Orbital Fulde-Ferrell-Larkin-Ovchinnikov state in an Ising superconductor.

In superconductors possessing both time and inversion symmetries, the Zeeman effect of an external magnetic field can break the time-reversal symmetry, forming a conventional Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state characterized by Cooper pairings with finite momentum1,2. In superconductors lacking (local) inversion symmetry, the Zeeman effect may still act as the underlying mechanism of FFLO states by interacting with spin-orbit coupling (SOC). Specifically, the interplay between the Zeeman effect and Rashba SOC can lead to the formation of more accessible Rashba FFLO states that cover broader regions in the phase diagram3-5. However, when the Zeeman effect is suppressed because of spin locking in the presence of Ising-type SOC, the conventional FFLO scenarios are no longer effective. Instead, an unconventional FFLO state is formed by coupling the orbital effect of magnetic fields with SOC, providing an alternative mechanism in superconductors with broken inversion symmetries6-8. Here we report the discovery of such an orbital FFLO state in the multilayer Ising superconductor 2H-NbSe2. Transport measurements show that the translational and rotational symmetries are broken in the orbital FFLO state, providing the hallmark signatures of finite-momentum Cooper pairings. We establish the entire orbital FFLO phase diagram, consisting of a normal metal, a uniform Ising superconducting phase and a six-fold orbital FFLO state. This study highlights an alternative route to achieving finite-momentum superconductivity and provides a universal mechanism to preparing orbital FFLO states in similar materials with broken inversion symmetries.

New magnetic phase of the chiral skyrmion material Cu2OSeO3.

The lack of inversion symmetry in the crystal lattice of magnetic materials gives rise to complex noncollinear spin orders through interactions of a relativistic nature, resulting in interesting physical phenomena, such as emergent electromagnetism. Studies of cubic chiral magnets revealed a universal magnetic phase diagram composed of helical spiral, conical spiral, and skyrmion crystal phases. We report a remarkable deviation from this universal behavior. By combining neutron diffraction with magnetization measurements, we observe a new multidomain state in Cu2OSeO3. Just below the upper critical field at which the conical spiral state disappears, the spiral wave vector rotates away from the magnetic field direction. This transition gives rise to large magnetic fluctuations. We clarify the physical origin of the new state and discuss its multiferroic properties.

Inducing ferromagnetism and Kondo effect in platinum by paramagnetic ionic gating.

Electrically controllable magnetism, which requires the field-effect manipulation of both charge and spin degrees of freedom, has attracted growing interest since the emergence of spintronics. We report the reversible electrical switching of ferromagnetic (FM) states in platinum (Pt) thin films by introducing paramagnetic ionic liquid (PIL) as the gating media. The paramagnetic ionic gating controls the movement of ions with magnetic moments, which induces itinerant ferromagnetism on the surface of Pt films, with large coercivity and perpendicular anisotropy mimicking the ideal two-dimensional Ising-type FM state. The electrical transport of the induced FM state shows Kondo effect at low temperature, suggesting spatially separated coexistence of Kondo scattering beneath the FM interface. The tunable FM state indicates that paramagnetic ionic gating could serve as a versatile method to induce rich transport phenomena combining field effect and magnetism at PIL-gated interfaces.

Micropatterned 2D Hybrid Perovskite Thin Films with Enhanced Photoluminescence Lifetimes.

The application of luminescent materials in display screens and devices requires micropatterned structures. In this work, we have successfully printed microstructures of a two-dimensional (2D), orange-colored organic/inorganic hybrid perovskite ((C6H5CH2NH3)2PbI4) using two different soft lithography techniques. Notably, both techniques yield microstructures with very high aspect ratios in the range of 1.5-1.8. X-ray diffraction reveals a strong preferential orientation of the crystallites along the c-axis in both patterned structures, when compared to nonpatterned, drop-casted thin films. Furthermore, (time-resolved) photoluminescence (PL) measurements reveal that the optical properties of (C6H5CH2NH3)2PbI4 are conserved upon patterning. We find that the larger grain sizes of the patterned films with respect to the nonpatterned film give rise to an enhanced PL lifetime. Thus, our results demonstrate easy and cost-effective ways to manufacture patterns of 2D organic/inorganic hybrid perovskites, while even improving their optical properties. This demonstrates the potential use of color-tunable 2D hybrids in optoelectronic devices.

Helimagnon Resonances in an Intrinsic Chiral Magnonic Crystal.

We experimentally study magnetic resonances in the helical and conical magnetic phases of the chiral magnetic insulator Cu_{2}OSeO_{3} at the temperature T=5 K. Using a broadband microwave spectroscopy technique based on vector network analysis, we identify three distinct sets of helimagnon resonances in the frequency range 2 GHz≤f≤20 GHz with low magnetic damping α≤0.003. The extracted resonance frequencies are in accordance with calculations of the helimagnon band structure found in an intrinsic chiral magnonic crystal. The periodic modulation of the equilibrium spin direction that leads to the formation of the magnonic crystal is a direct consequence of the chiral magnetic ordering caused by the Dzyaloshinskii-Moriya interaction. The mode coupling in the magnonic crystal allows excitation of helimagnons with wave vectors that are multiples of the spiral wave vector.

The Role of Connectivity on Electronic Properties of Lead Iodide Perovskite-Derived Compounds.

We use a layered solution crystal growth method to synthesize high-quality single crystals of two different benzylammonium lead iodide perovskite-like organic/inorganic hybrids. The well-known (C6H5CH2NH3)2PbI4 phase is obtained in the form of bright orange platelets, with a structure comprised of single ⟨100⟩-terminated sheets of corner-sharing PbI6 octahedra separated by bilayers of the organic cations. The presence of water during synthesis leads to formation of a novel minority phase that crystallizes in the form of nearly transparent, light yellow bar-shaped crystals. This phase adopts the monoclinic space group P21/n and incorporates water molecules, with structural formula (C6H5CH2NH3)4Pb5I14·2H2O. The crystal structure consists of ribbons of edge-sharing PbI6 octahedra separated by the organic cations. Density functional theory calculations including spin-orbit coupling show that these edge-sharing PbI6 octahedra cause the band gap to increase with respect to corner-sharing PbI6 octahedra in (C6H5CH2NH3)2PbI4. To gain systematic insight, we model the effect of the connectivity of PbI6 octahedra on the band gap in idealized lead iodide perovskite-derived compounds. We find that increasing the connectivity from corner-, via edge-, to face-sharing causes a significant increase in the band gap. This provides a new mechanism to tailor the optical properties in organic/inorganic hybrid compounds.

Vacancies in functional materials for clean energy storage and harvesting: the perfect imperfection.

Vacancies exist throughout nature and determine the physical properties of materials. By manipulating the density and distribution of vacancies, it is possible to influence their physical properties such as band-gap, conductivity, magnetism, etc. This can generate exciting applications in the fields of water treatment, energy storage, and physical devices such as resistance-change memories. In this review, we focus on recent progress in vacancy engineering for the design of materials for energy harvesting applications. A brief discription of the concept of vacancies, the way to create and control them, as well as their fundamental properties, is first provided. Then, emphasis is placed on the strategies used to tailor vacancies for metal-insulator transitions, electronic structures, and introducing magnetism in non-magnetic materials. Finally, we present representative applications of different structures with vacancies as active electrode materials of lithium or sodium ion batteries, catalysts for water splitting, and hydrogen evolution.

Polar Nature of (CH3NH3)3Bi2I9 Perovskite-Like Hybrids.

High-quality single crystals of perovskite-like (CH3NH3)3Bi2I9 hybrids have been synthesized, using a layered-solution crystal-growth technique. The large dielectric constant is strongly affected by the polar ordering of its constituents. Progressive dipolar ordering of the methylammonium cation upon cooling below 300 K gradually converts the hexagonal structure (space group P63/mmc) into a monoclinic phase (C2/c) at 160 K. A well-pronounced, ferrielectric phase transition at 143 K is governed by in-plane ordering of the bismuth lone pair that breaks inversion symmetry and results in a polar phase (space group P21). The dielectric constant is markedly higher in the C2/c phase above this transition. Here, the bismuth lone pair is disordered in-plane, allowing the polarizability to be substantially enhanced. Density functional theory calculations estimate a large ferroelectric polarization of 7.94 µC/cm2 along the polar axis in the P21 phase. The calculated polarization has almost equal contributions of the methylammonium and Bi3+ lone pair, which are fairly decoupled.

Metal-Insulator Transition Induced by Spin Reorientation in Fe7Se8 Grain Boundaries.

Fe7Se8 exists as a hexagonal NiAs-like crystal structure with a large number of ordered intrinsic vacancies. It is an ideal candidate for studying the effect of defects on properties such as magnetism and electrical transport. In this work, highly crystalline Fe7Se8 with the 3c crystal structure was synthesized by a solid-state reaction. Sharp changes in the magnetization at 100 K confirm a rotation of the spins from the ab plane to the c axis with decreasing temperature. We observe an interesting metal-insulator transition at the same temperature as the spin-direction changes. We propose that locked spins in the grain boundaries induce electron localization and result in the metal-insulator transition. Electron localization is confirmed by X-ray photoelectron spectroscopy of the Fe 2p peaks, which exhibit two characteristic satellite peaks. This mechanism is also verified by comparing it with the properties of the 4c-Fe7Se8 crystal structure.

Controlling the volatility of the written optical state in electrochromic DNA liquid crystals.

Liquid crystals are widely used in displays for portable electronic information display. To broaden their scope for other applications like smart windows and tags, new material properties such as polarizer-free operation and tunable memory of a written state become important. Here, we describe an anhydrous nanoDNA-surfactant thermotropic liquid crystal system, which exhibits distinctive electrically controlled optical absorption, and temperature-dependent memory. In the liquid crystal isotropic phase, electric field-induced colouration and bleaching have a switching time of seconds. Upon transition to the smectic liquid crystal phase, optical memory of the written state is observed for many hours without applied voltage. The reorientation of the DNA-surfactant lamellar layers plays an important role in preventing colour decay. Thereby, the volatility of optoelectronic state can be controlled simply by changing the phase of the material. This research may pave the way for developing a new generation of DNA-based, phase-modulated, photoelectronic devices.

Self-assembly of ferromagnetic organic-inorganic perovskite-like films.

Perovskite-based organic-inorganic hybrids hold great potential as active layers in electronics or optoelectronics or as components of biosensors. However, many of these applications require thin films grown with good control over structure and thickness--a major challenge that needs to be addressed. The work presented here is an effort towards this goal and concerns the layer-by-layer deposition at ambient conditions of ferromagnetic organic-inorganic hybrids consisting of alternating CuCl4-octahedra and organic layers. The Langmuir-Blodgett technique used to assemble these structures provides intrinsic control over the molecular organization and film thickness down to the molecular level. Magnetic characterization reveals that the coercive field for these thin films is larger than that for solution-grown layered bulk crystals. The strategy presented here suggests a promising cost effective route to facilitate the excellently controlled growth of sophisticated materials on a wide variety of substrates that have properties relevant for the high density storage media and spintronic devices.

Anionogenic mixed valency in KxBa1-xO2-δ.

We have synthesized members of an isostructural solid solution series KxBa1-xO2-δ (x < 0.41, δ < 0.11) containing mixed-valent dioxygen anions. Synthesis in liquid ammonia solution allows a continuous range of compounds to be prepared. X-ray and neutron diffraction show that KxBa1-xO2-δ adopts the tetragonal rocksalt-derived structure of the end members KO2 and BaO2, without any structural phase transition down to 5 K, the lowest temperature studied here. We identify four oxygen-oxygen stretching modes above 750 cm(-1) in the measured Raman spectra, unlike the spectra of KO2 and BaO2 which both contain just a single mode. We use density functional theory calculations to show that the stretching modes in KxBa1-xO2-δ arise from in-phase and anti-phase coupling of the stretching of nearest-neighbor oxygen dimers when the valence state of the dimers lies between -1 and -2 because of mixed cation coordination. This coupling is a direct signature of a novel type of anionogenic mixed valency.

Antiferromagnetic S=1/2 spin chain driven by p-orbital ordering in CsO2.

We demonstrate, using a combination of experiment and density functional theory, that orbital ordering drives the formation of a one-dimensional (1D) S=1/2 antiferromagnetic spin chain in the 3D rocksalt structure of cesium superoxide (CsO2). The magnetic superoxide anion (O2(-)) exhibits degeneracy of its 2p-derived molecular orbitals, which is lifted by a structural distortion on cooling. A spin chain is then formed by zigzag ordering of the half-filled superoxide orbitals, promoting a superexchange pathway mediated by the p(z) orbitals of Cs(+) along only one crystal direction. This scenario is analogous to the 3d-orbital-driven spin chain found in the perovskite KCuF3 and is the first example of an inorganic quantum spin system with unpaired p electrons.

A two-dimensional magnetic hybrid material based on intercalation of a cationic Prussian blue analog in montmorillonite nanoclay.

A highly ordered two-dimensional hybrid magnetic nanocomposite has been prepared by synthesizing and intercalating a new cationic aluminum-hydroxy ferric ferrocyanide compound into a cation-adsorbing nanoclay (montmorillonite). Chemical and structural properties were investigated by X-ray diffraction, transmission electron microscopy, thermogravimetric and differential thermal analyses, Fourier transform infrared, X-ray photoemission, and Mössbauer spectroscopies. Elemental analysis was based on proton-induced gamma ray emission and X-ray fluorescence spectroscopy data, N/C elemental ratios, and cation-exchange capacity measurements. Magnetic properties were studied by SQUID magnetometry. The results suggest: (i) that the cationic Prussian blue analog comprises Al-hydroxy cations embedded into a monolayer thick two-dimensional ferric ferrocyanide array; and (ii) that the clay-Prussian blue nanohybrid consists of such arrays stacked between the clay layers. The latter material orders ferromagnetically at approximately 5K showing a hundred times higher remanence than that of the starting material, soluble Prussian blue (ammonium ferric ferrocyanide).

Dynamics of spin and orbital phase transitions in YVO3.

YVO3 exhibits a well separated sequence of orbital and spin order transitions at 200 and 116 K, followed by a combined spin-orbital reorientation at 77 K. It is shown that the spin order can be destroyed by a sufficiently strong optical pulse within less than 4 ps. In contrast, the orbital reordering transition from C-type to G-type orbital order is slower than 100 ps and goes via an intermediate nonthermal phase. We propose that the dynamics of phase transitions is subjected to symmetry relations between the associated phases.

Large coupled magnetoresponses in EuNbO2N.

We have explored a new strategy to discover materials with large resistive or capacitive responses to magnetic fields by synthesizing EuMO2N (M = Nb, Ta) perovskites that combine ferromagnetic order of S = 7/2 Eu2+ spins with possible off-center distortions of the d0 M5+ cations enhanced by covalent bonding to N. EuNbO2N shows colossal magnetoresistances at low temperatures and a giant magnetocapacitance. However, the latter response originates from a microstructural effect rather than an intrinsic multiferroism.

Selective co-aggregation of gold nanoparticles functionalised with complementary hydrogen-bonding groups.

Molecular recognition between two species of Au55 clusters bearing complementary hydrogen-bonding groups provides a facile route to accomplish solution-based assembly of two-component nanoparticle aggregates.

Carbon nanotubes encapsulating superconducting single-crystalline tin nanowires.

Superconducting low dimensional systems are the natural choice for fast and sensitive infrared detection, because of their quantum nature and the low-noise, cryogenic operation environment. On the other hand, monochromatic and coherent electron beams, emitted from superconductors and carbon-based nanostructured materials, respectively, are significant for the development of electron optical systems such as electron microscopes and electron-beam nanofabrication systems. Here we describe for the first time a simple method which yields carbon nanotubes encapsulating single crystalline superconducting tin nanowires by employing the catalytic chemical vapor deposition method over solid tin dioxide. The superconducting tin nanowires, with diameters 15-35 nm, are covered with well-graphitized carbon walls and show, due to their reduced diameters, a critical magnetic field (Hc) more than 30 times higher than the value of bulk metallic tin.

Low-temperature structure of rubrene single crystals grown by vapor transport.

We report the crystal structure of rubrene, C42H28 (5,6,11,12-tetraphenyltetracene), in the temperature interval 100-300 K. The crystals are grown by physical vapor transport in an open system. The crystal structure is orthorhombic over the entire temperature range.