Deterministic Single-Row-Droplet Catalyst Formation for Uniform Growth Integration of High-Density Silicon Nanowires.

Planar silicon nanowires (SiNWs), grown by using low temperature catalytic approaches, are excellent 1D channel materials for developing high-performance logics and sensors. However, a deterministic position and size control of the metallic catalyst droplets, that lead to the growth of SiNWs, remains still a significant challenge for reliable device integration. In this work, we present a convenient but powerful edge-trimming catalyst formation strategy, which can help to produce a rather uniform single-row of indium (In) catalyst droplets of Dcat = 67 ± 5 nm in diameter, with an exact one-droplet-on-one-step arrangement. This approach marks a significant achievement in self-assembled catalyst formation and offers a foundation to attain a reliable and scalable growth of density SiNW channels, via an in-plane solid-liquid-solid (IPSLS) mechanism, with a uniform diameter down to Dnw = 35 ± 4 nm, and do not rely on high-precision lithography techniques. Prototype SiNW-based field effect transistors (FETs) are also fabricated, with a high Ion/Ioff current ratio and small subthreshold swing of >107 and 262 mV·dec-1, respectively, indicating a reliable new routine to integrate a wide range of SiNW-based logic, sensor, and display applications.

Reactive Oxygen Species Scavenging Injectable Hydrogel Potentiates the Therapeutic Potential of Mesenchymal Stem Cells in Skin Flap Regeneration.

Cell-based therapies offer tremendous potential for skin flap regeneration. However, the hostile microenvironment of the injured tissue adversely affects the longevity and paracrine effects of the implanted cells, severely reducing their therapeutic effectiveness. Here, an injectable hydrogel (nGk) with reactive oxygen species (ROS) scavenging capability, which can amplify the cell viability and functions of encapsulated mesenchymal stem cells (MSCs), is employed to promote skin flap repair. nGk is formulated by dispersing manganese dioxide nanoparticles (MnO2 NPs) in a gelatin/κ-carrageenan hydrogel, which exhibits satisfactory injectable properties and undergoes a sol-gel phase transition at around 40 °C, leading to the formation of a solid gel at physiological temperature. MnO2 NPs enhance the mechanical properties of the hydrogel and give it the ability to scavenge ROS, thus providing a cell-protective system for MSCs. Cell culture studies show that nGk can mitigate the oxidative stress, improve cell viability, and boost stem cell paracrine function to promote angiogenesis. Furthermore, MSC-loaded nGk (nGk@MSCs) can improve the survival of skin flaps by promoting angiogenesis, reducing inflammatory reactions, and attenuating necrosis, providing an effective approach for tissue regeneration. Collectively, injectable nGk has substantial potential to enhance the therapeutic benefits of MSCs, making it a valuable delivery system for cell-based therapies.

Adhesive Nanoparticle-in-Microgel System with ROS Scavenging Capability and Hemostatic Activity for Postoperative Adhesion Prevention.

Postoperative adhesion is a noteworthy clinical complication in abdominal surgery due to the existing physical barriers are unsatisfactory and inefficient in preventing its occurrence. In this work, an elaborate nanoparticle-in-microgel system (nMGel) is presented for postoperative adhesion prevention. nMGel is facilely formed by crosslinking manganese dioxide (MnO2) nanoparticles-loaded gelatin microspheres with polydopamine using a modified emulsification-chemical crosslinking method, generating a nano-micron spherical hydrogel. After drying, powdery nMGel with sprayability can perfectly cover irregular wounds and maintains robust tissue adhesiveness even in a wet environment. Additionally, nMGel possesses prominent antioxidant and free radical scavenging activity, which protects cell viability and preserves cell biological functions in an oxidative microenvironment. Furthermore, nMGel displays superior hemostatic property as demonstrated in mouse tail amputation models and liver trauma models. Importantly, nMGel can be conveniently administrated in a mouse cecal defect model to prevent adhesion between the injured cecum and the peritoneum by reducing inflammation, oxidative stress, collagen synthesis, and angiogenesis. Thus, the bioactive nMGel offers a practical and efficient approach for ameliorating postsurgical adhesion.

Biosafe Polydopamine-Decorated MnO2 Nanoparticles with Hemostasis and Antioxidative Properties for Postoperative Adhesion Prevention.

Surgical bleeding and cumulative oxidative stress are significant factors in the development of postoperative adhesions, which are always associated with adverse patient outcomes. However, effective strategies for adhesion prevention are currently lacking in clinical practice. In this study, we propose a solution using polydopamine-decorated manganese dioxide nanoparticles (MnO2@PDA) with rapid hemostasis and remarkable antioxidant properties to prevent postsurgical adhesion. The PDA modification provides MnO2@PDA with enhanced tissue adhesiveness and hemocompatibility with negligible hemolysis. Furthermore, MnO2@PDA exhibits impressive antioxidant and free radical scavenging properties, protecting cells from the negative effects of oxidative stress. The hemostatic activity of MnO2@PDA is evaluated in a mouse truncated tail model and a liver injury model, with results demonstrating reduced bleeding time and volume. The in vivo test on a mouse cecal abrasion model shows that MnO2@PDA exhibits excellent antiadhesion properties coupled with alleviated inflammation around the damaged tissue. Therefore, MnO2@PDA, which exhibits high biosafety, rapid hemostasis, and beneficial antioxidant capacity, displays exceptional antiadhesion performance, holding great potential for clinical applications to prevent postoperative adhesion.

Single-nanowire-morphed mechanical slingshot for directional shooting delivery of micro-payloads.

Stretching elastomer bands to accumulate strain energy, for a sudden projectile launching, has been an old hunting skill that will continue to find new applications in miniaturized worlds. In this work, we explore the use of highly resilient and geometry-tailored ultrathin crystalline silicon nanowires (SiNWs) as elastic medium to fabricate the first, and the smallest, mechanical slingshot. These NW-morphed slingshots were first grown on a planar surface, with desired layout, and then mounted upon standing pillar frames, with a unique self-hooking structure that allows for a facile and reliable assembly, loading and shooting maneuver of microsphere payloads. Impressively, the elastic spring design can help to store 10 times more strain energy into the NW springs, compared with the straight ones under the same pulling force, which has been strong enough to overcome the sticky van der Waals (vdW) force at the touching interfaces that otherwise will hinder a reliable releasing onto soft surface with low-surface energy or adhesion force, and to achieve a directional shooting delivery of precise amount of tiny payload units onto delicate target with the least impact damage. This NW-morphing construction strategy also provides a generic protocol/platform to fast design, prototype, and deploy new nanoelectromechanical and biological applications at extremely low costs.

Ultracompact single-nanowire-morphed grippers driven by vectorial Lorentz forces for dexterous robotic manipulations.

Ultracompact and soft pairwise grippers, capable of swift large-amplitude multi-dimensional maneuvering, are widely needed for high-precision manipulation, assembly and treatment of microscale objects. In this work, we demonstrate the simplest construction of such robotic structures, shaped via a single-nanowire-morphing and powered by geometry-tailored Lorentz vectorial forces. This has been accomplished via a designable folding growth of ultralong and ultrathin silicon NWs into single and nested omega-ring structures, which can then be suspended upon electrode frames and coated with silver metal layer to carry a passing current along geometry-tailored pathway. Within a magnetic field, the grippers can be driven by the Lorentz forces to demonstrate swift large-amplitude maneuvers of grasping, flapping and twisting of microscale objects, as well as high-frequency or even resonant vibrations to overcome sticky van de Waals forces in microscale for a reliable releasing of carried payloads. More sophisticated and functional teamwork of mutual alignment, precise passing and selective light-emitting-diode unit testing and installation were also successfully accomplished via pairwise gripper collaborations. This single-nanowire-morphing strategy provides an ideal platform to rapidly design, construct and prototype a wide range of advanced ultracompact nanorobotic, mechanical sensing and biological manipulation functionalities.

Molecular 14 C evidence for contrasting turnover and temperature sensitivity of soil organic matter components.

Climate projection requires an accurate understanding for soil organic carbon (SOC) decomposition and its response to warming. An emergent view considers that environmental constraints rather than chemical structure alone control SOC turnover and its temperature sensitivity (i.e., Q10 ), but direct long-term evidence is lacking. Here, using compound-specific radiocarbon analysis of soil profiles along a 3300-km grassland transect, we provide direct evidence for the rapid turnover of lignin-derived phenols compared with slower-cycling molecular components of SOC (i.e., long-chain lipids and black carbon). Furthermore, in contrast to the slow-cycling components whose turnover is strongly modulated by mineral association and exhibits low Q10 , lignin turnover is mainly regulated by temperature and has a high Q10 . Such contrasts resemble those between fast-cycling (i.e., light) and mineral-associated slow-cycling fractions from globally distributed soils. Collectively, our results suggest that warming may greatly accelerate the decomposition of lignin, especially in soils with relatively weak mineral associations.

Ultra-Confined Catalytic Growth Integration of Sub-10 nm 3D Stacked Silicon Nanowires Via a Self-Delimited Droplet Formation Strategy.

Fabricating ultrathin silicon (Si) channels down to critical dimension (CD) <10 nm, a key capability to implementing cutting-edge microelectronics and quantum charge-qubits, has never been accomplished via an extremely low-cost catalytic growth. In this work, 3D stacked ultrathin Si nanowires (SiNWs) are demonstrated, with width and height of Wnw  = 9.9 ± 1.2 nm (down to 8 nm) and Hnw  = 18.8 ± 1.8 nm, that can be reliably grown into the ultrafine sidewall grooves, approaching to the CD of 10 nm technology node, thanks to a new self-delimited droplet control strategy. Interestingly, the cross-sections of the as-grown SiNW channels can also be easily tailored from fin-like to sheet-like geometries by tuning the groove profile, while a sharply folding guided growth indicates a unique capability to produce closely-packed multiple rows of stacked SiNWs, out of a single run growth, with the minimal use of catalyst metal. Prototype field effect transistors are also successfully fabricated, achieving Ion/off ratio and sub-threshold swing of >106 and 125 mV dec-1 , respectively. These results highlight the unexplored potential of versatile catalytic growth to compete with, or complement, the advanced top-down etching technology in the exploitation of monolithic 3D integration of logic-in-memory, neuromorphic and charge-qubit applications.

Highly Stretchable High-Performance Silicon Nanowire Field Effect Transistors Integrated on Elastomer Substrates.

Quasi-1D silicon nanowires (SiNWs) field effect transistors (FETs) integrated upon large-area elastomers are advantageous candidates for developing various high-performance stretchable electronics and displays. In this work, it is demonstrated that an orderly array of slim SiNW channels, with a diameter of <80 nm, can be precisely grown into desired locations via an in-plane solid-liquid-solid (IPSLS) mechanism, and reliably batch-transferred onto large area polydimethylsiloxane (PDMS) elastomers. Within an optimized discrete FETs-on-islands architecture, the SiNW-FETs can sustain large stretching strains up to 50% and repetitive testing for more than 1000 cycles (under 20% strain), while achieving a high hole carrier mobility, Ion /Ioff current ratio and subthreshold swing (SS) of ≈70 cm2 V-1 s-1 , >105  and 134 - 277 mV decade-1 , respectively, working stably in an ambient environment over 270 days without any passivation protection. These results indicate a promising new routine to batch-manufacture and integrate high-performance, scalable and stretchable SiNW-FET electronics that can work stably in harsh and large-strain environments, which is a key capability for future practical flexible display and wearable electronic applications.

Designable Integration of Silicide Nanowire Springs as Ultra-Compact and Stretchable Electronic Interconnections.

Stretchable electronics are finding widespread applications in bio-sensing, skin-mimetic electronics, and flexible displays, where high-density integration of elastic and durable interconnections is a key capability. Instead of forming a randomly crossed nanowire (NW) network, here, a large-scale and precise integration of highly conductive nickel silicide nanospring (SiNix -NS) arrays are demonstrated, which are fabricated out of an in-plane solid-liquid-solid guided growth of planar Si nanowires (SiNWs), and subsequent alloy-forming process that boosts the channel conductivity over 4 orders of magnitude (to 2 × 104 S cm-1 ). Thanks to the narrow diameter of the serpentine SiNix -NS channels, the elastic geometry engineering can be accomplished within a very short interconnection distance (down to ≈3 µm), which is crucial for integrating high-density displays or logic units in a rigid-island and elastic-interconnection configuration. Deployed over soft polydimethylsiloxane thin film substrate, the SiNix -NS array demonstrates an excellent stretchability that can sustain up to 50% stretching and for 10 000 cycles (at 15%). This approach paves the way to integrate high-density inorganic electronics and interconnections for high-performance health monitoring, displays, and on-skin electronic applications, based on the mature and rather reliable Si thin film technology.

Nanostripe-Confined Catalyst Formation for Uniform Growth of Ultrathin Silicon Nanowires.

Uniform growth of ultrathin silicon nanowire (SiNW) channels is the key to accomplishing reliable integration of various SiNW-based electronics, but remains a formidable challenge for catalytic synthesis, largely due to the lack of uniform size control of the leading metallic droplets. In this work, we explored a nanostripe-confined approach to produce highly uniform indium (In) catalyst droplets that enabled the uniform growth of an orderly SiNW array via an in-plane solid-liquid-solid (IPSLS) guided growth directed by simple step edges. It was found that the size dispersion of the In droplets could be reduced substantially from Dcatpl = 20 ± 96 nm on a planar surface to only Dcatns = 88 ± 13 nm when the width of the In nanostripe was narrowed to Wstr= 100 nm, which could be qualitatively explained in a confined diffusion and nucleation model. The improved droplet uniformity was then translated into a more uniform growth of ultrathin SiNWs, with diameter of only Dnw= 28 ± 4 nm, which has not been reported for single-edge guided IPSLS growth. These results lay a solid basis for the construction of advanced SiNW-derived field-effect transistors, sensors and display applications.

Highly Sensitive Ammonia Gas Detection at Room Temperature by Integratable Silicon Nanowire Field-Effect Sensors.

Toxic gas monitoring at room temperature (RT) is of great concern to public health and safety, where ultrathin silicon nanowires (SiNWs), with diameter <80 nm, are ideal one-dimensional candidates to achieve high-performance field-effect sensing. However, a precise integration of the tiny SiNWs as active gas sensor channels has not been possible except for the use of expensive and inefficient electron beam lithography and etching. In this work, we demonstrate an integratable fabrication of field-effect sensors based on orderly SiNW arrays, produced via step-guided in-plane solid-liquid-solid growth. The back-gated SiNW sensors can be tuned into suitable subthreshold detection regime to achieve an outstanding field-effect sensitivity (75.8% @ 100 ppm NH3), low detection limit (100 ppb), and excellent selectivity to NH3 gas at RT, with fast response/recovery time scales (Tres/Trec) of 20 s (at 100 ppb NH3) and excellent repeatability and high stability over 180 days. These outstanding sensing performances can be attributed to the fast charge transfer between adsorbed NH3 molecules and the exposed SiNW channels, indicating a convenient strategy to fabricate and deploy high-performance gas detectors that are widely needed in the booming marketplace of wearable or portable electronics.

Ab Initio Design, Shaping, and Assembly of Free-Standing Silicon Nanoprobes.

Free-standing silicon nanoprobes (SiNPs) are critical tools for intracellular bioelectrical signal recording, while a scalable fabrication of these tiny SiNPs with ab initio geometry designs has not been possible. In this work, we demonstrate a novel growth shaping of slim Si nanowires (SiNWs) into SiNPs with sharp tips (curvature radii <300 nm), tunable angles of 30°, 60°, to 120° and even programmable triangle/circular shapes. A precise growth integration of orderly single, double, and quadruple SiNPs at prescribed locations enables convenient electrode connection, transferring and mounting these tiny tips onto movable arms to serve as long-protruding (over 4-20 µm) nanoprobes. Mechanical flexibility, resilience, and field-effect sensing functionality of the SiNPs were systematically testified in liquid nanodroplet and cell environments. This highly reliable and economic manufacturing of advanced SiNPs holds a strong potential to boost and open up the market implementations of a wide range of intracellular sensing, monitoring, and editing applications.

Superfast Growth Dynamics of High-Quality Silicon Nanowires on Polymer Films via Self-Selected Laser-Droplet-Heating.

Growing high quality silicon nanowires (SiNWs) at elevated temperature on cooler polymer films seems to be contradictive but highly desirable for building high performance flexible and wearable electronics. In this work, we demonstrate a superfast (vnw > 3.5 µm·s-1) growth of high quality SiNWs on polymer/glass substrates, powered by self-selected laser at 808 nm heating of indium catalyst droplets that absorb amorphous Si layer to produce SiNWs. Because of the tiny heat capacity of the nanodroplets, the SiNW growth can be quickly heated up and frozen via rapid laser ON/OFF switching, enabling a deterministic diameter modulation in the ultralong SiNWs. Finally, prototype field effect transistors are also fabricated upon the laser-droplet-heating grown SiNWs with a high Ion/Ioff ratio of >104 and reasonable subthreshold swing of 386 mV·dec-1, opening a generic new route to integrate high-quality NW channels directly upon large area and lightweight polymer substrates for developing high-performance flexible electronics.

Photoelectric Cardiac Pacing by Flexible and Degradable Amorphous Si Radial Junction Stimulators.

Implanted pacemakers are usually bulky and rigid electronics that are constraint by limited battery lifetimes, and need to be installed and repaired via surgeries that risk secondary infection and injury. In this work, a flexible self-powered photoelectric cardiac stimulator is demonstrated based on hydrogenated amorphous Si (a-Si:H) radial p-i-n junctions (RJs), constructed upon standing Si nanowires grown directly on aluminum thin foils. The flexible RJ stimulators, with an open-circuit voltage of 0.67 V and short-circuit current density of 12.7 mA cm-2 under standard AM1.5G illumination, can be conformally attached to the uneven tissue surface to pace heart-beating under modulated 650 nm laser illumination. In vivo pacing evaluations on porcine hearts show that the heart rate can be effectively controlled by the external photoelectric stimulations, to increase from the normal rate of 101-128 beating min-1 . Importantly, the a-Si:H RJ units are highly biofriendly and biodegradable, with tunable lifetimes in phosphate-buffered saline environment controlled by surface coating and passivation, catering to the needs of short term or lasting cardiac pacing applications. This implantable a-Si:H RJ photoelectric stimulation strategy has the potential to establish eventually a self-powered, biocompatible, and conformable cardiac pacing technology for clinical therapy.

Coupled boron-doping and geometry control of tin-catalyzed silicon nanowires for high performance radial junction photovoltaics.

Geometry and doping control in silicon nanowires (SiNWs) are both crucial aspects in fabricating three-dimensional (3D) radial junction thin film solar cells, while the coupling between them remains a peculiar aspect to be better understood. In this work, we focus on the geometry evolution and the doping effects realized in tin-catalyzed SiNWs grown via a plasma-enhanced vapor-liquid-solid procedure by using different diborane (B2H6) dopant flows. It is shown that with the increase of B2H6 flow rate from 0.3 to 2.1 SCCM, the radial growth of SiNWs is greatly accelerated by more than 30%, while the length is shortened to 50%. This can be related to the enhanced chemisorption probability of SiHx radicals, with the addition of B2H6, on the SiNW sidewall during silane (SiH4) plasma deposition in PECVD system, which leads to easier nucleation directly on the sidewalls and faster radial expansion of the SiNWs. A trade-off has to be sought between seeking a strong light trapping and ensuring a sufficient doping for high-quality PIN junction with the increase of B2H6 doping flow. These new understandings lay a critical basis for understanding and searching for an optimal growth control for constructing high-performance 3D radial junction thin-film solar cells.

Electrical Potential Specified Release of BSA/Hep/Polypyrrole Composite Film and Its Cellular Responses.

A facile strategy is needed for accurate time-space supply of suitable growth factors or drugs. Polypyrrole (PPy) was able to carry almost all kinds of negatively charged biomolecules through anodizing method, which made it an appropriate way for codeposition of multiple molecules. The difference in the conjugation between different molecules and PPy makes it possible for selective release when the redox state of PPy changes. In this work, bovine serum albumin (BSA) and heparin (Hep) were chosen to be the model molecules in view of their differences in the level of electronegativity and molecular weight. Double-layer deposition method was used to improve the biocompatibility of PPy/BSA/Hep film. It was found the content of BSA and Hep in the film can be controlled by regulating deposition current and time. BSA release was facilitated under positive voltage and then promote the proliferation of preosteoblasts, while Hep release was promoted under negative voltage and enhance cell differentiation. Our work provides a dual-molecule model in PPy for selective release and further explores the mechanism of release selectivity, this discovery has potential applications in tissue engineering and regenerative medicine.

Surface hydroxylation regulates cellular osteogeneses on TiO2 and Ta2O5 nanorod films.

Titanium and tantalum have been widely used for orthopedic and dental implant applications. However, how their inherent surface features regulate cellular osteogeneses still remains elusive. In this study, we engineered two distinct TiO2 and Ta2O5 nanorod films as the two model oxidized surfaces to investigate their intrinsic osteogenic behaviors. The results indicated that the distinctive gradient on zeta potential against pH, corresponding to the deprotonation rate, but not the hydroxyl amount or hydroxylation polarity played a critical role on the cellular osteogenic performance. TiO2 nanorod film with a higher deprotonation rate significantly upregulated the expression of osteogeneses-related gene and protein, comparing to that of Ta2O5 nanorod film. These results might be attributed to that surface with higher deprotonation rateprovided more Bronsted acid-base surface sites to react with protein residues, leading to a mild change in conformation of the absorbed proteins, and subsequently facilitating to trigger the integrin-focal adhesion cytoskeleton actin transduction pathway. This study, therefore, provides a new insight into the understanding the role of material surface hydroxylation on cellular osteogenic responses.

Enhanced Repairing of Critical-Sized Calvarial Bone Defects by Mussel-Inspired Calcium Phosphate Cement.

The goal of this study is to investigate the biological response of mussel-inspired calcium phosphate cement (CPC) in vivo. Polydopamine (PDA), which is analogous to that of mussel adhesive proteins, was added in CPC. PDA-CPC was implanted into the femur, muscle, and critical-sized calvarial bone defects of rabbits. Histomorphometry of the sequential fluorescence sections showed that PDA-CPC was capable of forming more newborn bone than the control-CPC. More new bone, bone marrow cavity, and blood vessel were observed in PDA-CPC than in the control-CPC in decalcified and undecalcified histological sections. Necrosis bone was not observed in PDA-CPC, whereas it appeared in the control-CPC after 2 weeks. The histological sections in muscle witnessed that there was more ingrowth of collagen in PDA-CPC than that in the control-CPC. There were no significantly difference in the number of leukocyte between PDA-CPC and the control-CPC in blood. It was confirmed that the addition of PDA enhanced the bone repairing ability and biocompatibility of PDA-CPC. Push-out testing indicated that PDA increased the bonding strength between PDA-CPC and host bone in the early stage. These present results indicated that PDA-CPC might be one potential bone graft with gratifying biocompatibility and enhanced bone repairing.

Charge injection based electrical stimulation on polypyrrole planar electrodes to regulate cellular osteogenic differentiation.

In this study, polypyrrole (Ppy) electrodes were prepared to support an electrical stimulation to MC3T3-E1 cells for regulating their osteogenic differentiation. The charge injection capacity (C Q) of the Ppy electrodes could be adjusted by the Ppy thickness, and a higher C Q could make the electrode able to produce a higher charge injection quantity (Q inj) at applied voltage. The Q inj onto electrode could be considered as the intensity of the stimulation pulse to cells, and the pulse frequency means the number of electric stimulation with Q inj at one second. Hence, we conducted the present work in the view of Q inj. When the cells were electrically stimulated for 1 hour per day, the electrodes with Q inj ranged in 0.08-0.15 µQ had an obvious role in enhancing cellular osteogenic differentiation whereas Q inj of lower than 0.03 µQ or more than 0.30 µQ gave the stimulations with no or negative effects. And the stimulation with 1 or 25 Hz showed to enhance the differentiation, whereas the stimulation with 50 Hz gave an inhibiting effect. We further found the osteogenic differentiation potential triggered by electrical simulation was related to cell growth stage, and the stimulation carried out at early stage (day 2-5) during 8 days cell culture showed more contribution to enhancing osteogenic differentiation than that at later stage (day 6-8). It is proposed that the desired stimulation effects require that an appropriate voltage-gated calcium ion channel and efficient intracellular calcium ion oscillation are well activated. This work therefore reveals Q inj as an important electrode parameter to decide effective simulations and provides an insight into understanding of the role of electrode material characters in regulating cellular osteogenic differentiation during stimulation.