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.

Emergent zero-field anomalous Hall effect in a reconstructed rutile antiferromagnetic metal.

The anomalous Hall effect (AHE) that emerges in antiferromagnetic metals shows intriguing physics and offers numerous potential applications. Magnets with a rutile crystal structure have recently received attention as a possible platform for a collinear-antiferromagnetism-induced AHE. RuO2 is a prototypical candidate material, however the AHE is prohibited at zero field by symmetry because of the high-symmetry [001] direction of the Néel vector at the ground state. Here, we show AHE at zero field in Cr-doped rutile, Ru0.8Cr0.2O2. The magnetization, transport and density functional theory calculations indicate that appropriate doping of Cr at Ru sites reconstructs the collinear antiferromagnetism in RuO2, resulting in a rotation of the Néel vector from [001] to [110] while maintaining a collinear antiferromagnetic state. The AHE with vanishing net moment in the Ru0.8Cr0.2O2 exhibits an orientation dependence consistent with the [110]-oriented Hall vector. These results demonstrate that material engineering by doping is a useful approach to manipulate AHE in antiferromagnetic metals.

Coexistence of Both Localized Electronic States and Electron Gas at Rutile TiO2 Surfaces.

Localized electron polarons formed through the coupling of excess electrons and ionic vibrations play a key role in the functionalities of materials. However, the mechanism of the coexistence of delocalized electrons and localized polarons remains underexplored. Here, the discovery of high-mobility 2D electron gas at the rutile TiO2 surfaces through argon ion irradiation induced oxygen vacancies is reported. Strikingly, the electron gas forms localized electronic states at lower temperatures, resulting in an abrupt metal-insulator transition. Moreover, it is found that the low-temperature conductivity in the insulating state is dominated by excess free electrons with a high mobility of ≈103 cm2 V-1 s-1 , whereas the carrier density is dramatically suppressed with decreasing temperature. Remarkably, it reveals that the application of an electric field can lead to a collapse of the localized states, resulting in a metallic state. These results reveal the strongly correlated/coupled nature between the localized electrons and high-mobility electrons and offer a new pathway to probe and harvest the exotic electron states at the complex oxide surfaces.

Manipulating the insulator-metal transition through tip-induced hydrogenation.

Manipulating the insulator-metal transition in strongly correlated materials has attracted a broad range of research activity due to its promising applications in, for example, memories, electrochromic windows and optical modulators1,2. Electric-field-controlled hydrogenation using ionic liquids3-6 and solid electrolytes7-9 is a useful strategy to obtain the insulator-metal transition with corresponding electron filling, but faces technical challenges for miniaturization due to the complicated device architecture. Here we demonstrate reversible electric-field control of nanoscale hydrogenation into VO2 with a tunable insulator-metal transition using a scanning probe. The Pt-coated probe serves as an efficient catalyst to split hydrogen molecules, while the positive-biased voltage accelerates hydrogen ions between the tip and sample surface to facilitate their incorporation, leading to non-volatile transformation from insulating VO2 into conducting HxVO2. Remarkably, a negative-biased voltage triggers dehydrogenation to restore the insulating VO2. This work demonstrates a local and reversible electric-field-controlled insulator-metal transition through hydrogen evolution and presents a versatile pathway to exploit multiple functional devices at the nanoscale.

Analog memristive synapse based on topotactic phase transition for high-performance neuromorphic computing and neural network pruning.

Inspired by the human brain, nonvolatile memories (NVMs)-based neuromorphic computing emerges as a promising paradigm to build power-efficient computing hardware for artificial intelligence. However, existing NVMs still suffer from physically imperfect device characteristics. In this work, a topotactic phase transition random-access memory (TPT-RAM) with a unique diffusive nonvolatile dual mode based on SrCoO x is demonstrated. The reversible phase transition of SrCoO x is well controlled by oxygen ion migrations along the highly ordered oxygen vacancy channels, enabling reproducible analog switching characteristics with reduced variability. Combining density functional theory and kinetic Monte Carlo simulations, the orientation-dependent switching mechanism of TPT-RAM is investigated synergistically. Furthermore, the dual-mode TPT-RAM is used to mimic the selective stabilization of developing synapses and implement neural network pruning, reducing ~84.2% of redundant synapses while improving the image classification accuracy to 99%. Our work points out a new direction to design bioplausible memristive synapses for neuromorphic computing.

Reversible manipulation of the magnetic state in SrRuO3 through electric-field controlled proton evolution.

Ionic substitution forms an essential pathway to manipulate the structural phase, carrier density and crystalline symmetry of materials via ion-electron-lattice coupling, leading to a rich spectrum of electronic states in strongly correlated systems. Using the ferromagnetic metal SrRuO3 as a model system, we demonstrate an efficient and reversible control of both structural and electronic phase transformations through the electric-field controlled proton evolution with ionic liquid gating. The insertion of protons results in a large structural expansion and increased carrier density, leading to an exotic ferromagnetic to paramagnetic phase transition. Importantly, we reveal a novel protonated compound of HSrRuO3 with paramagnetic metallic as ground state. We observe a topological Hall effect at the boundary of the phase transition due to the proton concentration gradient across the film-depth. We envision that electric-field controlled protonation opens up a pathway to explore novel electronic states and material functionalities in protonated material systems.

Electric Field-Controlled Multistep Proton Evolution in H x SrCoO2.5 with Formation of H-H Dimer.

Ionic evolution-induced phase transformation can lead to wide ranges of novel material functionalities with promising applications. Here, using the gating voltage during ionic liquid gating as a tuning knob, the brownmillerite SrCoO2.5 is transformed into a series of protonated H x SrCoO2.5 phases with distinct hydrogen contents. The unexpected electron to charge-neutral doping crossover along with the increase of proton concentration from x = 1 to 2 suggests the formation of exotic charge neutral H-H dimers for higher proton concentration, which is directly visualized at the vacant tetrahedron by scanning transmission electron microscopy and then further supported by first principles calculations. Although the H-H dimers cause no change of the valency of Co2+ ions, they result in clear enhancement of electronic bandgap and suppression of magnetization through lattice expansion. These results not only reveal a hydrogen chemical state beyond anion and cation within the complex oxides, but also suggest an effective pathway to design functional materials through tunable ionic evolution.

Manipulate the Electronic and Magnetic States in NiCo2 O4 Films through Electric-Field-Induced Protonation at Elevated Temperature.

Ionic-liquid-gating- (ILG-) induced proton evolution has emerged as a novel strategy to realize electron doping and manipulate the electronic and magnetic ground states in complex oxides. While the study of a wide range of systems (e.g., SrCoO2.5 , VO2 , WO3 , etc.) has demonstrated important opportunities to incorporate protons through ILG, protonation remains a big challenge for many others. Furthermore, the mechanism of proton intercalation from the ionic liquid/solid interface to whole film has not yet been revealed. Here, with a model system of inverse spinel NiCo2 O4 , an increase in system temperature during ILG forms a single but effective method to efficiently achieve protonation. Moreover, the ILG induces a novel phase transformation in NiCo2 O4 from ferrimagnetic metallic into antiferromagnetic insulating with protonation at elevated temperatures. This study shows that environmental temperature is an efficient tuning knob to manipulate ILG-induced ionic evolution.