A correlated ferromagnetic polar metal by design.

Polar metals have recently garnered increasing interest because of their promising functionalities. Here we report the experimental realization of an intrinsic coexisting ferromagnetism, polar distortion and metallicity in quasi-two-dimensional Ca3Co3O8. This material crystallizes with alternating stacking of oxygen tetrahedral CoO4 monolayers and octahedral CoO6 bilayers. The ferromagnetic metallic state is confined within the quasi-two-dimensional CoO6 layers, and the broken inversion symmetry arises simultaneously from the Co displacements. The breaking of both spatial-inversion and time-reversal symmetries, along with their strong coupling, gives rise to an intrinsic magnetochiral anisotropy with exotic magnetic field-free non-reciprocal electrical resistivity. An extraordinarily robust topological Hall effect persists over a broad temperature-magnetic field phase space, arising from dipole-induced Rashba spin-orbit coupling. Our work not only provides a rich platform to explore the coupling between polarity and magnetism in a metallic system, with extensive potential applications, but also defines a novel design strategy to access exotic correlated electronic states.

Key influence factors in magneto-controlled motion of micro-nano graphite flakes.

Magneto-controlling micro-nano materials' motion is a promising way that enable the noncontact, remote, and nondestructive controlling of their macrostructure as well as functionalities. Here, an optical microscope with an electromagnet was constructed to in-situ monitor the magneto-controlled motion process microscopically. Taking micro-nano graphite flake (MGF) as a model system, we experimentally demonstrate the key factors which influence the magneto-controlling of materials' motion. First, the product of intensity and gradient of the magnetic field (B▽B) has been confirmed as the dominant driving force and the flipping direction of the MGFs is accordingly determined by the vector direction of B×▽B. Second, quantitatively comparative experiments further revealed that the threshold driving force has an exponential relationship with the structural aspect ratio (b/a) of MGFs. Third, the critical magneto-driving force is found as proportional to the viscosity of the solvent. In addition, we also discovered the delay effect, fatigue effects, and the multiple cycle acceleration effect in magneto-controlled flakes flipping. Accordingly, a dynamic model is developed that describes the flip of the diamagnetic flake under external magnetic field excitation considering the shape factor. It is shown experimentally that the model accurately predicts the flip dynamics of the flake under different magnetic field conditions. These findings can be used to achieve magneto-controlling materials' macrostructure as well as their functionalities.

Reversible Structural Transformation between Polar Polymorphs of Li2GeTeO6.

Li2GeTeO6 prepared at ambient pressure adopts the corundum derivative ordered ilmenite structure (rhombohedral R3). When heated at 1073 K and 3-5 GPa, the as-made Li2GeTeO6 can convert into a LiSbO3-derived Li2TiTeO6-type phase (orthorhombic Pnn2), which is the third LiSbO3-derived double A2BB'O6 phase in addition to Li2TiTeO6 and Li2SnTeO6. This Pnn2 Li2GeTeO6 phase spontaneously reverts to the R3 phase if annealed up to 1023 K at ambient pressure. Although the crystal structural analyses and second harmonic generation measurements clearly demonstrate the polar nature of both the R3 and Pnn2 phases, P( E) and dielectric measurements do not show any convincing ferroelectric response. Given the large estimated spontaneous polarization (17 and 80 µC/cm2), the absence of ferroelectric behavior could be attributed to the random domain distribution and leakage due to Li-ion migration.

Formation of ZnO4 Tetrahedra and ZnO6 Octahedra in TeZnO3 Synthesized under High Pressure.

A new TeZnO3 phase was synthesized by high-pressure techniques. Different from the ambient-pressure orthorhombic phase composed of ZnO5 units, the current high-pressure one crystallizes to a monoclinic structure with space group P21/ n. Moreover, both ZnO4 tetrahedral and ZnO6 octahedral polyhedra are found to occur in this new phase, providing a unique Zn-based material system that simultaneously possesses two distinct coordinated units. Because the outermost orbitals are fully occupied for both Zn2+ and Te4+, the compound exhibits diamagnetism and strong insulating behavior with a wide bandgap as large as 6.0 eV. Dielectric constant and specific heat measurements show a broad anomaly around 240 K. Low-temperature synchrotron X-ray diffraction reveals an isostructural phase transition at this temperature.

Temperature-modulated crystal growth and performance for highly reproducible and efficient perovskite solar cells.

The annealing temperature (Ta) effect on CH3NH3PbI3 perovskite solar cells (PSCs) was studied. By utilizing a two-step technique, the Ta dependences of the optical absorption, grain size, and crystallinity of a CH3NH3PbI3 thin film have been revealed. It is found that the grain size of the CH3NH3PbI3 film increases monotonically with Ta. Meanwhile, the decomposed PbI2 emerges when Ta exceeds 120 °C and its content increases rapidly as Ta increases further. Consequently, the optical absorption of the CH3NH3PbI3 film and the efficiency of PSCs reach their maximum at Ta = 120 °C simultaneously. The highest and average device performances of PSCs achieved via this method are 17.61% and 16.40%, respectively. These results confirm the key role played by temperature and provide a route to the performance-optimization of PSCs.

Publisher's Note: Direct Imaging of Dynamic Glassy Behavior in a Strained Manganite Film [Phys. Rev. Lett. 115, 265701 (2015)].

This corrects the article DOI: 10.1103/PhysRevLett.115.265701.

Direct Imaging of Dynamic Glassy Behavior in a Strained Manganite Film.

Complex many-body interaction in perovskite manganites gives rise to a strong competition between ferromagnetic metallic and charge-ordered phases with nanoscale electronic inhomogeneity and glassy behaviors. Investigating this glassy state requires high-resolution imaging techniques with sufficient sensitivity and stability. Here, we present the results of a near-field microwave microscope imaging on the strain-driven glassy state in a manganite film. The high contrast between the two electrically distinct phases allows direct visualization of the phase separation. The low-temperature microscopic configurations differ upon cooling with different thermal histories. At sufficiently high temperatures, we observe switching between the two phases in either direction. The dynamic switching, however, stops below the glass transition temperature. Compared with the magnetization data, the phase separation was microscopically frozen, while spin relaxation was found in a short period of time.

Crystallinity Tuning of Na3 V2 (PO4 )3 : Unlocking Sodium Storage Capacity and Inducing Pseudocapacitance Behavior.

As a promising cathode material of sodium-ion batteries, Na3 V2 (PO4 )3 (NVP) has attracted extensive attention in recent years due to its high stability and fast Na+ ion diffusion. However, the reversible capacity based on the two-electron reaction mechanism is not satisfactory limited by the inactive M1 lattice sites during the insertion/extraction process. Herein, self-supporting 3D porous NVP materials with different crystallinity are fabricated on carbon foam substrates by a facile electrostatic spray deposition method. The V5+ /V4+ redox couple is effectively activated and the three-electron reactions are realized in NVP for sodium storage by a proper crystallinity tuning. In a disordered NVP sample, an ultra-high specific capacity of 179.6 mAh g-1 at 0.2 C is achieved due to the coexistence of redox reactions of the V4+ /V3+ and V5+ /V4+ couples. Moreover, a pseudocapacitive charge storage mechanism induced by the disordered structure is first observed in the NVP electrode. An innovative model is given to understand the disorder-induced-pseudocapacitance phenomenon in this polyanion cathode material.

Twisting, untwisting, and retwisting of elastic Co-based nanohelices.

The reversible transformation of a nanohelix is one of the most exquisite and important phenomena in nature. However, nanomaterials usually fail to twist into helical crystals. Considering the irreversibility of the previously studied twisting forces, the reverse process (untwisting) is more difficult to achieve, let alone the retwisting of the untwisted crystalline nanohelices. Herein, we report a new reciprocal effect between molecular geometry and crystal structure which triggers a twisting-untwisting-retwisting cycle for tri-cobalt salicylate hydroxide hexahydrate. The twisting force stems from competition between the condensation reaction and stacking process, different from the previously reported twisting mechanisms. The resulting distinct nanohelices give rise to unusual structure elasticity, as reflected in the reversible change of crystal lattice parameters and the mutual transformation between the nanowires and nanohelices. This study proposes a fresh concept for designing reversible processes and brings a new perspective in crystallography.

Coherent Phonon-Induced Gigahertz Optical Birefringence and Its Manipulation in SrTiO3.

Birefringence, which modulates the polarization of electromagnetic wave, has been commercially developed and widely used in modern photonics. Fostered by high-frequency signal processing and communications, feasible birefringence technologies operating in gigahertz (GHz) range are highly desired. Here, a coherent phonon-induced GHz optical birefringence and its manipulation in SrTiO3 (STO) crystals are demonsrated. With ultrafast laser pumping, the coherent acoustic phonons with low damping are created in the transducer/STO structures. A series of transducer layers are examined and the optimized one with relatively high photon-phonon conversion efficiency, i.e., semiconducting LaRhO3 film, is obtained. The most intriguing finding here is that, by virtue of high sensitivity to strain perturbation of STO, GHz optical birefringence can be induced by the coherent acoustic phonons and the birefringent amplitudes possess crystal orientation dependence. Optical manipulation of both coherent phonons and its induced GHz birefringence by double pump technique are also realized. These findings reveal an alternative mechanism of ultrafast optical birefringence control, and offer prospects for applications in high-frequency acoustic-optics devices.

Emergent, Non-Aging, Extendable, and Rechargeable Exchange Bias in 2D Fe3 GeTe2 Homostructures Induced by Moderate Pressuring.

As a crucial concept in magnetism and spintronics, exchange bias (ExB) measures the asymmetry in the hysteresis loop of a pinned ferromagnet (FM)/antiferromagnet (AFM) interface. Previous studies are mainly focused on FM/AFM heterostructures composed of conventional bulk materials, whose complex interfaces prohibit precise control and full understanding of the phenomenon. Here, the enabling power of 2D magnets is exploited to demonstrate the emergence, non-aging, extendability, and rechargeability of ExB in van der Waals Fe3 GeTe2 homostructures, upon moderate pressuring. The emergence of the ExB is attributed to a local stress-induced FM-to-AFM transition, as validated using first-principles calculations, and confirmed in magneto-optical Kerr effect and second harmonic generation measurements. It is also observed that, negligible ExB aging before the training effect suddenly takes place through avalanching, pronounced delay of the avalanche via timed pressure repetition (extendability), ExB recovery in the post-training sample upon refreshed pressuring (rechargeability), and demonstrate its versatile tunability. These striking findings offer unprecedented insights into the underlying principles of ExB and its training, with immense technological applications in sight.

Magneto-electrochemistry driven ultralong-life Zn-VS2 aqueous zinc-ion batteries.

The development of high energy density and long cycle lifespan aqueous zinc ion batteries is hindered by the limited cathode materials and serious zinc dendrite growth. In this work, a defect-rich VS2 cathode material is manufactured by in situ electrochemical defect engineering under high charge cut-off voltage. Owing to the rich abundant vacancies and lattice distortion in the ab plane, the tailored VS2 can unlock the transport path of Zn2+ along the c-axis, enabling 3D Zn2+ transport along both the ab plane and c-axis, and reduce the electrostatic interaction between VS2 and zinc ions, thus achieving excellent rate capability (332 mA h g-1 and 227.8 mA h g-1 at 1 A g-1 and 20 A g-1, respectively). The thermally favorable intercalation and 3D rapid transport of Zn2+ in the defect-rich VS2 are verified by multiple ex situ characterizations and density functional theory (DFT) calculations. However, the long cycling stability of the Zn-VS2 battery is still unsatisfactory due to the Zn dendrite issue. It can be found that the introduction of an external magnetic field enables changing the movement of Zn2+, suppressing the growth of zinc dendrites, and resulting in enhanced cycling stability from about 90 to 600 h in the Zn||Zn symmetric cell. As a result, a high-performance Zn-VS2 full cell is realized by operating under a weak magnetic field, which shows an ultralong cycle lifespan with a capacity of 126 mA h g-1 after 7400 cycles at 5 A g-1, and delivers the highest energy density of 304.7 W h kg-1 and maximum power density of 17.8 kW kg-1.

Probing the Néel-Type Antiferromagnetic Order and Coherent Magnon-Exciton Coupling in Van Der Waals VPS3.

2D van der Waals (vdW) antiferromagnets have received intensive attention due to their terahertz resonance, multilevel magnetic-order states, and ultrafast spin dynamics. However, accurately identifying their magnetic configuration still remains a challenge owing to the lack of net magnetization and insensitivity to external fields. In this work, the Néel-type antiferromagnetic (AFM) order in 2D antiferromagnet VPS3 with the out-of-plane anisotropy, which is demonstrated by the temperature-dependent spin-phonon coupling and second-harmonic generation (SHG), is experimentally probed. This long-range AFM order even persists at the ultrathin limit. Furthermore, strong interlayer exciton-magnon coupling (EMC) upon the Néel-type AFM order is detected based on the monolayer WSe2 /VPS3 heterostructure, which induces an enhanced excitonic state and further certifies the Néel-type AFM order of VPS3 . The discovery provides optical routes as the novel platform to study 2D antiferromagnets and promotes their potential applications in magneto-optics and opto-spintronic devices.

Active and Smart Terahertz Electro-Optic Modulator Based on VO2 Structure.

Modulating terahertz (THz) waves actively and smartly through an external field is highly desired in the development of THz spectroscopic devices. Here, we demonstrate an active and smart electro-optic THz modulator based on a strongly correlated electron oxide vanadium dioxide (VO2). With milliampere current excitation on the VO2 thin film, the transmission, reflection, absorption, and phase of THz waves can be modulated efficiently. In particular, the antireflection condition can be actively achieved and the modulation depth reaches 99.9%, accompanied by a 180° phase switching. Repeated and current scanning experiments confirm the high stability and multibit modulation of this electro-optic modulation. Most strikingly, by utilizing a feedback loop of "THz-electro-THz" geometry, a smart electro-optic THz control is realized. For instance, the antireflection condition can be stabilized precisely no matter what the initial condition is and how the external environment changes. The proposed electro-optic THz modulation method, taking advantage of strongly correlated electron material, opens up avenues for the realization of THz smart devices.

Phonon-Related Monochromatic THz Radiation and its Magneto-Modulation in 2D Ferromagnetic Cr2 Ge2 Te6.

Searching multiple types of terahertz (THz) irradiation source is crucial for the THz technology. In addition to the conventional fermionic cases, bosonic quasi-/particles also promise energy-efficient THz wave emission. Here, by utilizing a 2D ferromagnetic Cr2 Ge2 Te6 crystal, first a phonon-related magneto-tunable monochromatic THz irradiation source is demonstrated. With a low-photonic-energy broadband THz pump, a strong THz irradiation with frequency ≈0.9 THz and bandwidth ≈0.25 THz can be generated and its conversion efficiency could even reach 2.1% at 160 K. Moreover, it is intriguing to find that such monochromatic THz irradiation can be efficiently modulated by external magnetic field below 160 K. According to both experimental and theoretical analyses, the emergent THz irradiation is identified as the emission from the phonon-polariton and its temperature and magnetic field dependent behaviors confirm the large spin-lattice coupling in this 2D ferromagnetic crystal. These observations provide a new route for the creation of tunable monochromatic THz source which may have great practical interests in future applications in photonic and spintronic devices.

Magnetic field effect on the photocatalytic degradation of methyl orange by commercial TiO2 powder.

In this work, by taking commercial P25 hydrophilic titanium dioxide (TiO2) as a photocatalyst, the magnetic field effect (MFE) on the photodegradation rate of methyl orange is studied. It is found that a relatively lower magnetic field B = 0.28 T can efficiently enhance the photodegradation efficiency of commercial TiO2 by 24%. However, the photodegradation efficiency of commercial TiO2 will be suppressed slightly by 7% under a magnetic field of 0.5 T. Moreover, such MFE on the photocatalyst is dependent on the settling state of the reaction solution. Additional experiments on the degradation of other pollutants (methylene blue) and with other photocatalysts (g-C3N4) indicate that the MFE is a ubiquitous phenomenon in the photocatalytic degradation process. These observations suggest that the magnetic field can be taken as an efficient strategy to regulate the catalytic process of commercial catalysts and improve the catalytic efficiency.

Magneto-Revealing and Acceleration of Hidden Kirkendall Effect in Galvanic Replacement Reaction.

Rate and product control are crucial for a chemical process and are useful in a wide range of applications. Traditionally, thermodynamic parameters, such as temperature or pressure, have been used to control the chemical reactions. Here, by using the fabrication of a hollow MnxFeyO4 nanostructure as a model system, we report an experimental tuning of both chemical reaction rate and product by a high magnetic field. A 12 times magneto-acceleration of the galvanic replacement (GR) reaction was observed. Moreover, it is first demonstrated that a magnetic field can unravel and accelerate the hidden Kirkendall effect (KE) in addition to the pristine GR reaction. With coaction of magneto-tuned KE and GR, not only the rate but also the composition as well as magnetic property of the products could be modulated. These observations suggest that not only is a magnetic field a variable parameter that cannot be ignored, but also it can effectively control both rate and product in a chemical reaction, which provides a new route for chemical process controlling and shape/composition designing in material synthesis.

Magnetic field tuning of spin resonance in TmFeO3 single crystal probed with THz transient.

TmFeO3, a canted antiferromagnet, has two intrinsic spin resonance modes in the terahertz (THz) frequency regime: quasi-ferromagnetic (q-FM) mode and quasi-antiferromagnetic (q-AFM) mode. Both the q-FM and q-AFM modes show strong magnetic field and temperature dependence. Hereby, by employing THz time-domain spectroscopy combined with external magnetic field and low temperature system, we systematically investigated the magnetic field induced frequency shift of q-FM and q-AFM modes as well as the temperature driven spin reorientation phase transition in TmFeO3 single crystal. In contrast to the isotropic temperature dependent two-mode, the magnetic field dependence of two-mode is strongly anisotropic: the magnetic field applied along c-axis (a-axis) can harden (soften) the spin resonance frequency of q-FM mode for Γ4 phase of TmFeO3, and the field applied along b-axis shows negligible frequency shift for the q-FM mode, with the q-AFM mode relatively stable. The present study provides solid evidence that the magnetic anisotropy in rare earth orthoferrite plays a dominant role in the q-FM mode and the occurrence of spin reorientation phase transition. With the magnetic anisotropic energy obtained from the temperature dependent q-FM and q-AFM mode frequencies, we can predict both magnetic field and temperature dependence of spin resonance in TmFeO3 single crystal via phenomenological analysis.

Polar Rectification Effect in Electro-Fatigued SrTiO3-Based Junctions.

Rectifying semiconductor junctions are crucial to electronic devices. They convert alternating current into a direct one by allowing unidirectional charge flows. Analogous to the current-flow rectification for itinerary electrons, here, a polar rectification that is based on the localized oxygen vacancies (OVs) in a Ti/fatigued-SrTiO3 (fSTO) Schottky junction is first demonstrated. The fSTO with OVs is produced by an electrodegradation process. The different movabilities of localized OVs and itinerary electrons in the fSTO yield a unidirectional electric polarization at the interface of the junction under the coaction of external and built-in electric fields. Moreover, the fSTO displays a pre-ferroelectric state located between paraelectric and ferroelectric phases. The pre-ferroelectric state has three sub-states and can be easily driven into a ferroelectric state by an external electric field. These observations open up opportunities for potential polar devices and may underpin many useful polar-triggered electronic phenomena.

Photoinduced Broad-band Tunable Terahertz Absorber Based on a VO2 Thin Film.

The demand for terahertz (THz) communication and detection fuels continuous research for high performance of THz absorption materials. In addition to varying the materials and their structure passively, an alternative approach is to modulate a THz wave actively by tuning an external stimulus. Correlated oxides are ideal materials for this because the effects of a small external control parameter can be amplified by inner electronic correlations. Here, by utilizing an unpatterned strongly correlated electron oxide VO2 thin film, a photoinduced broad-band tunable THz absorber is realized first. The absorption, transmission, reflection, and phase of THz waves can all be actively controlled by an external pump laser above room temperature. By varying the laser fluence, the average broad-band absorption can be tuned from 18.9 to 74.7% and the average transmission can be tuned from 9.2 to 69.2%. Meanwhile, a broad-band antireflection is obtained at 5.6 mJ/cm2, and a π-phase shift of a reflected THz wave is achieved when the fluence increases greater than 5.7 mJ/cm2. Apart from other modulators, the photoexcitation-assisted dual-phase competition is identified as the origin of this active THz multifunctional modulation. Our work suggests that advantages of controllable phase separation in strongly correlated electron systems could provide viable routes in the creation of active optical components for THz waves.