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Interfacial strain plays a vital role in determining the coupling strength between the magnetic and electrically ordered phases in magnetoelectric (ME) nanostructures. The interfacial strain and its gradient size in a polycrystalline trilayer ME composite with a specific microstructure were estimated by grazing incident X-ray diffraction (GI-XRD). The average interfacial strain was estimated to have a maximum value of ∼7%, and was found to be relaxed at a length scale of 25–35 nm away from the interface. The optimized gradient size estimated from the trilayer ME composite was utilized to fabricate multilayers with specific periodicities ("Δ") and tested for the inverse piezomagnetic effect to estimate the optimum periodicity required to have enhanced ME coupling. Multilayers with periodicity (∼40 nm) compared to multilayers with relaxed/partial interfacial strain exhibited ∼25 to 26% increment in piezoelectric coefficient (d33) in the presence of a magnetic field. The constraint imposed on polarization by interfacial strain reflects on the enhancement of stiffness and introduces a quicker linear response to the piezoelectric displacement. In contrast, the partially strained and/or strain-relaxed layers exhibited nonlinear responses in polarization switching. The linear piezoelectric displacement in these strain-engineered ME composites makes them a potential candidate for device applications like actuators and transducers. [ABSTRACT FROM AUTHOR]

The use of sequential catalytic growth (SCG) to encapsulate iron, nickel-iron and iron-cobalt phosphide catalyst nanoparticles periodically along the entire lengths of carbon nanotubes is demonstrated. The results show that the SCG mechanism can be used to grow carbon nanotubes that contain regularly spaced room-temperature-ferromagnetic nanoparticles.

An innovative approach is described for the production of single-crystal iron oxide nanorings by using a solution-based route. An easily scaled-up method is described for preparing tailor-made iron oxide nanorings that have met the demands of a variety of applications ranging from medicine to magnetoelectronics.

We present an innovative approach to the production of single-crystal iron oxide nanorings employing a solution-based route. Single-crystal hematite (α-Fe[sub2]O[sub3]) nanorings were synthesized using a double anion-assisted hydrothermal method (involving phosphate and sulfate ions), which can be divided into two stages: (1) formation of capsule-shaped α-Fe[sub2]O[sub3] nanoparticles and (2) preferential dissolution along the long dimension of the elongated nanoparticles (the c axis of α-Fe[sub2]O[sub3]) to form nanorings. The shape of the nanorings is mainly regulated by the adsorption of phosphate ions on faces parallel to c axis of α-Fe[sub2]O[sub3] during the nanocrystal growth, and the hollow structure is given by the preferential dissolution of the α-Fe[sub2]O[sub3] along the c axis due to the strong coordination of the sulfate ions. By varying the ratios of phosphate and sulfate ions to ferric ions, we were able to control the size, morphology, and surface architecture to produce a variety of three-dimensional hollow nanostructures. These can then be converted to magnetite (Fe[sub3]O[sub4]) and maghemite (γ-Fe[sub2]O[sub3]) by a reduction or reduction-oxidation process while preserving the same morphology. The structures and magnetic properties of these single-crystal α-Fe[sub2]O[sub3], Fe[sub3]O[sub4], and γ-Fe[sub2]O[sub3] nanorings were characterized by various analytical techniques. Employing off-axis electron holography, we observed the classical single-vortex magnetic state in the thin magnetite nanorings, while the thicker rings displayed an intriguing three-dimensional magnetic configuration. This work provides an easily scaled-up method for preparing tailor-made iron oxide nanorings that could meet the demands of a variety of applications ranging from medicine to magnetoelectronics. [ABSTRACT FROM AUTHOR]

Ga-doped Li 7 La 3 Zr 2 O 12 garnet solid electrolytes exhibit the highest Li-ion conductivities among the oxide-type garnet-structured solid electrolytes, but instabilities toward Li metal hamper their practical application. The instabilities have been assigned to direct chemical reactions between LiGaO 2 coexisting phases and Li metal by several groups previously. Yet, the understanding of the role of LiGaO 2 in the electrochemical cell and its electrochemical properties is still lacking. Here, we are investigating the electrochemical properties of LiGaO 2 through electrochemical tests in galvanostatic cells versus Li metal and complementary ex situ studies via confocal Raman microscopy, quantitative phase analysis based on powder X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electron energy loss spectroscopy. The results demonstrate considerable and surprising electrochemical activity, with high reversibility. A three-stage reaction mechanism is derived, including reversible electrochemical reactions that lead to the formation of highly electronically conducting products. The results have considerable implications for the use of Ga-doped Li 7 La 3 Zr 2 O 12 electrolytes in all-solid-state Li-metal battery applications and raise the need for advanced materials engineering to realize Ga-doped Li 7 La 3 Zr 2 O 12 for practical use.

Concurrent structural and electronic transformations in VO 2 thin films are of 2-fold importance: enabling fine-tuning of the emergent electrical properties in functional devices, yet creating an intricate interfacial domain structure of transitional phases. Despite the importance of understanding the structure of VO 2 thin films, a detailed real-space atomic structure analysis in which the oxygen atomic columns are also resolved is lacking. Moreover, intermediate atomic structures have remained elusive due to the lack of robust atomically resolved quantitative analysis. Here, we directly resolve both V and O atomic columns and discover the presence of intermediate monoclinic (M2) phase nanolayers (less than 2 nm thick) in epitaxially grown VO 2 films on a TiO 2 (001) substrate, where the dominant part of VO 2 undergoes a transition from the tetragonal (rutile) phase to the monoclinic M1 phase. Strain analysis suggests that the presence of the M2 phase is related to local strain gradients near the TiO 2 /VO 2 interface. We unfold the crucial role of imaging the spatial configurations of the oxygen anions (in addition to V cations) by utilizing atomic-resolution electron microscopy. Our approach can be used to unravel the structural transitions in a wide range of correlated oxides, offering substantial implications for, e.g., optoelectronics and ferroelectrics.

Two-dimensional van der Waals (vdW) heterostructures are an attractive platform for studying exchange bias due to their defect-free and atomically flat interfaces. Chromium thiophosphate (CrPS 4 ), an antiferromagnetic material, possesses uncompensated magnetic spins in a single layer, rendering it a promising candidate for exploring exchange bias phenomena. Recent findings have highlighted that naturally oxidized vdW ferromagnetic Fe 3 GeTe 2 exhibits exchange bias, attributed to the antiferromagnetic coupling of its ultrathin surface oxide layer (O-FGT) with the underlying unoxidized Fe 3 GeTe 2 . Anomalous Hall measurements are employed to scrutinize the exchange bias within the CrPS 4 /(O-FGT)/Fe 3 GeTe 2 heterostructure. This analysis takes into account the contributions from both the perfectly uncompensated interfacial CrPS 4 layer and the interfacial oxide layer. Intriguingly, a distinct and nonmonotonic exchange bias trend is observed as a function of temperature below 140 K. The occurrence of exchange bias induced by a "preset field" implies that the prevailing phase in the polycrystalline surface oxide is ferrimagnetic Fe 3 O 4 . Moreover, the exchange bias induced by the ferrimagnetic Fe 3 O 4 is significantly modulated by the presence of the van der Waals antiferromagnetic CrPS 4 layer, forming a heterostructure, along with additional iron oxide phases within the oxide layer. These findings underscore the intricate and complex nature of exchange bias in van der Waals heterostructures, highlighting their potential for tailored manipulation and control.

This work investigates the effect of copper substitution on the magnetic properties of SmCo 5 thin films synthesized by molecular beam epitaxy. A series of thin films with varying concentrations of Cu were grown under otherwise identical conditions to disentangle structural and compositional effects on the magnetic behavior. The combined experimental and theoretical studies show that Cu substitution at the Co 3g sites not only stabilizes the formation of the SmCo 5 structure but also enhances magnetic anisotropy and coercivity. Density functional theory calculations indicate that Sm(Co 4 Cu 3g ) 5 possesses a higher single-ion anisotropy as compared to pure SmCo 5 . In addition, X-ray magnetic circular dichroism reveals that Cu substitution causes an increasing decoupling of the Sm 4f and Co 3d moments. Scanning transmission electron microscopy confirms predominantly SmCo 5 phase formation and reveals nanoscale inhomogeneities in the Cu and Co distribution. Our study based on thin film model systems and advanced characterization as well as modeling reveals novel aspects of the complex interplay of intrinsic and extrinsic contributions to magnetic hysteresis in rare-earth-based magnets, i.e., the combination of increased intrinsic anisotropy due to Cu substitution and the extrinsic effect of inhomogeneous elemental distribution of Cu and Co.

Using a combination of in situ bulk and surface characterization techniques, we provide atomic-scale insight into the complex surface and bulk dynamics of a LaNiO 3 perovskite material during heating in vacuo . Driven by the outstanding activity LaNiO 3 in the methane dry reforming reaction (DRM), attributable to the decomposition of LaNiO 3 during DRM operation into a Ni//La 2 O 3 composite, we reveal the Ni exsolution dynamics both on a local and global scale by in situ electron microscopy, in situ X-ray diffraction and in situ X-ray photoelectron spectroscopy. To reduce the complexity and disentangle thermal from self-activation and reaction-induced effects, we embarked on a heating experiment in vacuo under comparable experimental conditions in all methods. Associated with the Ni exsolution, the remaining perovskite grains suffer a drastic shrinkage of the grain volume and compression of the structure. Ni particles mainly evolve at grain boundaries and stacking faults. Sophisticated structure analysis of the elemental composition by electron-energy loss mapping allows us to disentangle the distribution of the different structures resulting from LaNiO 3 decomposition on a local scale. Important for explaining the DRM activity, our results indicate that most of the Ni moieties are oxidized and that the formation of NiO occurs preferentially at grain edges, resulting from the reaction of the exsolved Ni particles with oxygen released from the perovskite lattice during decomposition via a spillover process from the perovskite to the Ni particles. Correlating electron microscopy and X-ray diffraction data allows us to establish a sequential two-step process in the decomposition of LaNiO 3 via a Ruddlesden-Popper La 2 NiO 4 intermediate structure. Exemplified for the archetypical LaNiO 3 perovskite material, our results underscore the importance of focusing on both surface and bulk characterization for a thorough understanding of the catalyst dynamics and set the stage for a generalized concept in the understanding of state-of-the art catalyst materials on an atomic level., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Arrays of interacting 2D nanomagnets display unprecedented electromagnetic properties via collective effects, demonstrated in artificial spin ices and magnonic crystals. Progress toward 3D magnetic metamaterials is hampered by two challenges: fabricating 3D structures near intrinsic magnetic length scales (sub-100 nm) and visualizing their magnetic configurations. Here, we fabricate and measure nanoscale magnetic gyroids, periodic chiral networks comprising nanowire-like struts forming three-connected vertices. Via block copolymer templating, we produce Ni 75 Fe 25 single-gyroid and double-gyroid (an inversion pair of single-gyroids) nanostructures with a 42 nm unit cell and 11 nm diameter struts, comparable to the exchange length in Ni-Fe. We visualize their magnetization distributions via off-axis electron holography with nanometer spatial resolution and interpret the patterns using finite-element micromagnetic simulations. Our results suggest an intricate, frustrated remanent state which is ferromagnetic but without a unique equilibrium configuration, opening new possibilities for collective phenomena in magnetism, including 3D magnonic crystals and unconventional computing.

Photodriven dipole reordering of the intercalated organic molecules in halide perovskites has been suggested to be a critical degree of freedom, potentially affecting physical properties, device performance, and stability of hybrid perovskite-based optoelectronic devices. However, thus far a direct atomically resolved dipole mapping under device operation condition, that is, illumination, is lacking. Here, we map simultaneously the molecule dipole orientation pattern and the electrostatic potential with atomic resolution using photoexcited cross-sectional scanning tunneling microscopy and spectroscopy. Our experimental observations demonstrate that a photodriven molecule dipole reordering, initiated by a photoexcited separation of electron-hole pairs in spatially displaced orbitals, leads to a fundamental reshaping of the potential landscape in halide perovskites, creating separate one-dimensional transport channels for holes and electrons. We anticipate that analogous light-induced polarization order transitions occur in bulk and are at the origin of the extraordinary efficiencies of organometal halide perovskite-based solar cells as well as could reconcile apparently contradictory materials' properties.

Octahedral faceted nanoparticles are highly attractive fuel cell catalysts as a result of their activity for the oxygen reduction reaction (ORR). However, their surface compositional and morphological stability currently limits their long-term performance in real membrane electrode assemblies. Here, we perform in situ heating of compositionally segregated PtNi 1.5 octahedral nanoparticles inside a transmission electron microscope, in order to study their compositional and morphological changes. The starting PtNi 1.5 octahedra have Pt-rich edges and concave Ni-rich {111} facets. We reveal a morphological evolution sequence, which involves transformation from concave octahedra to particles with atomically flat {100} and {111} facets, ideally representing truncated octahedra or cuboctahedra. The flat {100} and {111} facets are thought to comprise a thin Pt layer with a Ni-rich subsurface, which may boost catalytic activity. However, the transformation to truncated octahedra/cuboctahedra also decreases the area of the highly active {111} facets. The morphological and surface compositional evolution, therefore, results in a compromise between catalytic activity and morphological stability. Our findings are important for the design of more stable faceted PtNi nanoparticles with high activities for the ORR.

The interface of metal-oxide plays pivotal roles in catalytic reactions, but its catalytic function is still not clear. In this study, we report the high activity of nanostructured Ru/ceria (Ru-clusters/ceria) in the ethylene methoxycarbonylation (EMC) reaction in the absence of acid promoter. The catalyst offers 92% yield of MP with TOF of 8666 h -1 , which is about 2.5 times of homogeneous Pd catalyst (∼3500 h -1 ). The interfacial Lewis acid-base pair [Ru-O-Ce-Vö], which consists of acidic Ce-Vö (oxygen vacancy) site and basic interfacial oxygen of Ru-O-Ce linkage, acts as active site for the dissociation of methanol and the subsequent transfer of hydrogen to the activated ethylene, which is the key step in acid-promoter-free EMC reaction. The combination of 1 H MAS NMR, pyridine-IR and DFT calculations reveals the hydrogen species derived from methanol contains Brönsted acidity. The EMC reaction mechanism under acid-promoter-free condition over Ru-clusters/ceria catalyst is discussed.

We map electronic states, band gaps, and interface-bound charges at termination-engineered BiFeO 3 /La 0.7 Sr 0.3 MnO 3 interfaces using atomically resolved cross-sectional scanning tunneling microscopy. We identify a delicate interplay of different correlated physical effects and relate these to the ferroelectric and magnetic interface properties tuned by engineering the atomic layer stacking sequence at the interfaces. This study highlights the importance of a direct atomically resolved access to electronic interface states for understanding the intriguing interface properties in complex oxides.

In the presence of disorder, superconductivity exhibits short-range characteristics linked to localized Cooper pairs which are responsible for anomalous phase transitions and the emergence of quantum states such as the bosonic insulating state. Complementary to well-studied homogeneously disordered superconductors, superconductor-normal hybrid arrays provide tunable realizations of the degree of granular disorder for studying anomalous quantum phase transitions. Here, we investigate the superconductor-bosonic dirty metal transition in disordered nanodiamond arrays as a function of the dispersion of intergrain spacing, which ranges from angstroms to micrometers. By monitoring the evolved superconducting gaps and diminished coherence peaks in the single-quasiparticle density of states, we link the destruction of the superconducting state and the emergence of bosonic dirty metallic state to breaking of the global phase coherence and persistence of the localized Cooper pairs. The observed resistive bosonic phase transitions are well modeled using a series-parallel circuit in the framework of bosonic confinement and coherence.