Scalable Production of Highly Conductive 2D NbSe2 Monolayers with Superior Electromagnetic Interference Shielding Performance.

Thin, flexible, and electrically conductive films are in demand for electromagnetic interference (EMI) shielding. Two-dimensional NbSe2 monolayers have an electrical conductivity comparable to those of metals (106-107 S m-1) but are challenging for high-quality and scalable production. Here, we show that electrochemical exfoliation of flake NbSe2 powder produces monolayers on a large scale (tens of grams), at a high yield (>75%, monolayer), and with a large average lateral size (>20 µm). The as-exfoliated NbSe2 monolayer flakes are easily dispersed in diverse organic solvents and solution-processed into various macroscopic structures (e.g., free-standing films, coatings, patterns, etc.). Thermal annealing of the free-standing NbSe2 films reduces the interlayer distance of restacked NbSe2 from 1.18 to 0.65 nm and consequently enhances the electrical conductivity to 1.16 × 106 S m-1, which is superior to those of MXenes and reduced graphene oxide. The optimized NbSe2 film shows an EMI shielding effectiveness (SE) of 65 dB at a thickness of 5 µm (>110 dB for a 48-µm-thick film), among the highest in materials of similar thicknesses. Moreover, a laminate of two layers of the NbSe2 film (2 µm thick) with an insulating interlayer shows a high SE of 85 dB, surpassing that of the 20-µm-thick NbSe2 film (83 dB). A two-layer theoretical model is proposed, and it agrees with the experimental EMI SE of the laminated NbSe2 films. The ability to produce NbSe2 monolayers on a tens of grams scale will enable their diverse applications beyond EMI shielding.

Dynamically Cross-Linked, Self-Healable, and Stretchable All-Hydrogel Supercapacitor with Extraordinary Energy Density and Real-Time Pressure Sensing.

Wearable electronics with flexible, integrated, and self-powered multi-functions are becoming increasingly attractive, but their basic energy storage units are challenged in simultaneously high energy density, self-healing, and real-time sensing capability. To achieve this, a fully flexible and omni-healable all-hydrogel, that is dynamically crosslinked PVA@PANI hydrogel, is rationally designed and constructed via aniline/DMSO-emulsion-templated in situ freezing-polymerization strategy. The PVA@PANI sheet, not only possesses a honeycombed porous conductive mesh configuration with superior flexibility that provides numerous channels for unimpeded ions/electron transport and maximizes the utilization efficiency of pseudocapacitive PANI, but also can conform to complicated body surface, enabling effective detection and discrimination of body movements. As a consequence, the fabricated flexible PVA@PANI sheet electrode demonstrates an unprecedented specific capacitance (936.8 F g-1 ) and the assembled symmetric flexible all-solid-state supercapacitor delivers an extraordinary energy density of 40.98 Wh kg-1 , outperforming the previously highest-reported values of stretchable PVA@PANI hydrogel-based supercapacitors. What is more, such a flexible supercapacitor electrode enables precisely monitoring the full-range human activities in real-time, and fulfilling a quick response and excellent self-recovery. These outstanding flexible sensing and energy storage performances render this emerging PVA@PANI hydrogel highly promising for the next-generation wearable self-powered sensing electronics.

Self-sacrifice-template epitaxial growth of hierarchical MnO2@NiCo2O4 heterojunction electrode for high-performance asymmetric supercapacitor.

Constructing three-dimensional (3D) hierarchical bimetallic pseudocapacitive materials with abundant opening channel and heterojunction structures is rather promising but still challenging for high-performance supercapacitors. Herein, a self-sacrifice-template epitaxial growth strategy was proposed for the first time to construct 3D hierarchical bimetallic pseudocapacitive material. By using this strategy, NiCo2O4 nanowires (NiCo2O4NW) arrayed randomly to form a porous shell via in-situ epitaxial growth fully enclosing a MnO2 tube core, forming multiple transport channels and nano-heterojunctions between MnO2 and NiCo2O4NW, which facilitates electron transfer, i.e. exhibiting high electronic conductivity than any single component. As a result of the self-sacrifice-template epitaxial growth method, special hollow tectorum-like 3D hierarchical structure with considerable inter-nanowire space and hollow interior space enables easy access of electrolyte to NiCo2O4NW surface and MnO2 core, thereby resulting in highly exposed redox active sites of MnO2 core and NiCo2O4NW shell for energy storage. Comprehensive evaluations confirmed MnO2@NiCo2O4NW was a supercapacitor electrode candidate, delivering a superior energy density of 106.37 Wh kg-1. Such performance can be ascribed to the synergistic coupling effect of 3D hierarchical tube and nano-heterojunction structures. The proposed self-sacrifice-template epitaxial growth strategy provides important guidance for designing high-performance energy storage materials.

Coexistence of ferroelectricity and ferromagnetism in hex-GeS nanowires.

The existence of one-dimensional (1D) ferroelectricity and ferromagnetism provides an opportunity to expand the field of research in low-dimensional magnetoelectric and multiferroics and explore the future development of high-performance nanometer devices. Here, we predict a novel 1D ferroelectric hex-GeS nanowire with coexisting ferromagnetism. The electric polarization comes from the atomic displacements between Ge and S atoms, and it exhibits a far-higher than room temperature ferroelectric Curie temperature TEc = 830 K. The ferromagnetism, stemming from the Stoner instability, can be tuned by hole doping and maintained over a wide range of hole concentrations. Additionally, an indirect-direct-indirect band gap transition can be achieved via strain engineering and the bonding nature of the near-band-edge electronic orbitals revealed this transition mechanism. These results offer a platform to investigate 1D ferroelectric and ferromagnetic systems, and the presented hex-GeS nanowire demonstrates the potential for high-performance electronic and spintronic applications.

Mesoporous Amorphous Bulk Material Electrodes for Ultrahigh Volumetric Capacity Electrochemical Capacitors.

Retaining satisfactory electrochemical performances under high-mass electrode-active-matter loadings is important for energy storage. However, the performance decreases with increasing mass loadings due to a reduction in the ion/electron transport. In this study, a novel mesoporous amorphous bulk (MAB) material strategy is proposed. Co-based hydroxide KCo1.3 (OH)3.6 is directly electro-deposited on the Ni foam for cathode. Comprehensive structural characterizations confirm the mesoporous, amorphous, and bulk features for KCo1.3 (OH)3.6 . The fabricated whole MAB-KCo1.3 (OH)3.6 @Ni electrode exhibits an ultrahigh full volumetric capacity (123.7 mAh cm-3 ) with high KCo1.3 (OH)3.6 mass loading (11.7 mg cm-2 ) and excellent cycling stability. Along with the MAB-KCo1.3 (OH)3.6 , the mesoporous amorphous features enable fast ion diffusion and provide sufficient electroactive sites for redox reactions. In addition, the bulk nature not only facilitates the electron mobility but also guarantees structural and chemical stability. Therefore, the proposed MAB strategy and explored KCo1.3 (OH)3.6 material demonstrate considerable prospects for designing electrode materials and practical applications.

Hole-Pinned Defect Clusters for a Large Dielectric Constant up to GHz in Zinc and Niobium Codoped Rutile SnO2.

High permittivity materials for a gigahertz (GHz) communication technology have been actively sought for some time. Unfortunately, in most materials, the dielectric constant starts to drop as frequencies increase through the megahertz (MHz) range. In this work, we report a large dielectric constant of ∼800 observed in defect-mediated rutile SnO2 ceramics, which is nearly frequency and temperature independent over the frequency range of 1 mHz to 35 GHz and temperature range of 50-450 K. Experimental and theoretical investigations demonstrate that the origin of the high dielectric constant can be attributed to the formation of locally well-defined Zn2+-Nb4+ defect clusters, which create hole-pinned defect dipoles. We believe that this work provides a promising strategy to advance dipole polarization theory and opens up a direction for the design and development of high frequency, broadband dielectric materials for use in future communication technology.

A low-temperature solution-processed indium incorporated zinc oxide electron transport layer for high-efficiency lead sulfide colloidal quantum dot solar cells.

Colloidal quantum dot solar cells (CQDSCs) have achieved remarkable progress recently in terms of mainly surface passivation and composition-matching matrices on CQDs, while improving the overall photoelectric conversion efficiency (PCE) through electron transport layer (ETL) modifications is less explored. We report a low-temperature solution route to synthesize donor (Al3+/Ga3+/In3+) incorporated zinc oxide (AZO/GZO/IZO) ETL films for PbS CQDSCs. Spectroscopic characterization studies indicate that the IZO ETL fabricated with 150 °C annealing can increase the bandgap the most from 3.56 eV to 3.74 eV, possesses enhanced light transmission (∼94%) and finer particle sizes, and importantly shows the most suitable band alignment and charge transfer ability. Well-dispersed PbS CQDs of around 3 nm are synthesized by a N2-protected reflux method and are surface exchanged with 1-ethyl-3-methylimidazolium iodide (EMII) to allow I- grafting and ethanedithiol (EDT) for the active layer and hole transport layer, respectively. The IZO based PbS CQDSC, with a device architecture of ITO/IZO/PbS-EMII/PbS-EDT/Au, shows an enhanced PCE of 11.1% (comparatively 18% higher than that of the ZnO ETL), a VOC value of 0.64 V, and a JSC of 25.8 mA cm-2. The improved performances benefit from the higher recombination resistance and constrained photoluminescence emission with the utilization of the IZO ETL that provides a superior charge transfer property.

Lattice Defect Engineering Enables Performance-Enhanced MoS2 Photodetection through a Paraelectric BaTiO3 Dielectric.

Carrier mobility and density are intrinsically important in nanophoto/electronic devices. High-dielectric-constant coupled polarization-field gate ferroelectrics are frequently studied and partially capable in achieving large-scale tuning of photoresponse, but their light absorption and carrier density seem generally ineffective. This raises questions about whether a similarly high-dielectric-constant paraelectric gate dielectric could enable tuning and how the principles involved could be established. In this study, by deliberately introducing lattice defects in high-dielectric-constant paraelectric, cubic BaTiO3 (c-BTO) was explored to fabricate MoS2 photodetectors with ultrahigh detection ability and outstanding field-effect traits. An organic-metal-based spin-coating cum annealing method was used for the c-BTO synthesis, with an optimized thickness (300 nm), by introducing lattice defects properly but maintaining a large dielectric constant (55 at 1k Hz) and low dielectric loss (0.06 at 1k Hz), which renders the enhanced visible-light region absorption. As a result of the synergistically enhanced mobility and photoabsorption, the MoS2/BTO FET exhibits promising merits, for example, on/off ratio, subthreshold swing, and mobilities for high-performance photodetectors with excellent responsivity (600 AW-1) and detectivity (1.25 × 1012 Jones). Thus, this work facilitates the establishment of a lattice defect induced sub-bandgap absorption landmap for synergistically enhanced photoresponse for high-performance photodetector exploration.

Influence of Cu on the Improvement of Magnetic Properties and Structure of L10 FePt Nanoparticles.

L10 ordered FePt and FePtCu nanoparticles (NPs) with a good dispersion were successfully fabricated by a simple, green, one-step solid-phase reduction method. Fe (acac)3, Pt (acac)2, and CuO as the precursors were dispersed in NaCl and annealed at different temperatures with an H2-containing atmosphere. As the annealing temperature increased, the chemical order parameter (S), average particle size (D), coercivity (Hc), and saturation magnetization (Ms) of FePt and FePtCu NPs increased and the size distribution range of the particles became wider. The ordered degree, D, Hc, and Ms of FePt NPs were greatly improved by adding 5% Cu. The highest S, D, Hc, and Ms were obtained when FePtCu NPs annealed at 750 °C, which were 0.91, 4.87 nm, 12,200 Oe, and 23.38 emu/g, respectively. The structure and magnetic properties of FePt and FePtCu NPs at different annealing temperatures were investigated and the formation mechanism of FePt and FePtCu NPs were discussed in detail.

Controllable synthesis of in situ grown titanate hierarchical microspheres and subsequent chemical modifications for superhydrophobic and oil-water separation properties.

Sodium titanate nanowire-assembled microspheres on titanium mesh have been synthesized through controlling an over the surface acidification and hydrothermal process in terms of a proposed in situ "nucleation-cum-growth" solution chemistry strategy. These directly grown microspheres crystallize in an orthorhombic lepidocrocite layered structure of sodium titanate with the composition of Na1.8Ti1.95□0.05O4.8 (□ ∼ vacancy) determined by the XRD, Raman and SEM-EDX techniques. An individual microsphere has a uniform size of around 10 microns while the constituent nanowires have a diameter of 100 nm growing along the [110] orientation. Owing to the specially well-defined hierarchical structure and robust in situ interfaces, these titanate nanowire-assembled microspheres, after 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (OFP) surface modification, could achieve superhydrophobicity. This work demonstrates an in situ "nucleation-cum-growth" synthesis strategy and facile functionalization towards superhydrophobicity for oil-water separation, which might extend to a broad variety of oxide nanowire systems to fabricate well-defined structures for wettability tailoring and multi-functional applications.

Nanoscale Surface Disorder for Enhanced Solar Absorption and Superior Visible-Light Photocatalytic Property in Ti-Rich BaTiO3 Nanocrystals.

Lattice disorder has emerged as a novel strategy to realize visible-light photocatalytic activity, but many existing studies often involved reduction states simultaneously. Photocatalysts based on only the lattice disorder but without the reduction states are still quite lacking and challenging. To this end, we explored a new type of lattice disorder in terms of the surface atom nonstoichiometry strategy in BaTiO3. Well-dispersed tetragonal BaTiO3 nanocrystals with a uniform size (∼20 nm) and cuboid morphology were hydrothermally synthesized through controlling over t-butylamine and oleic acid. HRTEM coupled with structural evolution analysis reveals the existence of a Ti-rich layer on BaTiO3 nanocrystals with surface atom disorder, which gives an overall Ti/Ba ratio of 1.50:1. This is mainly dominated by the oriented adsorption between oleic acid and surface Ba2+ of the nucleus during solution reaction. Such a surface disorder and Ti-rich nonstoichiometry effect could facilitate the enhanced visible-light absorption with a wavelength span of 400-700 nm that enables the superior visible-light photocatalytic property, which is not subject to the reduction states. This work demonstrates a first white material presenting a new type of lattice disorder that would be helpful for a wide range of photocatalyst explorations.

Marked Enhancement of Roll-Off Frequency in FeCoN Synthetic Antiferromagnetic Films Deposited by Oblique Incidence.

A series of FeCoN films were successfully deposited on glass substrates in a magnetron sputtering system. Using oblique incidence method and FeCoN/Ru/FeCoN synthetic antiferromagnetic (SAF) structure, two additional anisotropies energy were introduced: oblique incidence anisotropy and exchange anisotropy energy, which marked enhancement of the effective magnetic anisotropy (Hk). The increment of Hk results in a significant improvement in the roll-off frequency of these films. The roll-off frequency of FeCoN/Ru/FeCoN films with SAF structure can reach up to 8.6 GHz. A feasible approach to conveniently controlling Hk of soft magnetic thin films by using oblique deposition and SAF structure can further improve their properties for the potential applications in the high frequency region.

High Density Static Charges Governed Surface Activation for Long-Range Motion and Subsequent Growth of Au Nanocrystals.

How a heavily charged metal nanocrystal, and further a dual-nanocrystals system behavior with continuous electron charging? This refers to the electric dynamics in charged particles as well as the crystal growth for real metal particles, but it is still opening in experimental observations and interpretations. To this end, we performed an in-situ electron-beam irradiation study using transmission electron microscopy (TEM) on the Au nanocrystals that freely stand on the nitride boron nanotube (BNNT). Au nanocrystalline particles with sizes of 2⁻4 nm were prepared by a well-controlled sputtering method to stand on the BNNT surface without chemical bonding interactions. Au nanoparticles presented the surface atomic disorder, diffusion phenomena with continuous electron-beam irradiation, and further, the long-range motion that contains mainly the three stages: charging, activation, and adjacence, which are followed by final crystal growth. Firstly, the growth process undergoes the lattice diffusion and subsequently the surface-dominated diffusion mechanism. These abnormal phenomena and observations, which are fundamentally distinct from classic cases and previous reports, are mainly due to the overcharging of Au nanoparticle that produces a surface activation state in terms of high-energy plasma. This work therefore brings about new observations for both a single and dual-nanocrystals system, as well as new insights in understanding the resulting dynamics behaviors.

Colossal permittivity behavior and its origin in rutile (Mg1/3Ta2/3)xTi1-xO2.

This work investigates the synthesis, chemical composition, defect structures and associated dielectric properties of (Mg2+, Ta5+) co-doped rutile TiO2 polycrystalline ceramics with nominal compositions of (Mg2+1/3Ta5+2/3) x Ti1-x O2. Colossal permittivity (>7000) with a low dielectric loss (e.g. 0.002 at 1 kHz) across a broad frequency/temperature range can be achieved at x = 0.5% after careful optimization of process conditions. Both experimental and theoretical evidence indicates such a colossal permittivity and low dielectric loss intrinsically originate from the intragrain polarization that links to the electron-pinned [Formula: see text] defect clusters with a specific configuration, different from the defect cluster form previously reported in tri-/pent-valent ion co-doped rutile TiO2. This work extends the research on colossal permittivity and defect formation to bi-/penta-valent ion co-doped rutile TiO2 and elucidates a likely defect cluster model for this system. We therefore believe these results will benefit further development of colossal permittivity materials and advance the understanding of defect chemistry in solids.

The Formation of Defect-Pairs for Highly Efficient Visible-Light Catalysts.

Highly efficient visible-light catalysts are achieved through forming defect-pairs in TiO2 nanocrystals. This study therefore proposes that fine-tuning the chemical scheme consisting of charge-compensated defect-pairs in balanced concentrations is a key missing step for realizing outstanding photocatalytic performance. This research benefits photocatalytic applications and also provides new insight into the significance of defect chemistry for functionalizing materials.

Impact of hole doping on spin transition in perovskite-type cobalt oxides.

Series of perovskite PrCo1-xNixO3-δ (x = 0-0.4) were prepared and carefully investigated to understand the spin state transition driven by hole doping and further to reveal the effect of spin state transition on electronic conduction. It is shown that with increasing doping level, the transition temperature Ts for Co(3+) ions from low-spin (LS) to intermediate-spin (IS) reduces from 211.9 K for x = 0 to 190.5 K for x = 0.4. XPS and FT-IR spectra demonstrate that hole doping promoted this transition due to a larger Jahn-Teller distortion. Moreover, a thermal activation of spin disorder caused by thermal population of the spin states for Co ions has a great impact on the electrical transport of these perovskite samples. This work may shed light on the comprehension of spin transition in cobalt oxides through hole doping, which is promising for finding new strategies of enhancing electronic conduction, especially for energy and catalysis applications.

Electric-field-induced AFE-FE transitions and associated strain/preferred orientation in antiferroelectric PLZST.

Electric-field-induced, antiferroelectric-ferroelectric (AFE-FE) phase transitions are common for AFE materials. To date, the strain and preferred orientation evolution as well as the role of the intermediate FE state during the successive AFE-FE-AFE phase transitions has not been clear. To this end, we have herein studied a typical AFE Pb0.97La0.02(Zr0.56Sn0.33Ti0.11)O3 (PLZST) material using in-situ neutron diffraction. It is striking that the AFE-FE phase transition is not fully reversible: in the electric-field-induced FE state, the induced strain exhibits an elliptical distribution, which in turn leads to significant preferred orientation in the final AFE state after withdrawal of the applied electric-field. The ω-dependent neutron diffraction patterns show clear evidence of the induced strain distribution and associated preferred orientation arising from the AFE-FE phase transition. The current work also provides an explanation for several temperature and electric-field dependent dielectric anomalies as well as unrecovered strain change which appear in AFE materials after exposure to sufficiently high electric fields.

Colossal Dielectric Behavior of Ga+Nb Co-Doped Rutile TiO2.

Stimulated by the excellent colossal permittivity (CP) behavior achieved in In+Nb co-doped rutile TiO2, in this work we investigate the CP behavior of Ga and Nb co-doped rutile TiO2, i.e., (Ga(0.5)Nb(0.5))(x)Ti(1-x)O2, where Ga(3+) is from the same group as In(3+) but with a much smaller ionic radius. Colossal permittivity of up to 10(4)-10(5) with an acceptably low dielectric loss (tan δ = 0.05-0.1) over broad frequency/temperature ranges is obtained at x = 0.5% after systematic synthesis optimizations. Systematic structural, defect, and dielectric characterizations suggest that multiple polarization mechanisms exist in this system: defect dipoles at low temperature (∼10-40 K), polaronlike electron hopping/transport at higher temperatures, and a surface barrier layer capacitor effect. Together these mechanisms contribute to the overall dielectric properties, especially apparent observed CP. We believe that this work provides comprehensive guidance for the design of new CP materials.

Anchoring High-Concentration Oxygen Vacancies at Interfaces of CeO(2-x)/Cu toward Enhanced Activity for Preferential CO Oxidation.

Catalysts are urgently needed to remove the residual CO in hydrogen feeds through selective oxidation for large-scale applications of hydrogen proton exchange membrane fuel cells. We herein propose a new methodology that anchors high concentration oxygen vacancies at interface by designing a CeO2-x/Cu hybrid catalyst with enhanced preferential CO oxidation activity. This hybrid catalyst, with more than 6.1% oxygen vacancies fixed at the favorable interfacial sites, displays nearly 100% CO conversion efficiency in H2-rich streams over a broad temperature window from 120 to 210 °C, strikingly 5-fold wider than that of conventional CeO2/Cu (i.e., CeO2 supported on Cu) catalyst. Moreover, the catalyst exhibits a highest cycling stability ever reported, showing no deterioration after five cycling tests, and a super long-time stability beyond 100 h in the simulated operation environment that involves CO2 and H2O. On the basis of an arsenal of characterization techniques, we clearly show that the anchored oxygen vacancies are generated as a consequence of electron donation from metal copper atoms to CeO2 acceptor and the subsequent reverse spillover of oxygen induced by electron transfer in well controlled nanoheterojunction. The anchored oxygen vacancies play a bridging role in electron capture or transfer and drive molecule oxygen into active oxygen species to interact with the CO molecules adsorbed at interfaces, thus leading to an excellent preferential CO oxidation performance. This study opens a window to design a vast number of high-performance metal-oxide hybrid catalysts via the concept of anchoring oxygen vacancies at interfaces.

Atomic-scale control of TiO6 octahedra through solution chemistry towards giant dielectric response.

The structures of many important functional oxides contain networks of metal-oxygen polyhedral units i.e. MOn. The correlation between the configurations and connectivities of these MOn to properties is essentially important to be well established to conduct the design, synthesis and application of new MOn-based functional materials. In this paper, we report on an atomic-scale solution-chemistry approach that for the first time enables TiO6 octahedral network control starting from metastable brookite TiO2 through simultaneously tuning pH values and interfering ions (Fe(3+), Sc(3+), and Sm(3+)). The relationship between solution chemistry and the resultant configuration/connectivity of TiO6 octahedra in TiO2 and lepidocrocite titanate is mapped out. Apart from differing crystalline phases and morphologies, atomic-scale TiO6 octahedral control also endows numerous defect dipoles for giant dielectric responses. The structural and property evolutions are well interpreted by the associated H(+)/OH(-) species in solution and/or defect states associated with Fe(3+) occupation within TiO6 octahedra. This work therefore provides fundamental new insights into controlling TiO6 octahedral arrangement essential for atomic-scale structure-property design.