Colossal angular magnetoresistance in ferrimagnetic nodal-line semiconductors.

Efficient magnetic control of electronic conduction is at the heart of spintronic functionality for memory and logic applications1,2. Magnets with topological band crossings serve as a good material platform for such control, because their topological band degeneracy can be readily tuned by spin configurations, dramatically modulating electronic conduction3-10. Here we propose that the topological nodal-line degeneracy of spin-polarized bands in magnetic semiconductors induces an extremely large angular response of magnetotransport. Taking a layered ferrimagnet, Mn3Si2Te6, and its derived compounds as a model system, we show that the topological band degeneracy, driven by chiral molecular orbital states, is lifted depending on spin orientation, which leads to a metal-insulator transition in the same ferrimagnetic phase. The resulting variation of angular magnetoresistance with rotating magnetization exceeds a trillion per cent per radian, which we call colossal angular magnetoresistance. Our findings demonstrate that magnetic nodal-line semiconductors are a promising platform for realizing extremely sensitive spin- and orbital-dependent functionalities.

Robust Luttinger Liquid State of 1D Dirac Fermions in a Van der Waals System Nb9Si4Te18.

We report on the Tomonaga-Luttinger liquid (TLL) behavior in fully degenerate 1D Dirac Fermions. A ternary van der Waals material Nb9Si4Te18 incorporates in-plane NbTe2 chains, which produce a 1D Dirac band crossing Fermi energy. Tunneling conductance of electrons confined within NbTe2 chains is found to be substantially suppressed at Fermi energy, which follows a power law with a universal temperature scaling, hallmarking a TLL state. The obtained Luttinger parameter of ∼0.15 indicates a strong electron-electron interaction. The TLL behavior is found to be robust against atomic-scale defects, which might be related to the Dirac electron nature. These findings, combined with the tunability of the compound and the merit of a van der Waals material, offer a robust, tunable, and integrable platform to exploit non-Fermi liquid physics.

Ferrorotational Selectivity in Ilmenites.

Unlike what happens in conventional ferroics, the ferrorotational (FR) domain manipulation and visualization in FR materials are nontrivial as they are invariant under both space-inversion and time-reversal operations. FR domains have recently been observed by using the linear electrogyration (EG) effect and X-ray diffraction (XRD) diffraction mapping. However, ferrorotational selectivity, such as the selective processing of the FR domains and direct visualization of the FR domains, e.g., under an optical microscope, would be the next step to study the FR domains and their possible applications in technology. Unexpectedly, we discovered that the microscopic FR structural distortions in ilmenite crystals can be directly coupled with macroscopic mechanical rotations in such a way that FR domains can be visualized under an optical microscope after innovative rotational polishing, a combined ion milling with a specific rotational polishing, or a twisting-induced fracturing process. Thus, the FR domains could be a unique medium to register the memory of a rotational mechanical process due to a novel selective coupling between its microscopic structural rotations and an external macroscopic rotation. Analogous to the important enantioselectivity in modern chemistry and the pharmaceutical industry, this newly discovered ferrorotational selectivity opens up opportunities for FR manipulation and new FR functionality-based applications.

Isovalent Cation Ordering in the Polar Rhombohedral Perovskite Bi2 FeAlO6.

Ordering of cations in different structural types occurs when there is a significant difference in the oxidation states and ionic radii of the ions involved. Herein we report an unusual ordering of isovalent cations Fe3+ and Al3+ in the polar rhombohedral R3 double perovskite structure of Bi2 FeAlO6 synthesized at high-pressure (6 GPa) and high-temperature (1000 °C). This ordered structure is derived from the 1:1 combination of the polar oxides BiFeO3 (R3c) and BiAlO3 (R3c), which results in reduction of symmetry to an R3 structure where the Fe3+ and Al3+ ions are ordered in a rock salt manner. However, these ions remain disordered in BiFe1-x Alx O3 (x=0.2, 0.3, 0.4) perovskites with R3c structure. The ordered compound undergoes antiferromagnetic ordering at TN ≈280 K. The butterfly nature of piezoelectric displacement loop further confirms the polar nature of the cation-ordered Bi2 FeAlO6 .

The absence of ferroelectric polarization in layered and rock-salt ordered NaLnMnWO6 (Ln = La, Nd, Tb) perovskites.

The ordered perovskites, NaLnMnWO6 (Ln = La, Nd, Tb), are reported to exhibit simultaneous ordering of A-site cations (Na and Ln) in layered arrangement and B-site cations (Mn and W) in rock salt structure. They have been shown to crystallize in a monoclinic structure with the polar space group P21. Based on density functional calculations and group theoretical analysis, it has recently been proposed that NaLaMnWO6 should be ferroelectric with a relatively large polarization (16 µC cm(-2)). Contrary to this prediction, our electrical measurements such as conventional P-E loop, Positive-Up and Negative-Down (PUND), piezoelectric response and Second Harmonic Generation (SHG) reveal the absence of ferroelectric polarization in NaLnMnWO6 (Ln = La, Nd, Tb). A dielectric anomaly is observed just below room temperature (∼270 K) for all the three compounds, which is related to the change in conductivity as revealed by temperature dependent ac and dc resistivity. A pyrocurrent peak is also observed at the same temperature. However, its origin cannot be attributed to a ferroelectric transition.

Unconventional insulator-to-metal phase transition in Mn3Si2Te6.

The nodal-line semiconductor Mn3Si2Te6 is generating enormous excitment due to the recent discovery of a field-driven insulator-to-metal transition and associated colossal magnetoresistance as well as evidence for a new type of quantum state involving chiral orbital currents. Strikingly, these qualities persist even in the absence of traditional Jahn-Teller distortions and double-exchange mechanisms, raising questions about exactly how and why magnetoresistance occurs along with conjecture as to the likely signatures of loop currents. Here, we measured the infrared response of Mn3Si2Te6 across the magnetic ordering and field-induced insulator-to-metal transitions in order to explore colossal magnetoresistance in the absence of Jahn-Teller and double-exchange interactions. Rather than a traditional metal with screened phonons, the field-driven insulator-to-metal transition leads to a weakly metallic state with localized carriers. Our spectral data are fit by a percolation model, providing evidence for electronic inhomogeneity and phase separation. Modeling also reveals a frequency-dependent threshold field for carriers contributing to colossal magnetoresistance which we discuss in terms of polaron formation, chiral orbital currents, and short-range spin fluctuations. These findings enhance the understanding of insulator-to-metal transitions in new settings and open the door to the design of unconventional colossal magnetoresistant materials.

High-temperature concomitant metal-insulator and spin-reorientation transitions in a compressed nodal-line ferrimagnet Mn3Si2Te6.

Symmetry-protected band degeneracy, coupled with a magnetic order, is the key to realizing novel magnetoelectric phenomena in topological magnets. While the spin-polarized nodal states have been identified to introduce extremely-sensitive electronic responses to the magnetic states, their possible role in determining magnetic ground states has remained elusive. Here, taking external pressure as a control knob, we show that a metal-insulator transition, a spin-reorientation transition, and a structural modification occur concomitantly when the nodal-line state crosses the Fermi level in a ferrimagnetic semiconductor Mn3Si2Te6. These unique pressure-driven magnetic and electronic transitions, associated with the dome-shaped Tc variation up to nearly room temperature, originate from the interplay between the spin-orbit coupling of the nodal-line state and magnetic frustration of localized spins. Our findings highlight that the nodal-line states, isolated from other trivial states, can facilitate strongly tunable magnetic properties in topological magnets.

Large-Area Epitaxial Film Growth of van der Waals Ferromagnetic Ternary Chalcogenides.

Following the first experimental realization of intrinsic ferromagnetism in 2D van der Waals (vdW) crystals, several ternary metal chalcogenides with unprecedented long-range ferromagnetic order have been explored. However, the synthesis of large-area 2D ternary metal chalcogenide thin films is a great challenge, and a generalized synthesis has not been demonstrated yet. Here, a quick and scalable synthesis of epitaxially aligned ferromagnetic ternary metal chalcogenide thin films (Cr2 Ge2 Te6 , Cr2 Si2 Te6 , Mn3 Si2 Te6 ) is reported. The synthesis is based on the flux-controlled surface diffusion of Te on metal (Cr, Mn)-deposited wafer (Ge, Si) substrates. Magnetic anisotropy study of the epitaxial ternary thin films reveals the intrinsic magnetic easy axis; out-of-plane direction for Cr2 Ge2 Te6 and Cr2 Si2 Te6 , and in-plane direction for Mn3 Si2 Te6 . In addition to the synthesis, this work creates an opportunity for transfer-free device fabrication for realizing magnetoelectronics based on the electrical control of both charge and spin degrees of freedom in 2D ferromagnetic semiconductors.

New rare earth hafnium oxynitride perovskites with photocatalytic activity in water oxidation and reduction.

RHfO2N perovskites with R = La, Nd and Sm show a GdFeO3-type structure and are semiconductors with band gaps of 3.35, 3.40 and 2.85 eV and relative dielectric constants of 30, 16 and 28 respectively. These compounds have adequate reduction and oxidation potentials to conduct the overall water splitting reaction, and the analogous perovskite LaZrO2N with a band gap of 2.8 eV shows photocatalytic activity under visible light irradiation for O2 evolution.

Is CH3NH3PbI3 Polar?

In view of the continued controversy concerning the polar/nonpolar nature of the hybrid perovskite system, CH3NH3PbI3, we report the first investigation of a time-resolved pump-probe measurement of the second harmonic generation efficiency as well as using its more traditional form as a sensitive probe of the absence/presence of the center of inversion in the system both in its excited and ground states, respectively. Our results clearly show that SHG efficiency, if nonzero, is below the limit of detection, strongly indicative of a nonpolar or centrosymmetric structure. Our results on the same samples, based on temperature dependent single crystal X-ray diffraction and P-E loop measurements, are entirely consistent with the above conclusion of a centrosymmetric structure for this compound in all three phases, namely the high temperature cubic phase, the intermediate temperature tetragonal phase and the low temperature orthorhombic phase. It is important to note that all our experimental probes are volume averaging and performed on bulk materials, suggesting that basic material properties of CH3NH3PbI3 are consistent with a centrosymmetric, nonpolar structure.