Atomic Origins of Enhanced Ferroelectricity in Nanocolumnar PbTiO3 /PbO Composite Thin Films.

Nanocomposite films hold great promise for multifunctional devices by integrating different functionalities within a single film. The microstructure of the precipitate/secondary phase is an essential element in designing composites' properties. The interphase strain between the matrix and secondary phase is responsible for strain-mediated functionalities, such as magnetoelectric coupling and ferroelectricity. However, a quantitative microstructure-dependent interphase strain characterization has been scarcely studied. Here, it is demonstrated that the PbTiO3 (PTO)/PbO composite system can be prepared in nano-spherical and nanocolumnar configurations by tuning the misfit strain, confirmed by a three-dimensional reconstructive microscopy technique. With the atomic resolution quantitative microscopy with a depth resolution of a few nanometers, it is discovered that the strained region in PTO is much larger and more uniform in nanocolumnar compared to nano-spherical composites, resulting in much enhanced ferroelectric properties. The interphase strain between PbO and PTO in the nanocolumnar structure leads to a giant c/a ratio of 1.20 (bulk value of 1.06), accompanied by a Ti polarization displacement of 0.48 Å and an effective ferroelectric polarization of 241.7 µC cm-2 , three times compared to the bulk value. The quantitative atomic-scale strain and polarization analysis on the interphase strain provides an important guideline for designing ferroelectric nanocomposites.

Perpendicular Magnetic Anisotropy and Dzyaloshinskii-Moriya Interaction at an Oxide/Ferromagnetic Metal Interface.

We report on the study of both perpendicular magnetic anisotropy (PMA) and Dzyaloshinskii-Moriya interaction (DMI) at an oxide/ferromagnetic metal (FM) interface, i.e., BaTiO_{3} (BTO)/CoFeB. Thanks to the functional properties of the BTO film and the capability to precisely control its growth, we are able to distinguish the dominant role of the oxide termination (TiO_{2} vs BaO) from the moderate effect of ferroelectric polarization in the BTO film, on the PMA and DMI at an oxide/FM interface. We find that the interfacial magnetic anisotropy energy of the BaO-BTO/CoFeB structure is 2 times larger than that of the TiO_{2}-BTO/CoFeB, while the DMI of the TiO_{2}-BTO/CoFeB interface is larger. We explain the observed phenomena by first principles calculations, which ascribe them to the different electronic states around the Fermi level at oxide/ferromagnetic metal interfaces and the different spin-flip process. This study paves the way for further investigation of the PMA and DMI at various oxide/FM structures and thus their applications in the promising field of energy-efficient devices.

Atomic-Scale Control of Magnetism at the Titanite-Manganite Interfaces.

Complex oxide thin-film heterostructures often exhibit magnetic properties different from those known for bulk constituents. This is due to the altered local structural and electronic environment at the interfaces, which affects the exchange coupling and magnetic ordering. The emergent magnetism at oxide interfaces can be controlled by ferroelectric polarization and has a strong effect on spin-dependent transport properties of oxide heterostructures, including magnetic and ferroelectric tunnel junctions. Here, using prototype La2/3Sr1/3MnO3/BaTiO3 heterostructures, we demonstrate that ferroelectric polarization of BaTiO3 controls the orbital hybridization and magnetism at heterointerfaces. We observe changes in the enhanced orbital occupancy and significant charge redistribution across the heterointerfaces, affecting the spin and orbital magnetic moments of the interfacial Mn and Ti atoms. Importantly, we find that the exchange coupling between Mn and Ti atoms across the interface is tuned by ferroelectric polarization from ferromagnetic to antiferromagnetic. Our findings provide a viable route to electrically control complex magnetic configurations at artificial multiferroic interfaces, taking a step toward low-power spintronics.

Interfacial Coupling-Induced Ferromagnetic Insulator Phase in Manganite Film.

Interfaces with subtle differences in atomic and electronic structures in perovskite ABO3 heterostructures often yield intriguingly different properties, yet their exact roles remain elusive. Here, we report an integrated study of unusual transport, magnetic, and structural properties of Pr0.67Sr0.33MnO3 film on SrTiO3 substrate. The variations in the out-of-plane lattice constant and BO6 octahedral rotation across the Pr0.67Sr0.33MnO3/SrTiO3 interface strongly depend on the thickness of the Pr0.67Sr0.33MnO3 film. In the 12 nm film, a new interface-sensitive ferromagnetic polaronic insulator (FI') phase is formed during the cubic-to-tetragonal phase transition of SrTiO3, apparently due to the enhanced electron-phonon interaction and atomic disorder in the film. The transport properties of the FI' phase in the 30 nm film are masked because of the reduced interfacial coupling and smaller interface-to-volume ratio. This work demonstrates how thickness-dependent interfacial coupling leads to the formation of a theoretically predicted ferromagnetic-polaronic insulator, as illustrated in a new phase diagram, that is otherwise ferromagnetic metal (FM) in bulk form.

Anisotropic Melting Path of Charge-Ordering Insulator in LSMO/STO Superlattice.

Multiple phases coexist in manganite with simultaneously active couplings, and the transition among them depends on the relative intensities of different interactions. However, the melting path with variable intensities is unclear. The concentration and the ordering of oxygen vacancy in previous work are found to induce ferromagnetic charge-ordering insulator phase in [(La0.7 Sr0.3 MnO3 )10 /(SrTiO3 )5 ]n superlattice, which translates into metallic phase with magnetic field H and temperature T. In the current work, the H-T phase diagram for current I//[100] and I//[110] shows a large difference with H normal to the film plane, which is ascribed to the response of a variable range of hopping process to H with the in-plane anisotropic hopping probability of charge carrier. With H rotating from the out-of-plane to the in-plane direction, the preferred occupancy of the 3 d z 2 - r 2 $3{d}_{{z}^2 - {r}^2}$ orbital causes a decrease of spin-orbital coupling and lowers the activation energy, inducing a gentler melting process of a charge-ordering insulator. This work shows that the melting path of a charge-ordering insulator phase can be largely modulated in manganite with anisotropy.

Large-Scale Epitaxial Growth of Ultralong Stripe BiFeO3 Films and Anisotropic Optical Properties.

The controlled synthesis of large-scale ferroelectric domains with high uniformity is crucial for practical applications in next-generation nanoelectronics on the basis of their intriguing properties. Here, ultralong and highly uniform stripe domains in (110)-oriented BiFeO3 thin films are large-area synthesized through a pulsed laser deposition technique. Utilizing scanning transmission electron microscopy and piezoresponse force microscopy, we verified that the ferroelectric domains have one-dimensional 109° domains and the length of a domain is up to centimeter scale. More importantly, the ferroelectric displacement is directly determined on atomic-scale precision, further confirming the domain structure. We find that the unique one-dimensional ferroelectric domain significantly enhances the optical anisotropy. Furthermore, we demonstrate that the purely parallel domain patterns can be used to control photovoltaic current. These ultralong ferroelectric domains can be patterned into various functional devices, which may inspire research efforts to explore their properties and various applications.

Ferroelectric Self-Polarization Controlled Magnetic Stratification and Magnetic Coupling in Ultrathin La0.67Sr0.33MnO3 Films.

Multiferroic oxide heterostructures consisting of ferromagnetic and ferroelectric components hold the promise for nonvolatile magnetic control via ferroelectric polarization, advantageous for the low-dissipation spintronics. Modern understanding of the magnetoelectric coupling in these systems involves structural, orbital, and magnetic reconstructions at interfaces. Previous works have long proposed polarization-dependent interfacial magnetic structures; however, direct evidence is still missing, which requires advanced characterization tools with near-atomic-scale spatial resolutions. Here, extensive polarized neutron reflectometry (PNR) studies have determined the magnetic depth profiles of PbZr0.2Ti0.8O3/La0.67Sr0.33MnO3 (PZT/LSMO) bilayers with opposite self-polarizations. When the LSMO is 2-3 nm thick, the bilayers show two magnetic transitions on cooling. However, temperature-dependent magnetization is different below the lower-temperature transition for opposite polarizations. PNR finds that the LSMO splits into two magnetic sublayers, but the inter-sublayer magnetic couplings are of opposite signs for the two polarizations. Near-edge X-ray absorption spectroscopy further shows contrasts in both the Mn valences and the Mn-O bond anisotropy between the two polarizations. This work completes the puzzle for the magnetoelectric coupling model at the PZT/LSMO interface, showing a synergic interplay among multiple degrees of freedom toward emergent functionalities at complex oxide interfaces.

Perovskite Light-Emitting Diodes with Near Unit Internal Quantum Efficiency at Low Temperatures.

Room-temperature-high-efficiency light-emitting diodes based on metal halide perovskite FAPbI3 are shown to be able to work perfectly at low temperatures. A peak external quantum efficiency (EQE) of 32.8%, corresponding to an internal quantum efficiency of 100%, is achieved at 45 K. Importantly, the devices show almost no degradation after working at a constant current density of 200 mA m-2 for 330 h. The enhanced EQEs at low temperatures result from the increased photoluminescence quantum efficiencies of the perovskite, which is caused by the increased radiative recombination rate. Spectroscopic and calculation results suggest that the phase transitions of the FAPbI3 play an important role for the enhancement of exciton binding energy, which increases the recombination rate.

Magnetoelectric Coupling Induced Orbital Reconstruction and Ferromagnetic Insulating State in PbZr0.52Ti0.48O3/La0.67Sr0.33MnO3 Heterostructures.

Novel phenomena at the ferromagnetic/ferroelectric interface have generated much interest. Here, a ferromagnetic insulating state with the Curie temperature about 268-286 K in PbZr0.52Ti0.48O3/La0.67Sr0.33MnO3 heterostructures is induced and modulated by varying the PbZr0.52Ti0.48O3 thickness. An abnormally enlarged c/a ratio in La0.67Sr0.33MnO3 by strain-based coupling effect leads to d3z2-r2 orbital preferable occupancy. This orbital reconstruction modulates effective electron transfer and finally leads to a ferromagnetic insulating state. Valence change induced by charge-based coupling effect could be partially responsible for change in the Curie temperature in the strongly correlated electron system of La1-xSrxMnO3. This work provides a deeper understanding of strain effects near the ferromagnetic/ferroelectric interface, especially in a PbZr1-yTiyO3/La1-xSrxMnO3 heterostructure system.

Tuning Irreversible Magnetoresistance in Pr0.67Sr0.33MnO3 Film via Octahedral Rotation.

The oxygen octahedral rotation around the out-of-plane axis is explored to study its effect on metastable status, magnetic cluster glass in manganite. The antiphase rotation around the out-of-plane axis (TiO6 a0a0c-) of SrTiO3 enhances the Mn-O bond anisotropy along in-plane and out-of-plane directions and weakens the ferromagnetic interactions in a 12 nm Pr0.67Sr0.33MnO3 film on the (001) SrTiO3 substrate, which together promote the formation of magnetic cluster-glassiness and enlarges the irreversible magnetoresistance (MR) effect with enhanced relaxation time of charge carriers. The effect of TiO6 a0a0c- in the SrTiO3 substrate on material properties is obvious with a large irreversible MR effect for thin films, which fades away with the increase in film thickness. At 10 K, the irreversible MR is 0.91 for the 12 nm film and 0.22 for the 30 nm film. This work extends current understanding on interfacial coupling to metastable status and could help explore other systems in the perovskite structure with octahedral rotation.

Overcoming the Limits of the Interfacial Dzyaloshinskii-Moriya Interaction by Antiferromagnetic Order in Multiferroic Heterostructures.

Topologically protected magnetic states have a variety of potential applications in future spintronics owing to their nanoscale size (<100 nm) and unique dynamics. These fascinating states, however, usually are located at the interfaces or surfaces of ultrathin systems due to the short interaction range of the Dzyaloshinskii-Moriya interaction (DMI). Here, magnetic topological states in a 40-unit cells (16 nm) SrRuO3 layer are successfully created via an interlayer exchange coupling mechanism and the interfacial DMI. By controlling the thickness of an antiferromagnetic and ferromagnetic layer, interfacial ionic polarization, as well as the transformation between ferromagnetic and magnetic topological states, can be modulated. Using micromagnetic simulations, the formation and stability of robust magnetic skyrmions in SrRuO3 /BiFeO3 heterostructures are elucidated. Magnetic skyrmions in thick multiferroic heterostructures are promising for the development of topological electronics as well as rendering a practical approach to extend the interfacial topological phenomena to bulk via antiferromagnetic order.

Interfacial properties and in vitro cytotoxic effects of surface-modified near infrared absorbing Au-Au(2)S nanoparticles.

Near infrared (NIR) absorbing Au-Au(2)S nanoparticles were modified with surfactants of different hydrocarbon chain lengths to allow loading of anticancer drug, cisplatin. The interfacial interactions and surfactant chain length effects on drug loading, optical properties and cytotoxicity were discussed in this work. Short-chain surfactants were oriented closer to the surface normal and were adsorbed at higher densities. Surface modification also changed the optical properties of the particles. Notably, particles modified with short-chain surfactants exhibited a red shift, whereas particles modified with long-chain surfactants showed a blue shift. The in vitro cytotoxicity of drug-loaded surface-modified particles was dependent on the surfactants' chain length. Significant cytotoxicity was observed for 1 mg/ml of drug-loaded particles using surfactants with the shortest chain length. After NIR triggered drug release, the released Pt compounds were observed to be cytotoxic, while remaining nanoparticles did not exhibit any cytotoxicity. Also, the released Pt compounds upon NIR irradiation of drug-loaded particles were observed to be more toxic and had a different molecular structure from cisplatin.

Emergence of Topological Hall Effect in a SrRuO3 Single Layer.

Topological Hall effect (THE), appearing as bumps and/or dips in the Hall resistance curves, is considered as a hallmark of the skyrmion spin texture originated from the inversion symmetry breaking and spin-orbit interaction. Recently, Néel-type skyrmion is proposed based on the observed THE in 5d transition metal oxides heterostructures such as SrRuO3 /SrIrO3 bilayers, where the interfacial Dzyaloshinskii-Moriya interaction (DMI), due to the strong spin-orbit coupling (SOC) in SrIrO3 and the broken inversion symmetry at the interface, is believed to play a significant role. Here the emergence of THE in SrRuO3 single layers with thickness ranging from 3 to 6 nm is experimentally demonstrated. It is found that the oxygen octahedron rotation in SrRuO3 also has a significant effect on the observed THE. Furthermore, the THE may be continuously tuned by an applied electrical field. It is proposed that the large SOC of Ru ions together with the broken inversion symmetry, mainly from the interface, produce the DMI that is responsible for the observed THE. The emergence of the gate-tunable DMI in SrRuO3 single layer may stimulate further investigations of new spin-orbit physics in strong SOC oxides.

In vivo toxic studies and biodistribution of near infrared sensitive Au-Au(2)S nanoparticles as potential drug delivery carriers.

Near infrared (NIR) sensitive Au-Au(2)S nanoparticles are intensively being developed for biomedical applications including drug and gene delivery. Although all possible clinical applications will require compatibility of Au-Au(2)S nanoparticles with the biological milieu, their in vivo capabilities and limitations have not yet been explored. Au-Au(2)S nanoparticles and cisplatin-loaded Au-Au(2)S nanoparticles were successfully synthesized by the reduction of tetrachloroauric acid (HAuCl(4)) using sodium sulfide (Na(2)S), and cisplatin was loaded onto NIR sensitive Au-Au(2)S nanoparticles via an MUA (11-mercaptoundecanoic acid) layer. In this work, acute systemic toxicity in vivo, blood biochemistry assay, and tissue distribution in mice were carried out to further investigate the biocompatibility and biodistribution of these nanoparticles. The results from these studies demonstrated that both of nanoparticles (<200 microg/mL) might have a great advantage in biocompatibility and good biological safety.

Control of Synaptic Plasticity Learning of Ferroelectric Tunnel Memristor by Nanoscale Interface Engineering.

Brain-inspired computing is an emerging field, which intends to extend the capabilities of information technology beyond digital logic. The progress of the field relies on artificial synaptic devices as the building block for brainlike computing systems. Here, we report an electronic synapse based on a ferroelectric tunnel memristor, where its synaptic plasticity learning property can be controlled by nanoscale interface engineering. The effect of the interface engineering on the device performance was studied. Different memristor interfaces lead to an opposite virgin resistance state of the devices. More importantly, nanoscale interface engineering could tune the intrinsic band alignment of the ferroelectric/metal-semiconductor heterostructure over a large range of 1.28 eV, which eventually results in different memristive and spike-timing-dependent plasticity (STDP) properties of the devices. Bidirectional and unidirectional gradual resistance modulation of the devices could therefore be controlled by tuning the band alignment. This study gives useful insights on tuning device functionalities through nanoscale interface engineering. The diverse STDP forms of the memristors with different interfaces may play different specific roles in various spike neural networks.

Inhibition of DNA hybridization by small metal nanoparticles.

The inhibition of DNA hybridization by small metal nanoparticles has been examined in detail. DNA melting point analysis showed that the oligonucleotides adsorb strongly and nonspecifically on small metal nanoparticles, inhibiting the hybridization of complementary DNA sequences in common buffered solutions. The nonspecific interaction is even strong enough to disrupt pre-existing hydrogen bonds in short double-stranded DNA. The nonspecific interaction could be weakened by increasing the particle size. As an example, a core-shell assisted method was used to successfully assemble Pt nanoparticles by DNA hybridization that could not be done otherwise.

Effects of strain relaxation in Pr0.67Sr0.33MnO3 films probed by polarization dependent X-ray absorption near edge structure.

The Mn K edge X-ray absorption near edge structure (XANES) of Pr0.67Sr0.33MnO3 films with different thicknesses on (001) LaAlO3 substrate was measured, and the effects of strain relaxation on film properties were investigated. The films showed in-plane compressive and out-of-plane tensile strains. Strain relaxation occurred with increasing film thickness, affecting both lattice constant and MnO6 octahedral rotation. In polarization dependent XANES measurements using in-plane (parallel) and out-of-plane (perpendicular) geometries, the different values of absorption resonance energy Er confirmed the film anisotropy. The values of Er along these two directions shifted towards each other with increasing film thickness. Correlating with X-ray diffraction (XRD) results it is suggested that the strain relaxation decreased the local anisotropy and corresponding probability of electronic charge transfer between Mn 3d and O 2p orbitals along the in-plane and out-of-plane directions. The XANES results were used to explain the film-thickness dependent magnetic and transport properties.

Strain Engineering of Octahedral Rotations and Physical Properties of SrRuO3 Films.

Strain engineering is an effective way to modify functional properties of thin films. Recently, the importance of octahedral rotations in pervoskite films has been recognized in discovering and designing new functional phases. Octahedral behavior of SrRuO3 film as a popular electrode in heterostructured devices is of particular interest for its probable interfacial coupling of octahedra with the functional overlayers. Here we report the strain engineering of octahedral rotations and physical properties that has been achieved in SrRuO3 films in response to the substrate-induced misfit strains of almost the same amplitude but of opposite signs. It shows that the compressively strained film on NdGaO3 substrate displays a rotation pattern of a tetragonal phase whilst the tensilely strained film on KTaO3 substrate has the rotation pattern of the bulk orthorhombic SrRuO3 phase. In addition, the compressively strained film displays a perpendicular magnetic anisotropy while the tensilely strained film has the magnetic easy axis lying in the film plane. The results show the prospect of strain engineered octahedral architecture in producing desired property and novel functionality in the class of perovskite material.

Facile patterning of upconversion NaYF4:Yb,Er nanoparticles.

Different kinds of highly ordered patterns of NaYF(4):Yb,Er nanoparticles on gold substrates were fabricated using a simple method combining micro-contact printing and "breath figures" techniques. Ordered arrays of water droplets were first formed in the hydrophilic regions of patterned self-assembled monolayers (SAMs). This was subsequently submerged in a chloroform solution of NaYF(4):Yb,Er nanoparticles. The particles were spontaneously assembled at the interface of chloroform/water droplet surface, leading to different kinds of uniform patterns after solvent evaporation. The structures of NaYF(4):Yb,Er particles patterns depended on the dimension of the substrate, the concentration of the NaYF(4):Yb,Er nanoparticles and the water condensation process.

Effects of oleic acid surface coating on the properties of nickel ferrite nanoparticles/PLA composites.

Nickel ferrite nanoparticles with or without oleic acid surface coating were mixed with poly(D,L-lactide) (PLA) by double emulsion method. If the nanoparticles were prepared without oleic acid coating, they adsorbed on the PLA surface. If the nanoparticles were coated with oleic acid, they could be readily encapsulated within the PLA microspheres. A slight depression in glass transition temperature was found in all composites and it could be related to the interfacial energies between nanoparticles and PLA. Optimum mixed composite was achieved by reducing interfacial energy. However, loading capacity was limited in this composite. Increasing the amount of nickel ferrite nanoparticles was not useful to increase loading capacity. Cytotoxicity of the composite decreased significantly when nickel ferrite nanoparticles were effectively encapsulated in PLA microspheres.