally high stability and activity both at low and high temperatures (170-1100 °C) for CO oxidation in long-term operation, significantly exceeding catalysts prepared by traditional methods. The scalable feature of laser and huge MOF family make it a versatile method for the production of MNP-based nanocomposites in wide applications.

Laser Shock Tuning Dynamic Interlayer Coupling in Graphene-Boron Nitride Moiré Superlattices.

In the emergence of graphene and many two-dimensional (2D) materials, the most exciting applications come from stacking them into 3D devices, promising many excellent possibilities for neoteric electronics and optoelectronics. Layers of semiconductors, insulators, and conductors can be stacked to form van der Waals heterostructures, after the weak bonds formed between the layers. However, the interlayer coupling in these heterostructures is usually hard to modulate, resulting in difficulty to realize their emerging optical or electronic properties. Especially, the relationship between interlayer distance and interlayer coupling remains to be investigated, due to the lack of effective technology. In this work, we have used laser shocking to controllably tune the interlayer distance between graphene (Gr) and boron nitride (BN) in the Gr/BN/Gr heterostructures and the strains in the 2D heterolayers, providing a simple and effective way to modify their optic and electronic properties. After lase shocking, the reduction of interlayer distance is calculated by molecular dynamics (MD) simulation. Some atoms in Gr or BN are out-of-plane as well. In Raman measurements, the G peak in the heterostructure shows a red-shifted trend after laser shocking, indicating the strong phonon coupling in the interlayer. Moreover, the larger transparency after laser shocking also verifies the stronger photon coupling in the heterostructure. To investigate the effects of the interlayer coupling of heterostructure on its out-of-plane electronic behavior, we have investigated the electronic tunneling behavior. The heterostructure after laser shock reveals a lager tunneling current and lower tunneling threshold, proving an unexpected better electrical property. From DFT calculations, laser shocking can modulate the band gap structure of graphene in Gr/BN/Gr heterostructures; therefore, the heterostructures can be implemented as a unique photonic platform to modulate the emission characters of the anchored CdSe/ZnS core-shell quantum dots. Remarkably, the effective laser shocking method is also applicable to various otherwise noninteracting 2D materials, resulting in many new phenomena, which will lead science and technology to unexplored territories.

Nanoscale Laser Metallurgy and Patterning in Air Using MOFs.

We report metallurgy on the nanoscale to generate metal nanoparticles and their simultaneous patterning in a single step. This is achieved by the self-reduction of porous metal-organic framework crystals using nanosecond pulsed laser irradiation. Metal nanoparticles of Fe, Co, Ni, Cu, Zn, Cd, In, Bi, and Pb with uniform sizes (controllable between 3 to 200 nm) and gaps (as narrow as 2 nm) are produced by nine different metal-organic frameworks, where atomically dispersed non-noble metal ions are reduced and gathered across the pores. The instant light absorption and cooling at local positions by a laser allows for precise and efficient patterning of metal nanoparticles. This new method is suitable for device fabrication at a speed of 15 mm2 s-1 on glass, consuming only 1.5 W of power. A large variety of metal nanoparticle three-dimensional architectures are demonstrated, among which one architecture exhibits an enhanced plasmonic effect homogeneously across the entire pattern for the detection of molecules at an extremely low concentration (10-12 M). These architectures are extremely stable under air and humidity during production, use, and storage, without altering the oxidation state, for 6 months.

Scalable Nanoshaping of Hierarchical Metallic Patterns with Multiplex Laser Shock Imprinting Using Soft Optical Disks.

Large-area patterning of metals in nanoscale has always been a challenge. Traditional microfabrication processes involve many high-cost steps, including etching and high-vacuum deposit, which limit the development of functional nanostructures, especially multiscale metallic patterns. Here, multiplex laser shock imprinting (MLSI) process is introduced to directly manufacture hierarchical micro/nanopatterns at a high strain rate on metallic surfaces using soft optical disks with 1D periodic trenches as molds. The unique metal/polymer layered structures in inexpensive soft optical disks make them strong candidates of molds for MLSI processes. The feasibility of MLSI on hard metals toward soft molds is studied using theoretical simulation. In addition, various types of hierarchical structures are fabricated via MLSI, and their optical reflectance can be modulated via a combination of depth (laser power density), width (types of molds), and angles (rotation between molds). The optical properties have been studied with surface plasmon polariton modes theory. This work opens a new way of manufacturing hierarchical micro/nanopatterns on metals, which is promising for future applications in fields of plasmonics and metasurfaces.

Alpha Lead Oxide (α-PbO): A New 2D Material with Visible Light Sensitivity.

Even though transition metal dichalcogenides (TMDCs) are deemed to be novel photonic and optoelectronic 2D materials, the visible band gap being often limited to monolayer, hampers their potential in niche applications due to fabrication challenges. Uncontrollable defects and degraded functionalities at elevated temperature and under extreme environments further restrict their prospects. To address such limitations, the discovery of a new 2D material, α-PbO is reported. Micromechanical as well as sonochemical exfoliation of 2D atomic sheets of α-PbO are demonstrated and its optical behavior is investigated. Spectroscopic investigations indicate layer dependent band gaps. In particular, even multilayered PbO sheets exhibit visible band gap > 2 eV (direct) which is rare among semiconducting 2D materials. The emission lifetime of multilayer PbO atomic sheets is 7 ns (dim light) as compared to the monolayer which gives 2.5 ns lifetime and an intense light. Density functional theory calculations of layer dependent band structure of α-PbO matches well with experimental results. Experimental findings suggest that PbO atomic sheets exhibit hydrophobic nature, thermal robustness, microwave stability, anti-corrosive behaviour and acid resistance. This new low-cost, abundant and robust 2D material is expected to find many applications in the fields of electronics, optoelectronics, sensors, photocatalysis and energy storage.

Laser additive manufacturing bulk graphene-copper nanocomposites.

The exceptional mechanical properties of graphene make it an ideal nanofiller for reinforcing metal matrix composites (MMCs). In this work, graphene-copper (Gr-Cu) nanocomposites have been fabricated by a laser additive manufacturing process. Transmission electron microscopy (TEM), x-ray diffraction (XRD) and Raman spectroscopy were utilized to characterize the fabricated nanocomposites. The XRD, Raman spectroscopy, energy dispersive spectroscopy and TEM results demonstrated the feasibility of laser additive manufacturing of Gr-Cu nanocomposites. The microstructures were characterized by high resolution TEM and the results further revealed the interface between the copper matrix and graphene. With the addition of graphene, the mechanical properties of the composites were enhanced significantly. Nanoindentation tests showed that the average modulus value and hardness of the composites were 118.9 GPa and 3 GPa respectively; 17.6% and 50% increases were achieved compared with pure copper, respectively. This work demonstrates a new way to manufacture graphene copper nanocomposites with ultra-strong mechanical properties and provides alternatives for applications in electrical and thermal conductors.

Parallel Nanoshaping of Brittle Semiconductor Nanowires for Strained Electronics.

Semiconductor nanowires (SCNWs) provide a unique tunability of electro-optical property than their bulk counterparts (e.g., polycrystalline thin films) due to size effects. Nanoscale straining of SCNWs is desirable to enable new ways to tune the properties of SCNWs, such as electronic transport, band structure, and quantum properties. However, there are two bottlenecks to prevent the real applications of straining engineering of SCNWs: strainability and scalability. Unlike metallic nanowires which are highly flexible and mechanically robust for parallel shaping, SCNWs are brittle in nature and could easily break at strains slightly higher than their elastic limits. In addition, the ability to generate nanoshaping in large scale is limited with the current technologies, such as the straining of nanowires with sophisticated manipulators, nanocombing NWs with U-shaped trenches, or buckling NWs with prestretched elastic substrates, which are incompatible with semiconductor technology. Here we present a top-down fabrication methodology to achieve large scale nanoshaping of SCNWs in parallel with tunable elastic strains. This method utilizes nanosecond pulsed laser to generate shock pressure and conformably deform the SCNWs onto 3D-nanostructured silicon substrates in a scalable and ultrafast manner. A polymer dielectric nanolayer is integrated in the process for cushioning the high strain-rate deformation, suppressing the generation of dislocations or cracks, and providing self-preserving mechanism for elastic strain storage in SCNWs. The elastic strain limits have been studied as functions of laser intensity, dimensions of nanowires, and the geometry of nanomolds. As a result of 3D straining, the inhomogeneous elastic strains in GeNWs result in notable Raman peak shifts and broadening, which bring more tunability of the electrical-optical property in SCNWs than traditional strain engineering. We have achieved the first 3D nanostraining enhanced germanium field-effect transistors from GeNWs. Due to laser shock induced straining effect, a more than 2-fold hole mobility enhancement and a 120% transconductance enhancement are obtained from the fabricated back-gated field effect transistors. The presented nanoshaping of SCNWs provide new ways to manipulate nanomaterials with tunable electrical-optical properties and open up many opportunities for nanoelectronics, the nanoelectrical-mechanical system, and quantum devices.

Observation of Optical and Electrical In-Plane Anisotropy in High-Mobility Few-Layer ZrTe5.

Transition metal pentatelluride ZrTe5 is a versatile material in condensed-matter physics and has been intensively studied since the 1980s. The most fascinating feature of ZrTe5 is that it is a 3D Dirac semimetal which has linear energy dispersion in all three dimensions in momentum space. Structure-wise, ZrTe5 is a layered material held together by weak interlayer van der Waals force. The combination of its unique band structure and 2D atomic structure provides a fertile ground for more potential exotic physical phenomena in ZrTe5 related to 3D Dirac semimentals. However, the physical properties of its few-layer form have yet to be thoroughly explored. Here we report strong optical and electrical in-plane anisotropy of mechanically exfoliated few-layer ZrTe5. Raman spectroscopy shows a significant intensity change with sample orientations, and the behavior of angle-resolved phonon modes at the Γ point is explained by theoretical calculations. DC conductance measurement indicates a 50% of difference along different in-plane directions. The diminishing of resistivity anomaly in few-layer samples indicates the evolution of band structure with a reduced thickness. A low-temperature Hall experiment sheds light on more intrinsic anisotropic electrical transport, with a hole mobility of 3000 and 1500 cm2/V·s along the a-axis and c-axis, respectively. Pronounced quantum oscillations in magnetoresistance are observed at low temperatures with the highest electron mobility up to 44 000 cm2/V·s.

Fluorescence Lifetime Imaging of Nanoflares for mRNA Detection in Living Cells.

The expression level of tumor-related mRNA can reveal significant information about tumor progression and prognosis, so specific mRNA in cells provides an important approach for biological and disease studies. Here, fluorescence lifetime imaging of nanoflares in living cells was first employed to detect specific intracellular mRNA. We characterized the lifetime changes of the prepared nanoflares before and after the treatment of target mRNA and also compared the results with those of fluorescence intensity-based measurements both intracellularly and extracellularly. The nanoflares released the cy5-modified oligonucleotides and bound to the targets, resulting in a fluorescence lifetime lengthening. This work puts forward another dimension of detecting specific mRNA in cells and can also open new ways for detection of many other biomolecules.

Spectral plasmonic effect in the nano-cavity of dye-doped nanosphere-based photonic crystals.

We demonstrated three-dimensional PMMA-based photonic crystal (3D-PC) nanostructures attached to Au nanoparticles (AuNPs), which undergo self-organization into super lattice planes and enhance the fluorescence properties. This new structure exhibited interesting tunable spectral, peak broadening plasmonic behavior because of strong plasmonic interaction at high laser powers. The presented work provides an important tool to improve the efficiency of dye laser applications.

3D stereolithography printing of graphene oxide reinforced complex architectures.

Properties of polymer based nanocomposites reply on distribution, concentration, geometry and property of nanofillers in polymer matrix. Increasing the concentration of carbon based nanomaterials, such as CNTs, in polymer matrix often results in stronger but more brittle material. Here, we demonstrated the first three-dimensional (3D) printed graphene oxide complex structures by stereolithography with good combination of strength and ductility. With only 0.2% GOs, the tensile strength is increased by 62.2% and elongation increased by 12.8%. Transmission electron microscope results show that the GOs were randomly aligned in the cross section of polymer. We investigated the strengthening mechanism of the 3D printed structure in terms of tensile strength and Young's modulus. It is found that an increase in ductility of the 3D printed nanocomposites is related to increase in crystallinity of GOs reinforced polymer. Compression test of 3D GOs structure reveals the metal-like failure model of GOs nanocomposites.

Preparation and Effect of Lighting on Structures and Properties of GSH Capped ZnSe QDs.

L-glutathione (GSH) capped ZnSe quantum dots (QDs) were prepared by microwave-assisted aqueous synthesis. Then, the resulting QDs were illuminated under dark, ultraviolet light and incandescent light, respectively. Thereby effect of lighting on the structures and properties of QDs were studied systematically. It was revealed that particle size and element content of QDs took a sharp change after irradiation, while the crystal structure maintains nearly unaffected. Comparing to the ZnSe QDs under dark condition, counterparts irradiated by UV light possessed outstanding sphericity, size distribution and dispersion. And the content of sulfur (S) in ZnSe QDs irradiated by UV light was much higher relatively. The effect of lighting on vibration peaks of O-H was considerable. However, this effect was observed to be weak on other chemical bonds. The possible explanation ascribes to photo-chemical interactions can occur between S-H and O-H bonds on the surface of GSH ligand. The lighting induced GSH to occur photocatalytic oxidation on the surface of ZnSe QDs, which improved the optical properties of QDs. The effects of lighting rely on irradiation types, the sequence is UV light, incandescent light and dark from high to low.

Enhancing photo-induced ultrafast charge transfer across heterojunctions of CdS and laser-sintered TiO2 nanocrystals.

Enhancing the charge transfer process in nanocrystal sensitized solar cells is vital for the improvement of their performance. In this work we show a means of increasing photo-induced ultrafast charge transfer in successive ionic layer adsorption and reaction (SILAR) CdS-TiO2 nanocrystal heterojunctions using pulsed laser sintering of TiO2 nanocrystals. The enhanced charge transfer was attributed to both morphological and phase transformations. At sufficiently high laser fluences, volumetrically larger porous networks of the metal oxide were obtained, thus increasing the density of electron accepting states. Laser sintering also resulted in varying degrees of anatase to rutile phase transformation of the TiO2, producing thermodynamically more favorable conditions for charge transfer by increasing the change in free energy between the CdS donor and TiO2 acceptor states. Finally, we report aspects of apparent hot electron transfer as a result of the SILAR process which allows CdS to be directly adsorbed to the TiO2 surface.

Assessment of Surgical Effects on Patients with Obstructive Sleep Apnea Syndrome Using Computational Fluid Dynamics Simulations.

Obstructive sleep apnea syndrome is one of the most common sleep disorders. To treat patients with this health problem, it is important to detect the severity of this syndrome and occlusion sites in each patient. The goal of this study is to test the hypothesis that the cure of obstructive sleep apnea syndrome by maxillomandibular advancement surgery can be predicted by analyzing the effect of anatomical airway changes on the pressure effort required for normal breathing using a high-fidelity, 3-D numerical model. The employed numerical model consists of: 1) 3-D upper airway geometry construction from patient-specific computed tomographic scans using an image segmentation technique, 2) mixed-element mesh generation of the numerically constructed airway geometry for discretizing the domain of interest, and 3) computational fluid dynamics simulations for predicting the flow field within the airway and the degree of severity of breathing obstruction. In the present study, both laminar and turbulent flow simulations were performed to predict the flow field in the upper airway of the selected patients before and after maxillomandibular advancement surgery. Patients of different body mass indices were also studied to assess their effects. The numerical results were analyzed to evaluate the pressure gradient along the upper airway. The magnitude of the pressure gradient is regarded as the pressure effort required for breathing, and the extent of reduction of the pressure effort is taken to measure the success of the surgery. The description of the employed numerical model, numerical results from simulations of various patients, and suggestion for future work are detailed in this paper.

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.

Computational fluid dynamic analysis of the posterior airway space after maxillomandibular advancement for obstructive sleep apnea syndrome.

PURPOSE: This study evaluated the soft tissue change of the upper airway after maxillomandibular advancement (MMA) using computational fluid dynamics. MATERIALS AND METHODS: Eight patients with obstructive sleep apnea syndrome who required MMA were recruited into this study. All participants underwent pre- and postoperative computed tomography and then MMA by a single oral and maxillofacial surgeon. Upper airway computed tomographic datasets for these 8 patients were created with high-fidelity 3-dimensional numerical models for computational fluid dynamics. The 3-dimensional models were simulated and analyzed to study how changes in airway anatomy affect the pressure effort required for normal breathing. Airway dimensions, skeletal changes, apnea-hypopnea index, and pressure effort of pre- and postoperative 3-dimensional models were compared and correlations were interpreted. RESULTS: After MMA, laminar and turbulent air flows were significantly decreased at every level of the airway. The cross-sectional areas at the soft palate and tongue base were significantly increased. CONCLUSIONS: This study showed that MMA increased airway dimensions by increasing the distance from the occipital base to the pogonion. An increase of this distance showed a significant correlation with an improvement in the apnea-hypopnea index and a decreased pressure effort of the upper airway. Decreasing the pressure effort will decrease the breathing workload. This improves the condition of obstructive sleep apnea syndrome.

Laser shock-based platform for controllable forming of nanowires.

One-dimensional nanomaterials have attracted a great deal of research interest in the past few decades due to their unique mechanical, electrical, and optical properties. Changing the shape of nanowires (NWs) is both challenging and crucial to change the property and open wide functions of NWs, such as strain engineering, electronic transport, mechanical properties, band structure, and quantum properties, etc. Here we report a scalable strategy to conduct cutting, bending, and periodic straining of NWs by making use of laser shock pressure. Three-dimensional shaping of silver NWs is demonstrated, during which the Ag NWs exhibit very good ductility (strain-to-failure reaches 110%). Meanwhile, the high electrical conductivity of Ag NWs could retain well under controlled laser shock pressure. The microstructure observation indicates that the main deformation mechanism in Ag NWs under dynamic loading is formation of twinning and stacking fault, while dislocation motion and pile-up is less obvious. This method could be applied to semiconductor NWs as well.

Nanoscale strainability of graphene by laser shock-induced three-dimensional shaping.

Graphene has many promising physical properties. It has been discovered that local strain in a graphene sheet can alter its conducting properties and transport gaps. It is of great importance to develop scalable strain engineering techniques to control the local strains in graphene and understand the limit of the strains. Here, we present a scalable manufacturing process to generate three-dimensional (3D) nanostructures and thus induce local strains in the graphene sheet. This process utilizes laser-induced shock pressure to generate 3D tunable straining in the graphene sheet. The size dependent straining limit of the graphene and the critical breaking pressure are both studied. It is found that the graphene film can be formed to a circular mold (∼50 nm in diameter) with an aspect ratio of 0.25 and strain of 12%, and the critical breaking pressure is 1.77 GPa. These values were found to be decreasing with the increase of mold size. The local straining and breaking of graphene film are verified by Raman spectra. Large scale processing of the graphene sheet into nanoscale patterns is presented. The process could be scaled up to roll-to-roll process by changing laser beam size and scanning speed. The presented laser shock straining approach is a fast, tunable, and low-cost technique to realize strain engineering of graphene for its applications in nanoelectrical devices.