Interface-Driven Multiferroicity in Cubic BaTiO3-SrTiO3 Nanocomposites.

Perovskite multiferroics have drawn significant attention in the development of next-generation multifunctional electronic devices. However, the majority of existing multiferroics exhibit ferroelectric and ferromagnetic orderings only at low temperatures. Although interface engineering in complex oxide thin films has triggered many exotic room-temperature functionalities, the desired coupling of charge, spin, orbital and lattice degrees of freedom often imposes stringent requirements on deposition conditions, layer thickness and crystal orientation, greatly hindering their cost-effective large-scale applications. Herein, we report an interface-driven multiferroicity in low-cost and environmentally friendly bulk polycrystalline material, namely cubic BaTiO3-SrTiO3 nanocomposites which were fabricated through a simple, high-throughput solid-state reaction route. Interface reconstruction in the nanocomposites can be readily controlled by the processing conditions. Coexistence of room-temperature ferromagnetism and ferroelectricity, accompanying a robust magnetoelectric coupling in the nanocomposites, was confirmed both experimentally and theoretically. Our study explores the 'hidden treasure at the interface' by creating a playground in bulk perovskite oxides, enabling a broad range of applications that are challenging with thin films, such as low-power-consumption large-volume memory and magneto-optic spatial light modulator.

Observation of the interactions of silver nanoparticles (AgNPs) mediated by acid in the aquatic matrices using in-situ liquid cell transmission electron microscopy.

The properties of the solution matrix play a prominent role in determining the interactions between the silver nanoparticles (AgNPs) when they are present in the aquatic environment. Here, using in situ liquid cell transmission electron microscopy (LCTEM), we show that the interaction of AgNPs is predominantly affected by the solution pH. Reducing the pH in the solution will accelerate the aggregation of AgNPs due to the alteration of the charge cloud around the NPs. Aggregates formed in this scenario were non spherical and irregular shaped and were stable under the electron beam irradiation. Individual AgNPs and smaller aggregates moved randomly and approached the larger aggregates before the aggregation process came to an end. We found that during the aggregation process, the mode of jump to contact and the pairwise approach of aggregation differed according to the composition of the solution. Observations made using the LCTEM were further explained using empirical formulae. Our observation on the pH induced interactions provides important insights on predicting the behavior of AgNPs released through many anthropogenic activities in the environment.

Interface-Charge Induced Giant Electrocaloric Effect in Lead Free Ferroelectric Thin-Film Bilayers.

Conventional refrigeration methods based on compression-expansion cycles of greenhouse gases are environmentally threatening and cannot be miniaturized. Electrocaloric effects driven by electric fields are especially well suited for implementation of built-in cooling in portable electronic devices. However, most known electrocaloric materials present poor cooling performances near room temperature, contain toxic substances, and require high electric fields. Here, we show that lead-free ferroelectric thin-film bilayers composed of (Bi0.5Na0.5)TiO3-BaTiO3 (BNBT) and Ba(Zr0.2Ti0.8)O3-(Ba0.7Ca0.3)TiO3 (BCZT) display unprecedentedly large electrocaloric effects of ∼23 K near room temperature under moderate electric bias. The giant electrocaloric effect observed in BNBT/BCZT bilayers, which largely surpasses the sum of the individual caloric responses measured in BNBT and BCZT, is originated from the presence of compositional bound charges at their interface. Our discovery of interface charge-induced giant electrocaloric effects indicates that multilayered oxide heterostructures hold tremendous promise for developing highly efficient and scalable solid-state cooling applications.

Formation of Si Nanorods and Discrete Nanophases by Axial Diffusion of Si from Substrate into Au and AuPt Nanoalloy Nanorods.

Interdiffusion between Si substrate and nanorod arrays of Au, Pt, and AuPt nanoalloys is investigated at temperatures lower than the AuSi eutectic temperature. When the nanorod is pure Au, Si diffusion from the substrate is very rapid. Au atoms are completely replaced by Si, converting the nanostructure into one of Si nanorod arrays. Au is diffused out to the substrate. The Au nanorod arrays on Si are unstable. When the nanorod is pure Pt, however, no diffusion of Si into the nanorod or any silicide formation is observed. The Pt nanorods are stable on Si substrate. When the nanorods are an alloy of AuPt, interesting interactions occur. Si diffusion into the nanorods is rapid but the diffusing Si readily reacts with Pt forming PtSi while Au diffuses out to the substrate. After annealing, nanophases of Au, Pt, PtSi, and Si may be present within the nanorods. When the Pt content of the alloy is low (12 at%) all Pt atoms are converted to silicide and the extra Si atoms remain in elemental form, particularly near the tip of the nanorods. Hence, the presence of Au accelerates Si diffusion and the ensuing reaction to form PtSi, a phenomenon absents in pure Pt nanorods. When the Au content of the alloy is low, the Si diffusion would cease when all Au atoms have diffused out of the nanorod, thereby arresting the silicide formation resulting in excess Pt in elemental form within the nanorod. This is a technique of making Si nanorods with and without embedded PtSi nanophase consisting of heterojunctions which could have unique properties.

Achieving Site-Specificity in Multistep Colloidal Synthesis.

We show that partial inhibition of the emerging Ag domain can be achieved by controlling the growth dynamics. With the symmetry broken by the "fresh" surface, sequentially growth gives (Au sphere)-(Ag wire)-(Ag plate) triblock nanostructures. This new understanding opens doors to sophisticated synthetic designs, broadening the horizon of our search for functional architectures.

A "uniform" heterogeneous photocatalyst: integrated p-n type CuInS2/NaInS2 nanosheets by partial ion exchange reaction for efficient H2 evolution.

Single-crystalline-like P-N type CuInS2/NaInS2 heterogeneous nanosheets were synthesized by partial cation exchange reaction and show highly improved photocatalytic H2 evolution activity attributed to the increased efficiency of interfacial charge transfer.

Preparation of MoS2-MoO3 hybrid nanomaterials for light-emitting diodes.

A facile strategy to prepare MoS2 -MoO3 hybrid nanomaterials is developed, based on the heat-assisted partial oxidation of lithium-exfoliated MoS2  nanosheets in air followed by thermal-annealing-driven crystallization. The obtained MoS2 -MoO3 hybrid nanomaterial exhibits p-type conductivity. As a proof-of-concept application, an n-type SiC/p-type MoS2 -MoO3 heterojunction is used as the active layer for light-emitting diodes. The origins of the electroluminescence from the device are theoretically investigated. This facile synthesis and application of hybrid nanomaterials opens up avenues to develop new advanced materials for various functional applications, such as in electrics, optoelectronics, clean energy, and information storage.

Spirocyclic aromatic hydrocarbon-based organic nanosheets for eco-friendly aqueous processed thin-film non-volatile memory devices.

Supramolecular steric hindrance designs make pyrene-functionalized spiro[fluorene-9,7'-dibenzo[c,h]acridine]-5'-one (Py-SFDBAO) assemble into 2D nanostructures that facilitate aqueous phase large-area synthesis of high-quality and uniform crystalline thin films. Thin-film diodes using aqueous nanosheets as active layers exhibit a non-volatile bistable electrical switching feature with ON/OFF ratios of 6.0 × 10(4) and photoswitching with conductive gains of 10(2) -10(3). Organic nanosheets are potentially key components for eco-friendly aqueous dispersed organic nano-inks in the application of printed and flexible electronics.

Exciton localization and optical properties improvement in nanocrystal-embedded ZnO core-shell nanowires.

We present a comparative investigation of the morphological, structural, and optical properties of vertically aligned ZnO nanowires (NWs) before and after high energy argon ion (Ar(+)) milling. It is found that the outer regions of the as-grown sample change from crystalline to amorphous, and ZnO core-shell NWs with ZnO nanocrystals embedded are formed after Ar(+) milling. Optical properties of the ZnO NWs have been investigated systematically through power and temperature dependent photoluminescence measurements, and the phenomenon of exciton localization as well as the relevant favorable photoluminescence characteristics is elucidated. Interestingly, under high density optical pumping at room temperature, coherent random lasing action is observed, which is ascribed to exciton localization and strong scattering. Our results on the unique optical properties of localized exciton in ZnO core-shell nanostructures shed light on developing stable and high-efficiency excitonic optoelectronic devices such as light-emitting diodes and lasers.

Controlled growth of SnO2@Fe2O3 double-sided nanocombs as anodes for lithium-ion batteries.

A novel heterostructure is developed by grafting 1D SnO(2) nanorods onto both sides of pre-grown 2D Fe(2)O(3) nanoflakes, forming a comb-like rather than tree-like branched nanostructure. The SnO(2) nanorod branches are determined to grow along the [001] direction on the (±001) planes of Fe(2)O(3) nanoflakes. The resulting SnO(2)@Fe(2)O(3) nanocombs show stabilized cycling performance and improved volumetric energy density compared to pristine Fe(2)O(3) nanoflakes presumably due to the integration of SnO(2) branches as well as the 3D hierarchical structural features.

Kinetically controlled assembly of a spirocyclic aromatic hydrocarbon into polyhedral micro/nanocrystals.

Nonplane molecules with multiple large aromatic planes could be promising candidates to form various polyhedral micro/nanocrystals by manipulating the different π···π stacking, tuning the cohesive energies of crystal facets, and controlling the kinetic growth process. Spirocyclic aromatic hydrocarbons (SAHs) not only have two cross-shaped aromatic planes but also offer the feature of supramolecular steric hindrance, making it favorable for the heterogeneous kinetic growth into highly symmetric polyhedra. Herein, we report that a novel SAH compound, spiro[fluorene-9,7'-dibenzo[c,h]acridine]-5'-one (SFDBAO), can self-assemble into various monodispersed shapes such as hexahedra, octahedra, and decahedra through the variation of either different types of surfactants, such as Pluronic 123 (P123) and cetyltrimethyl ammonium bromide (CTAB), or growth parameters. In addition, the possible mechanism of crystal facet growth has been proposed according to the SEM, XRD, TEM, and SAED characterization of organic polyhedral micro/nanocrystals. The unique cruciform-shaped SAHs have been demonstrated as fascinating supramolecular synthons for various highly symmetric polyhedral assembling.

An unconventional role of ligand in continuously tuning of metal-metal interfacial strain.

We show that embedding of a surface ligand can dramatically affect the metal-metal interfacial energy, making it possible to create nanostructures in defiance of traditional wisdom. Despite matching Au-Ag lattices, Au-Ag hybrid NPs can be continuously tuned from concentric core-shell, eccentric core-shell, acorn, to dimer structures. This method can be extended to tune even Au-Au and Ag-Ag interfaces.

Engineering "hot" nanoparticles for surface-enhanced Raman scattering by embedding reporter molecules in metal layers.

Ag is deposited on the surface of Au nanoparticles functionalized with 4-mercaptobenzoic acid (MBA). Exceptionally strong surface-enhanced Raman scattering (SERS) signals are observed from the resulting colloid. Using SERS as a tool, evidence is obtained for the embedding of MBA inside the nanoscale metal layer.

Template free electrochemical deposition of ZnSb nanotubes for Li ion battery anodes.

ZnSb nanotubes were grown through a template free electrodeposition method under over-potential conditions. The growth of the nanotubes was attributed to the template effect from H(2) bubbles. Due to their hollow structure, the ZnSb nanotubes depicted better Li ion storage performance compared to that of ZnSb nanoparticles deposited under different conditions.

Controlled CVD growth of Cu-Sb alloy nanostructures.

Sb based alloy nanostructures have attracted much attention due to their many promising applications, e.g. as battery electrodes, thermoelectric materials and magnetic semiconductors. In many cases, these applications require controlled growth of Sb based alloys with desired sizes and shapes to achieve enhanced performance. Here, we report a flexible catalyst-free chemical vapor deposition (CVD) process to prepare Cu-Sb nanostructures with tunable shapes (e.g. nanowires and nanoparticles) by transporting Sb vapor to react with copper foils, which also serve as the substrate. By simply controlling the substrate temperature and distance, various Sb-Cu alloy nanostructures, e.g. Cu(11)Sb(3) nanowires (NWs), Cu(2)Sb nanoparticles (NPs), or pure Sb nanoplates, were obtained. We also found that the growth of Cu(11)Sb(3) NWs in such a catalyst-free CVD process was dependent on the substrate surface roughness. For example, smooth Cu foils could not lead to the growth of Cu(11)Sb(3) nanowires while roughening these smooth Cu foils with rough sand papers could result in the growth of Cu(11)Sb(3) nanowires. The effects of gas flow rate on the size and morphology of the Cu-Sb alloy nanostructures were also investigated. Such a flexible growth strategy could be of practical interest as the growth of some Sb based alloy nanostructures by CVD may not be easy due to the large difference between the condensation temperature of Sb and the other element, e.g. Cu or Co.

Reducing the symmetry of bimetallic Au@Ag nanoparticles by exploiting eccentric polymer shells.

We demonstrate a facile colloidal method for synthesizing Janus nanoparticles, whose eccentric polymer shells are exploited to fabricate eccentric bimetallic cores.