Two superconducting states with broken time-reversal symmetry in FeSe1-xSx.

Iron-chalcogenide superconductors FeSe1-xSx possess unique electronic properties such as nonmagnetic nematic order and its quantum critical point. The nature of superconductivity with such nematicity is important for understanding the mechanism of unconventional superconductivity. A recent theory suggested the possible emergence of a fundamentally new class of superconductivity with the so-called Bogoliubov Fermi surfaces (BFSs) in this system. However, such an ultranodal pair state requires broken time-reversal symmetry (TRS) in the superconducting state, which has not been observed experimentally. Here, we report muon spin relaxation (µSR) measurements in FeSe1-xSx superconductors for 0 ≤ x ≤ 0.22 covering both orthorhombic (nematic) and tetragonal phases. We find that the zero-field muon relaxation rate is enhanced below the superconducting transition temperature Tc for all compositions, indicating that the superconducting state breaks TRS both in the nematic and tetragonal phases. Moreover, the transverse-field µSR measurements reveal that the superfluid density shows an unexpected and substantial reduction in the tetragonal phase (x > 0.17). This implies that a significant fraction of electrons remain unpaired in the zero-temperature limit, which cannot be explained by the known unconventional superconducting states with point or line nodes. The TRS breaking and the suppressed superfluid density in the tetragonal phase, together with the reported enhanced zero-energy excitations, are consistent with the ultranodal pair state with BFSs. The present results reveal two different superconducting states with broken TRS separated by the nematic critical point in FeSe1-xSx, which calls for the theory of microscopic origins that account for the relation between nematicity and superconductivity.

Author Correction: Single Crystal Growth and Spin Polarization Measurements of Diluted Magnetic Semiconductor (BaK)(ZnMn)2As2.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Single Crystal Growth and Spin Polarization Measurements of Diluted Magnetic Semiconductor (BaK)(ZnMn)2As2.

Recently a new diluted magnetic semiconductor, (Ba,K)(Zn,Mn)2As2 (BZA), with high Curie temperature was discovered, showing an independent spin and charge-doping mechanism. This makes BZA a promising material for spintronics devices. We report the successful growth of a BZA single crystal for the first time in this study. An Andreev reflection junction, which can be used to evaluate spin polarization, was fabricated based on the BZA single crystal. A 66% spin polarization of the BZA single crystal was obtained by Andreev reflection spectroscopy analysis.

New Fluoride-arsenide Diluted Magnetic Semiconductor (Ba,K)F(Zn,Mn)As with Independent Spin and Charge Doping.

We report the discovery of a new fluoride-arsenide bulk diluted magnetic semiconductor (Ba,K)F(Zn,Mn)As with the tetragonal ZrCuSiAs-type structure which is identical to that of the "1111" iron-based superconductors. The joint hole doping via (Ba,K) substitution &spin doping via (Zn,Mn) substitution results in ferromagnetic order with Curie temperature up to 30 K and demonstrates that the ferromagnetic interactions between the localized spins are mediated by the carriers. Muon spin relaxation measurements confirm the intrinsic nature of the long range magnetic order in the entire volume in the ferromagnetic phase. This is the first time that a diluted magnetic semiconductor with decoupled spin and charge doping is achieved in a fluoride compound. Comparing to the isostructure oxide counterpart of LaOZnSb, the fluoride DMS (Ba,K)F(Zn,Mn)As shows much improved semiconductive behavior that would be benefit for further application developments.

Volume-wise destruction of the antiferromagnetic Mott insulating state through quantum tuning.

RENiO3 (RE=rare-earth element) and V2O3 are archetypal Mott insulator systems. When tuned by chemical substitution (RENiO3) or pressure (V2O3), they exhibit a quantum phase transition (QPT) between an antiferromagnetic Mott insulating state and a paramagnetic metallic state. Because novel physics often appears near a Mott QPT, the details of this transition, such as whether it is first or second order, are important. Here, we demonstrate through muon spin relaxation/rotation (µSR) experiments that the QPT in RENiO3 and V2O3 is first order: the magnetically ordered volume fraction decreases to zero at the QPT, resulting in a broad region of intrinsic phase separation, while the ordered magnetic moment retains its full value until it is suddenly destroyed at the QPT. These findings bring to light a surprising universality of the pressure-driven Mott transition, revealing the importance of phase separation and calling for further investigation into the nature of quantum fluctuations underlying the transition.

Verification of Anderson Superexchange in MnO via Magnetic Pair Distribution Function Analysis and ab initio Theory.

We present a temperature-dependent atomic and magnetic pair distribution function (PDF) analysis of neutron total scattering measurements of antiferromagnetic MnO, an archetypal strongly correlated transition-metal oxide. The known antiferromagnetic ground-state structure fits the low-temperature data closely with refined parameters that agree with conventional techniques, confirming the reliability of the newly developed magnetic PDF method. The measurements performed in the paramagnetic phase reveal significant short-range magnetic correlations on a ∼1 nm length scale that differ substantially from the low-temperature long-range spin arrangement. Ab initio calculations using a self-interaction-corrected local spin density approximation of density functional theory predict magnetic interactions dominated by Anderson superexchange and reproduce the measured short-range magnetic correlations to a high degree of accuracy. Further calculations simulating an additional contribution from a direct exchange interaction show much worse agreement with the data. The Anderson superexchange model for MnO is thus verified by experimentation and confirmed by ab initio theory.

Intra-unit-cell nematic charge order in the titanium-oxypnictide family of superconductors.

Understanding the role played by broken-symmetry states such as charge, spin and orbital orders in the mechanism of emergent properties, such as high-temperature superconductivity, is a major current topic in materials research. That the order may be within one unit cell, such as nematic, was only recently considered theoretically, but its observation in the iron-pnictide and doped cuprate superconductors places it at the forefront of current research. Here, we show that the recently discovered BaTi2Sb2O superconductor and its parent compound BaTi2As2O form a symmetry-breaking nematic ground state that can be naturally explained as an intra-unit-cell nematic charge order with d-wave symmetry, pointing to the ubiquity of the phenomenon. These findings, together with the key structural features in these materials being intermediate between the cuprate and iron-pnictide high-temperature superconducting materials, render the titanium oxypnictides an important new material system to understand the nature of nematic order and its relationship to superconductivity.

Ferromagnetic ordering in superatomic solids.

In order to realize significant benefits from the assembly of solid-state materials from molecular cluster superatomic building blocks, several criteria must be met. Reproducible syntheses must reliably produce macroscopic amounts of pure material; the cluster-assembled solids must show properties that are more than simply averages of those of the constituent subunits; and rational changes to the chemical structures of the subunits must result in predictable changes in the collective properties of the solid. In this report we show that we can meet these requirements. Using a combination of magnetometry and muon spin relaxation measurements, we demonstrate that crystallographically defined superatomic solids assembled from molecular nickel telluride clusters and fullerenes undergo a ferromagnetic phase transition at low temperatures. Moreover, we show that when we modify the constituent superatoms, the cooperative magnetic properties change in predictable ways.