Mechanistic formulation of inorganic membranes at the air-liquid interface.

Freestanding functional inorganic membranes, beyond the limits of their organic and polymeric counterparts1, may unlock the potentials of advanced separation2, catalysis3, sensors4,5, memories6, optical filtering7 and ionic conductors8,9. However, the brittle nature of most inorganic materials, and the lack of surface unsaturated linkages10, mean that it is difficult to form continuous membranes through conventional top-down mouldings and/or bottom-up syntheses11. Up to now, only a few specific inorganic membranes have been fabricated from predeposited films by selective removal of sacrificial substrates4-6,8,9. Here we demonstrate a strategy to switch nucleation preferences in aqueous systems of inorganic precursors, resulting in the formation of various ultrathin inorganic membranes at the air-liquid interface. Mechanistic study shows that membrane growth depends on the kinematic evolution of floating building blocks, which helps to derive the phase diagram based on geometrical connectivity. This insight provides general synthetic guidance towards any unexplored membranes, as well as the principle of tuning membrane thickness and through-hole parameters. Beyond understanding  a complex dynamic system, this study comprehensively expands the traditional notion of membranes in terms of composition, structure and functionality.

Decomposing and analyzing contact resonance frequency in contact mode voltage modulated scanning probe microscopies.

Contact mode voltage modulated scanning probe microscopy (SPM) techniques, such as switching spectroscopy piezoresponse force microscopy (SS-PFM), are powerful tools for detecting local electromechanical behaviors. However, interpreting their signals, especially the contact resonance frequency (f0), is difficult due to the complexity of the tip-sample contact and the signal tracking system. In a previous study, an interesting phenomenon on the variation of f0 was observed, showing distinctions between ferroelectric and non-ferroelectric materials. Therefore, it is believed that f0 conveys important information about the tip-sample contact which is real-timely affected by charge accumulation or polarization switching. In this study, principal component analysis (PCA) and correlation analysis are applied to decompose the signal of f0. The first and second principal components successfully restore most information of the original data, and they describe different features which are related to the surface morphology and electromechanical behavior, respectively. In addition, a customized method based on the PCA and correlation analysis of f0 can well distinguish the responses from different materials of which the amplitude and phase signals show "ferroelectric like" phenomena during the SS-PFM measurements.

Abnormal Ionic Conductivities in Halide NaBi3 O4 Cl2 Induced by Absorbing Water and a Derived Oxhydryl Group.

In hunting for safe and cost-effective materials for post-Li-ion energy storage, the design and synthesis of high-performance solid electrolytes (SEs) for all-solid-state batteries are bottlenecks. Many issues associated with chemical stability during processing and storage and use of the SEs in ambient conditions need to be addressed. Now, the effect of water as well as oxyhdryl group (. OH) on NaBi3 O4 Cl2 are investigated by evaluating ionic conductivity. The presence of water and . OH results in an increase in ionic conductivity of NaBi3 O4 Cl2 owing to diffusion of H2 O into NaBi3 O4 Cl2 , partially forming binding . OH through oxygen vacancy repairing. Ab initio calculations reveal that the electrons significantly accumulate around . OH and induce a more negative charge center, which can promote Na+ hopping. This finding is fundamental for understanding the essential role of H2 O in halide-based SEs and provides possible roles in designing water-insensitive SEs through control of defects.

Optically Governed Dynamic Surface Charge Redistribution of Hybrid Plasmo-Pyroelectric Nanosystems.

Though plasmonic effect is making some headway in the energy harvesting realm, its fundamental charge transfer mechanism to a large extent is attributed to the hot-carrier generation at the contact interface. Herein this work attempts to elucidate the physical origin of light induced plasmo-pyroelectric enhancement based on charge density manipulation on surface state in the vicinity of the metal-ferroelectric contact interface. More importantly, by tuning the band bending, it is shown that the charge density on the surface state of a hybrid plasmo-pyroelectric (BaTiO3 -Ag) nanosystem can be manipulated and largely increased under the resonant blue light illumination (363 nm). It is also demonstrated that owing to this effect, the spatial pyroelectric activity of a hybrid plasmo-pyroelectric nanosystem governs 46% enhancement in pyroelectric coefficient. This research highlights the optically regulated charge density in plasmo-pyroelectric nanosystems, which could pave a new avenue for energy harvesting/conversion devices with distinguished advantages in wireless, photonic-controlled, localized, and dynamic stimulation.

Spatially Probed Plasmonic Photothermic Nanoheater Enhanced Hybrid Polymeric-Metallic PVDF-Ag Nanogenerator.

Surface plasmon-based photonics offers exciting opportunities to enable fine control of the site, span, and extent of mechanical harvesting. However, the interaction between plasmonic photothermic and piezoresponse still remains underexplored. Here, spatially localized and controllable piezoresponse of a hybrid self-polarized polymeric-metallic system that correlates to plasmonic light-to-heat modulation of the local strain is demonstrated. The piezoresponse is associated to the localized plasmons that serve as efficient nanoheaters leading to self-regulated strain via thermal expansion of the electroactive polymer. Moreover, the finite-difference time-domain simulation and linear thermal model also deduce the local strain to the surface plasmon heat absorption. The distinct plasmonic photothermic-piezoelectric phenomenon mediates not only localized external stimulus light response but also enhances dynamic piezoelectric energy harvesting. The present work highlights a promising surface plasmon coordinated piezoelectric response which underpins energy localization and transfer for diversified design of unique photothermic-piezotronic technology.

Substrate-Friendly Growth of Large-Sized Ni(OH)2 Nanosheets for Flexible Electrochromic Films.

Large-area, 2D, anisotropic, direct growth of nanostructures is considered an effective and straightforward way to readily fulfill transparent, flexible technology requirements. In addition, formation of thin hybrid structures by combining with another 2D material brings about dimensional advantages, such as intimate heterostructure functionalities, large specific area, and optical transparency. Here, we demonstrate 2D planar growth of thin Ni(OH)2 nanosheets on arbitrary rigid and soft supports, by exploiting the growth strategies of oriented attachment induced by interfacial chemistry and the intrinsic driving force of layered structure constitution. Moreover, large-scale 2D heterohybrids have successfully been prepared by direct conformal growth of Ni(OH)2 nanosheets overlying MoO3 nanobelts. Unlike the exfoliation and transfer of 2D materials technique, this approach minimizes multiple process contamination and physical-handling structural defects. Accordingly, proof-of-concept flexible electrochromism is demonstrated in view of its prerequisite to the access of a large homogeneous material coating. The as-synthesized 2D layered structure affirms its optical and electrochemical superiority through the display of wide optical modulation, high coloration efficiency, good cyclic stability, and flexibility.

Sepsis Reduces Bone Strength Before Morphologic Changes Are Identifiable.

OBJECTIVES: Survivors of critical illness have an increased prevalence of bone fractures. However, early changes in bone strength, and their relationship to structural changes, have not been described. We aimed to characterize early changes in bone functional properties in critical illness and their relationship to changes in bone structure, using a sepsis rodent model. DESIGN: Experimental study. SETTING: Animal research laboratory. SUBJECTS: Adult Sprague-Dawley rats. INTERVENTIONS: Forty Sprague-Dawley rats were randomized to cecal ligation and puncture or sham surgery. Twenty rodents (10 cecal ligation and puncture, 10 sham) were killed at 24 hours, and 20 more at 96 hours. MEASUREMENTS AND MAIN RESULTS: Femoral bones were harvested for strength testing, microCT imaging, histologic analysis, and multifrequency scanning probe microscopy. Fracture loads at the femoral neck were significantly reduced for cecal ligation and puncture-exposed rodents at 24 hours (83.39 ± 10.1 vs 103.1 ± 17.6 N; p = 0.014) and 96 hours (81.60 ± 14.2 vs 95.66 ± 14.3 N; p = 0.047). Using multifrequency scanning probe microscopy, collagen elastic modulus was lower in cecal ligation and puncture-exposed rats at 24 hours (1.37 ± 0.2 vs 6.13 ± 0.3 GPa; p = 0.001) and 96 hours (5.57 ± 0.5 vs 6.13 ± 0.3 GPa; p = 0.006). Bone mineral elastic modulus was similar at 24 hours but reduced in cecal ligation and puncture-exposed rodents at 96 hours (75.34 ± 13.2 vs 134.4 ± 8.2 GPa; p < 0.001). There were no bone architectural or bone mineral density differences by microCT. Similarly, histologic analysis demonstrated no difference in collagen and elastin staining, and C-X-C chemokine receptor type 4, nuclear factor kappa beta, and tartrate-resistant acid phosphatase immunostaining. CONCLUSIONS: In a rodent sepsis model, trabecular bone strength is functionally reduced within 24 hours and is associated with a reduction in collagen and mineral elastic modulus. This is likely to be the result of altered biomechanical properties, rather than increased bone mineral turnover. These data offer both mechanistic insights and may potentially guide development of therapeutic interventions.

Probing electrochemically induced resistive switching of TiO2 using SPM techniques.

Resistive switching on the nanoscale is an emerging research field and Scanning Probe Microscopy (SPM) is a powerful tool for studies in this area. Under the SPM tip, the electrical field is very high due to the small tip radius on the order of tens of nanometers, and this can enable a range of ionic/electrochemical phenomena during the resistive switching of the materials under the SPM tip. Although the ionic/electrochemical phenomena have long been considered vital for the resistive switching of materials, a few pieces of experimental evidence, as well as the decoupling of the effects of the electrochemical processes at different stages, are still needed. In this work, we applied SPM based techniques to study resistive switching as well as the electrochemical phenomena during the resistive switching of the TiO2 thin films prepared using Pulse Laser Deposition (PLD). It was found that the reversible or irreversible electrochemical processes initiated at different voltages can promote or degrade the resistive switching behavior of TiO2. Combined with an electrical cell with environmental control, these electrochemical processes have been shown to require the involvement of moisture; the accumulation of oxygen vacancies, protons, and hydroxyls at the tip/TiO2 junction may contribute to the promoting effect of the reversible electrochemical process on resistive switching, while the oxygen vacancy ordering and the injection of protons and hydroxyls into the lattice may lead to the irreversible electrochemical process. This work provides a detailed insight into the characteristics, origins, and the effects of the electrochemical phenomena on resistive switching performance, and will provide a further understanding of the electrochemical phenomena in various functional materials.

Ultrathin BaTiO3-based ferroelectric tunnel junctions through interface engineering.

The ability to change states using voltage in ferroelectric tunnel junctions (FTJs) offers a route for lowering the switching energy of memories. Enhanced tunneling electroresistance in FTJ can be achieved by asymmetric electrodes or introducing metal-insulator transition interlayers. However, a fundamental understanding of the role of each interface in a FTJ is lacking and compatibility with integrated circuits has not been explored adequately. Here, we report an incisive study of FTJ performance with varying asymmetry of the electrode/ferroelectric interfaces. Surprisingly high TER (∼400%) can be achieved at BaTiO3 layer thicknesses down to two unit cells (∼0.8 nm). Further our results prove that band offsets at each interface in the FTJs control the TER ratio. It is found that the off state resistance (R(Off)) increases much more rapidly with the number of interfaces compared to the on state resistance (ROn). These results are promising for future low energy memories.

Voltage induced electrochemical reactions in the single lithium-rich layer-oxide nanoparticles.

As a crucial building block of the electrode in the lithium-ion battery (LIB), single nanoparticles that respond to an electric field have rarely been characterized experimentally. It is important to study the intrinsic properties of nanoparticles independently, excluding the effects from binders and additives. In this paper, isolated Li-rich layer-oxide (Li1.2Mn0.54Ni0.13Co0.13O2) nanoparticles are studied in comparison with individual Li2MnO3 and LiNi1/3Co1/3Mn1/3O2 nanoparticles. The bias triggered changes in morphology and material properties are characterized using dual-frequency scanning probe microscopy (SPM) techniques in ambient air, synthetic air, and an argon atmosphere. Inhomogeneous stiffness/composition is observed on single nanoparticles. The change in local Li(+)-ion concentration may contribute to the stiffness variation. Bias induced Li(+)-ion redistributions and electrochemical reactions are observed. Nanoparticles are fragmented at high voltage (>5 V) when an excessive amount of Li-ions are removed. This work further demonstrates the application of multi-frequency SPM techniques for the characterization of nanoparticles for energy storage applications.

In situ studies of lithium-ion diffusion in a lithium-rich thin film cathode by scanning probe microscopy techniques.

This paper presents in situ characterization of lithium-ion diffusion at nano- to micro-meter scales in a Li-rich layered oxide thin film cathode under external bias by using Electrochemical Strain Microscopy (ESM) and Atomic Force Microscopy (AFM) techniques. The local variations of the diffusion coefficient are calculated and visualized from the ESM images. The results indicate that the Li-ion movement is closely correlated with the changes in the surface topography when the Li-rich cathode is subjected to an external bias. Furthermore, bias-induced Li-ion redistribution is partially reversible. Topography evolution due to Li-ion diffusion and relaxation behaviour are observed. The results from this in situ study provide the insight into the Li-ion diffusion mechanism in the cathode material and pave the way for studying the details of the diffusion-related phenomenon in Li-ion battery materials.

Hydrated Calcium Vanadate Nanoribbons with a Stable Structure and Fast Ion Diffusion as a Cathode for Quasi-Solid-State Zinc-Ion Batteries.

We demonstrated the use of hydrated calcium vanadate (CaV6O16·3H2O, denoted as CaVO-2) as a cathode for aqueous zinc-ion batteries (AZIBs). Nanoribbons of hydrated calcium vanadate facilitated shortening of the Zn2+ transport distance and accelerated zinc-ion insertion. The introduction of interlayer structure water increased the interlayer spacing of calcium vanadate and as a "lubricant". Ca2+ insertion also expanded the interlayer spacing and further stabilized the interlayer structure of vanadium-based oxide. The density functional theory results showed that the introduction of Ca2+ and structured water could effectively improve the diffusion kinetics, resulting in the rapid transport of zinc ions. As a result, AZIBs based on the CaVO-2 cathode offered high specific capacity (329.6 mAh g-1 at 200 mA g-1) and fast charge/discharge capability (147 mAh g-1 at 10 A g-1). Impressively, quasi-solid-state zinc-ion batteries based on the CaVO-2 cathode and polyacrylamide-cellulose nanofiber hydrogel electrolytes maintained an outstanding specific capacity and long cycle life (162 mAh g-1 over 10 000 cycles at 5 A g-1). This study provided a reliable strategy for metal-ion insertion and the structural water introduction of oxides to produce a high-quality cathode for ZIBs. Meanwhile, it provides ideas for the combination of vanadium-based materials and gel electrolytes to construct solid-state zinc-ion batteries.

Optical Modulation of MoTe2/Ferroelectric Heterostructure via Interface Doping.

Optical modulation through interface doping offers a convenient and efficient way to control ferroelectric polarization, thereby advancing the utilization of ferroelectric heterostructures in nanoelectronic and optoelectronic devices. In this work, we fabricated heterostructures of MoTe2/BaTiO3/La0.7Sr0.3MnO3 (MoTe2/BTO/LSMO) and demonstrated opposite ultraviolet (UV) light-induced polarization switching behaviors depending on the varied thicknesses of MoTe2. The thickness-dependent band structure of MoTe2 film results in interface doping with opposite polarity in the respective heterostructures. The polarization field of BTO interacts with the interface charges, and an enhanced effective built-in field (Ebi) can trigger the transfer of massive UV light-induced carriers in both MoTe2 and BTO films. As a result, the interplay among the contact field of MoTe2/BTO, the polarization field, and the optically excited carriers determines the UV light-induced polarization switching behavior of the heterostructures. In addition, the electric transport characteristics of MoTe2/BTO/LSMO heterostructures reveal the interface barrier height and Ebi under opposite polarization states, as well as the presence of inherent in-gap trap states in MoTe2 and BTO films. These findings represent a further step toward achieving multifield modulation of the ferroelectric polarization and promote the potential applications in optoelectronic, logic, memory, and synaptic ferroelectric devices.

Efficient filter-in-centrifuge separation of low-concentration bacteria from blood.

Separating bacteria from infected blood is an important step in preparing samples for downstream bacteria detection and analysis. However, the extremely low bacteria concentration and extremely high blood cell count make efficient separation challenging. In this study, we introduce a method for separating bacteria from blood in a single centrifugation step, which involves sedimentation velocity-based differentiation followed by size-based cross-flow filtration over an inclined filter. Starting from 1 mL spiked whole blood, we recovered 32 ± 4% of the bacteria (Escherichia coli, Klebsiella pneumonia, or Staphylococcus aureus) within one hour while removing 99.4 ± 0.1% of the red blood cells, 98.4 ± 1.4% of the white blood cells, and 90.0 ± 2.6% of the platelets. Changing the device material could further increase bacteria recovery to >50%. We demonstrated bacterial recovery from blood spiked with 10 CFU mL-1. Our simple hands-off efficient separation of low-abundant bacteria approaches clinical expectations, making the new method a promising candidate for future clinical use.

Nano-hierarchical structure and electromechanical coupling properties of clamshell.

Electromechanical coupling is a nearly universal property of biomaterials, and may play an important role in many physiological and functional phenomena. The intrinsic or externally-generated electric field within biomaterials may also contribute to their predominant mechanical properties. Mollusc shells are well known for their outstanding mechanical properties, which are generally believed to originate from their hierarchical structures in multi-levels. This paper is therefore focused on the studies of the hierarchical structures and electromechanical coupling behaviors of clamshell from micro- to nano-levels, and in particular, the biopolymer concentrated regions. Detailed studies are performed to characterize the piezoelectric and ferroelectric properties of clamshell. It was found that the piezoresponse of clamshell is originated from the biopolymers between the mineral grains, as well as those intercalated within the mineral crystalline structure after the biomineralization process. Local ferroelectric hysteresis loops of clamshell have also been observed and analyzed on the samples with different orientations, biopolymer contents, or moisture contents. It is believed that the overall functioning of the clamshell or even other mollusc shells may incorporate many mechanisms interacting together, rather than originate from the hierarchical structure alone. This study of the electromechanical coupling effects of clamshell can be a path to have more comprehensive understandings of the properties and behaviors of mollusc shells.

Ferroelectric Engineered Electrode-Composite Polymer Electrolyte Interfaces for All-Solid-State Sodium Metal Battery.

To enhance the compatibility between the polymer-based electrolytes and electrodes, and promote the interfacial ion conduction, a novel approach to engineer the interfaces between all-solid-state composite polymer electrolyte and electrodes using thin layers of ferroelectrics is introduced. The well-designed and ferroelectric-engineered composite polymer electrolyte demonstrates an attractive ionic conductivity of 7.9 × 10-5 S cm-1 at room temperature. Furthermore, the ferroelectric engineering is able to effectively suppress the growth of solid electrolyte interphase (SEI) at the interface between polymer electrolytes and Na metal electrodes, and it can also enhance the ion diffusion across the electrolyte-ferroelectric-cathode/anode interfaces. Notably, an extraordinarily high discharge capacity of 160.3 mAh g-1 , with 97.4% in retention, is achieved in the ferroelectric-engineered all-solid-state Na metal cell after 165 cycles at room temperature. Moreover, outstanding stability is demonstrated that a high discharge capacity retention of 86.0% is achieved over 180 full charge/discharge cycles, even though the cell has been aged for 2 months. This work provides new insights in enhancing the long-cyclability and stability of solid-state rechargeable batteries.

Humidity Effects on Domain Structure and Polarization Switching of Pb(Zn1/3Nb2/3)O3-x%PbTiO3 (PZN-x%PT) Single Crystals.

The effect of relative humidity on the domain structure imaging and polarization switching process of Pb(Zn1/3Nb2/3)O3-x%PbTiO3 (PZN-x%PT) ferroelectric single crystals has been investigated by means of the piezoresponse force microscopy (PFM) and piezoresponse force spectroscopy (PFS) techniques. It was found that the PFM amplitude increases with the relative humidity, and that the ferroelectric hysteresis loops at different relative humidity levels show that the coercive bias decreases with the increase in relative humidity. These observed phenomena are attributed to the existence of the water layer between the probe tip and the sample surface in a humid atmosphere, which could affect the effect of the electric field distribution and screening properties at the ferroelectric sample surface. These results provide a better understanding of the water adsorption phenomena at the nanoscale in regard to the fundamental understanding of ferroelectrics' properties.

Temperature-Induced Phase Transition Characteristics of [001]-Oriented 0.93Pb(Zn1/3Nb2/3)O3-0.07PbTiO3 (PZN-7%PT) Single Crystal by Using Piezoresponse Force Microscopy.

The evolution of the domain structures of [001]-oriented relaxor ferroelectric 0.93PbZn1/3Nb2/3O3-0.07PbTiO3 (PZN-7%PT) single crystals as a function of temperature was investigated in situ by using piezoresponse force microscopy (PFM). It was found that the local domain structure of PZN-7%PT single crystals at room temperature is rhombohedral with nanoscale twins. Temperature-dependent domain structures showed that the phase transition process is a collective process and that the sample underwent a sequence of rhombohedral (R) → monoclinic (Mc) → tetragonal (T) → cubic (C) phase transformations when the temperature increased from 25 °C to 170 °C. The results provide direct observation of the phase transition evolution of PZN-7%PT single crystals as a function of temperature, which is of great significance to fully understand the relationships between the domain structure and phase structure of PZN-7%PT single crystals.

Response and Implication of NASICON Solid-State Electrolytes to Local Electrical Stimulation: From Surface Engineering to Interfacial Manipulation.

The surface feature of solid electrolytes fundamentally governs their own physical properties and significantly affects the interaction with the electrode materials. The evaluation of interfacial contact between the electrolyte and the metallic anode is largely relied on the macroscopic contact angle measurement, which is influenced by the intrinsic wettability and the microstructure of the electrolyte. In this work, the surface chemistry of the solid electrolyte is first regulated via facile thermal treatments. Then, scanning probe microscopy (SPM)-based techniques are comprehensively adopted to study the interaction between the electrolyte and metallic anode at the nanoscale. By manipulating the overpotential applied on the SPM tip, the mobile sodium ions at the subsurface of the solid electrolyte can be extracted toward the surface, and the eventual topography of the products is deliberately correlated with the sodium wettability. In this context, the impact of surface treatment on the sodium wettability of the surface layer is systematically evaluated based on the topographic evolution at the nanoscale. Furthermore, the local electrochemical reaction dynamics is revealed by correlating the surface ionic activity and current-voltage (I-V) curves. This work presents a new methodology to effectively evaluate the sodium wettability of the solid electrolyte, and these findings can provide meaningful implications to the surface engineering of ceramic electrolytes for high-performance solid-state batteries.

Nanoscale Ferroelectric Characterization with Heterodyne Megasonic Piezoresponse Force Microscopy.

Piezoresponse force microscopy (PFM), as a powerful nanoscale characterization technique, has been extensively utilized to elucidate diverse underlying physics of ferroelectricity. However, intensive studies of conventional PFM have revealed a growing number of concerns and limitations which are largely challenging its validity and applications. In this study, an advanced PFM technique is reported, namely heterodyne megasonic piezoresponse force microscopy (HM-PFM), which uses 106 to 108 Hz high-frequency excitation and heterodyne method to measure the piezoelectric strain at nanoscale. It is found that HM-PFM can unambiguously provide standard ferroelectric domain and hysteresis loop measurements, and an effective domain characterization with excitation frequency up to ≈110 MHz is demonstrated. Most importantly, owing to the high-frequency and heterodyne scheme, the contributions from both electrostatic force and electrochemical strain can be significantly minimized in HM-PFM. Furthermore, a special measurement of difference-frequency piezoresponse frequency spectrum (DFPFS) is developed on HM-PFM and a distinct DFPFS characteristic is observed on the materials with piezoelectricity. By performing DFPFS measurement, a truly existed but very weak electromechanical coupling in CH3NH3PbI3 perovskite is revealed. It is believed that HM-PFM can be an excellent candidate for the ferroelectric or piezoelectric studies where conventional PFM results are highly controversial.