Superconductivity under pressure in a chromium-based kagome metal.

Superconductivity in a highly correlated kagome system has been theoretically proposed for years (refs. 1-5), yet the experimental realization is hard to achieve6,7. The recently discovered vanadium-based kagome materials8, which exhibit both superconductivity9-11 and charge-density-wave orders12-14, are nonmagnetic8,9 and weakly correlated15,16. Thus these materials are unlikely to host the exotic superconductivity theoretically proposed. Here we report the discovery of a chromium-based kagome metal, CsCr3Sb5, which is contrastingly featured with strong electron correlations, frustrated magnetism and characteristic flat bands close to the Fermi level. Under ambient pressure, this kagome metal undergoes a concurrent structural and magnetic phase transition at 55 K, with a stripe-like 4a0 structural modulation. At high pressure, the phase transition evolves into two transitions, possibly associated with charge-density-wave and antiferromagnetic spin-density-wave orderings. These density-wave-like orders are gradually suppressed with pressure and, remarkably, a superconducting dome emerges at 3.65-8.0 GPa. The maximum of the superconducting transition temperature, Tcmax = 6.4 K, appears when the density-wave-like orders are completely suppressed at 4.2 GPa, and the normal state exhibits a non-Fermi-liquid behaviour, reminiscent of unconventional superconductivity and quantum criticality in iron-based superconductors17,18. Our work offers an unprecedented platform for investigating superconductivity in correlated kagome systems.

Evidence of electron interaction with an unidentified bosonic mode in superconductor CsCa2Fe4As4F2.

The kink structure in band dispersion usually refers to a certain electron-boson interaction, which is crucial in understanding the pairing in unconventional superconductors. Here we report the evidence of the observation of a kink structure in Fe-based superconductor CsCa2Fe4As4F2 using angle-resolved photoemission spectroscopy. The kink shows an orbital selective and momentum dependent behavior, which is located at 15 meV below Fermi level along the Γ - M direction at the band with dxz orbital character and vanishes when approaching the Γ - X direction, correlated with a slight decrease of the superconducting gap. Most importantly, this kink structure disappears when the superconducting gap closes, indicating that the corresponding bosonic mode (~ 9 ± 1 meV) is closely related to superconductivity. However, the origin of this mode remains unidentified, since it cannot be related to phonons or the spin resonance mode (~15 meV) observed by inelastic neutron scattering. The behavior of this mode is rather unique and challenges our present understanding of the superconducting paring mechanism of the bilayer FeAs-based superconductors.

Layer-Dependent Superconductivity in Iron-Based Superconductors CsCa2Fe4As4F2 and CaKFe4As4.

In the quasi-two-dimensional superconductor NbSe2, the superconducting transition temperature (Tc) is layer-dependent, decreasing by about 60% in the monolayer limit. However, for the extremely anisotropic copper-based high-Tc superconductor Bi2Sr2CaCu2O8+δ (Bi-2212), the Tc of the monolayer is almost identical with that of its bulk counterpart. To clarify the effect of dimensionality on superconductivity, here, we successfully fabricate ultrathin flakes of iron-based high-Tc superconductors CsCa2Fe4As4F2 and CaKFe4As4. It is found that the Tc of monolayer CsCa2Fe4As4F2 (after tuning to the optimal doping by ionic liquid gating) is about 20% lower than that of the bulk crystal, while the Tc of three-layer CaKFe4As4 decreases by 46%, showing a more pronounced dimensional effect than that of CsCa2Fe4As4F2. By carefully examining their anisotropy and the c-axis coherence length, we reveal the general trend and empirical law of the layer-dependent superconductivity in these quasi-two-dimensional superconductors.

Superconductivity and Charge-Density-Wave-Like Transition in Th2Cu4As5.

We report the synthesis, crystal structure, and physical properties of a novel ternary compound, Th2Cu4As5. The material crystallizes in a tetragonal structure with lattice parameters a = 4.0639(3) Å and c = 24.8221(17) Å. Its structure can be described as an alternating stacking of fluorite-type Th2As2 layers with antifluorite-type double-layered Cu4As3 slabs. The measurement of electrical resistivity, magnetic susceptibility, and specific heat reveals that Th2Cu4As5 undergoes bulk superconducting transition at 4.2 K. Additionally, all these physical quantities exhibit anomalies at 48 K, accompanied by a sign change in the Hall coefficient, suggesting a charge-density-wave-like (CDW) phase transition. Drawing from both experimental data and band calculations, we propose that the superconducting and CDW-like phase transitions are, respectively, associated with the Cu4As3 slabs and the As plane in the Th2As2 layers.

ThCr2Si2C: An Antiferromagnetic Metal with a Cr2C Square Lattice.

A quaternary compound, ThCr2Si2C, was synthesized by using the arc-melting technique. The compound adopts a tetragonal CeCr2Si2C-type crystal structure. The electronic resistivity and specific heat data exhibit metallic behavior, while the magnetic susceptibility displays a pronounced broad peak at around 370 K, indicating the antiferromagnetic phase transition. The first-principles calculations suggest A-type antiferromagnetic ordering of the Cr sublattice, which is confirmed by neutron diffraction experiments. By comparing the crystal structure of ThCr2Si2C with the isostructural Cr-based compounds, the magnetic state of Cr 3d orbital is discussed in terms of the band-filling effects and indirect spin exchange interaction.

Spin-Lattice Coupled Metamagnetism in Frustrated van der Waals Magnet CrOCl.

The long-range magnetic ordering in frustrated magnetic systems is stabilized by coupling magnetic moments to various degrees of freedom, for example, by enhancing magnetic anisotropy via lattice distortion. Here, the unconventional spin-lattice coupled metamagnetic properties of atomically-thin CrOCl, a van der Waals antiferromagnet with inherent magnetic frustration rooted in the staggered square lattice, are reported. Using temperature- and angle-dependent tunneling magnetoconductance (TMC), in complementary with magnetic torque and first-principles calculations, the antiferromagnetic (AFM)-to-ferrimagnetic (FiM) metamagnetic transitions (MTs) of few-layer CrOCl are revealed to be triggered by collective magnetic moment flipping rather than the established spin-flop mechanism, when external magnetic field (H) enforces a lattice reconstruction interlocked with the five-fold periodicity of the FiM phase. The spin-lattice coupled MTs are manifested by drastic jumps in TMC, which show anomalous upshifts at the transition thresholds and persist much higher above the AFM Néel temperature. While the MTs exhibit distinctive triaxial anisotropy, reflecting divergent magnetocrystalline anisotropy of the c-axis AFM ground state, the resulting FiM phase has an a-c easy plane in which the magnetization axis is freely rotated by H. At the 2D limit, such a field-tunable FiM phase may provide unique opportunities to explore exotic emergent phenomena and novel spintronics devices.

Orbital-Hybridization-Driven Charge Density Wave Transition in CsV3 Sb5 Kagome Superconductor.

Owing to its inherent non-trivial geometry, the unique structural motif of the recently discovered kagome topological superconductor AV3 Sb5 (A = K, Rb, Cs) is an ideal host of diverse topologically non-trivial phenomena, including giant anomalous Hall conductivity, topological charge order, charge density wave (CDW), and unconventional superconductivity. Despite possessing a normal-state CDW order in the form of topological chiral charge order and diverse superconducting gaps structures, it remains unclear how fundamental atomic-level properties and many-body effects including Fermi surface nesting, electron-phonon coupling, and orbital hybridization contribute to these symmetry-breaking phenomena. Here, the direct participation of the V3d-Sb5p orbital hybridization in mediating the CDW phase transition in CsV3 Sb5 is reported. The combination of temperature-dependent X-ray absorption and first-principles studies clearly indicates the inverse Star-of-David structure as the preferred reconstruction in the low-temperature CDW phase. The results highlight the critical role that Sb orbitals play and establish orbital hybridization as the direct mediator of the CDW states and structural transition dynamics in kagome unconventional superconductors. This is a significant step toward the fundamental understanding and control of the emerging correlated phases from the kagome lattice through the orbital interactions and provides promising approaches to novel regimes in unconventional orders and topology.

Structure and Physical Properties of the Layered Titanium-Based Pnictide Oxides (EuF)2Ti2Pn2O (Pn = Sb, Bi).

We report two novel titanium-based pnictide oxide compounds (EuF)2Ti2Pn2O (Pn = Sb, Bi), which are synthesized by replacing Sr2+ in (SrF)2Ti2Pn2O [Liu, R. H. Structure and Physical Properties of the Layered Pnictide-Oxides: (SrF)2Ti2Pn2O (Pn = As, Sb) and (SmO)2Ti2Sb2O. Chem. Mater. 2010, 22, 1503-1508] with Eu2+ using a solid-state reaction. (EuF)2Ti2Sb2O exhibits an obvious anomaly in resistivity and heat capacity at T ∼ 195 K, which may arise from the spin-density wave/charge-density wave instability. Similar features are also observed in BaTi2Pn2O, (SrF)2Ti2Pn2O, and Na2Ti2Pn2O (Pn = As and Sb) [Liu, R. H. Structure and Physical Properties of the Layered Pnictide-Oxides: (SrF)2Ti2Pn2O (Pn = As, Sb) and (SmO)2Ti2Sb2O. Chem. Mater. 2010, 22, 1503-1508, Ozawa, T. C. Chemistry of layered d-metal pnictide oxides and their potential as candidates for new superconductors. Sci. Technol. Adv. Mater. 2008, 9, 033003, Wang, X. F. Structure and physical properties for a new layered pnictide-oxide: BaTi2As2O. J. Phys.: Condens. Matter. 2010, 22, 075702, and Xu, H. C. Electronic structure of the BaTi2As2O parent compound of the titanium-based oxypnictide superconductor. Phys. Rev. B 2014, 89, 155108]. Magnetic susceptibility measurements indicate an antiferromagnetic transition at T ∼ 2.5 K for (EuF)2Ti2Sb2O. In particular, the electronic specific heat coefficients of both (EuF)2Ti2Sb2O and (EuF)2Ti2Bi2O are significantly enhanced compared to those of (SrF)2Ti2Pn2O, Na2Ti2Pn2O, and BaTi2Pn2O,1,5,6 which may be due to a strong electron correlation effect in this system. Thus, (EuF)2Ti2Pn2O (Pn = Sb, Bi) may provide new platforms for studying density wave, magnetic ordering, and electron correlation effects.

Mo3ReRuC: A Noncentrosymmetric Superconductor Formed in the MoReRu-Mo2C System.

A quaternary compound with the composition Mo3ReRuC is obtained in a previously unexplored MoReRu-Mo2C system. According to X-ray structural analysis, Mo3ReRuC crystallizes in the noncentrosymmetric space group P4132 [cubic ß-Mn-type structure, a = 6.8107(1) Å]. Below 7.7 K, Mo3ReRuC becomes a bulk type-II superconductor with an upper critical field close to the Pauli paramagnetic limit. The specific heat data give a large normalized jump ΔCp/γTc = 2.3 at Tc, which points to a strongly coupled superconducting state. First-principles calculations show that its electronic states at the Fermi level are mainly contributed by Mo, Re, and Ru atoms and strongly increased by the spin-orbit coupling. Our finding suggests that the intermediate phase between alloys and carbides may be a good place to look for ß-Mn-type noncentrosymmetric superconductors.

Pressure effect on magnetism and valence in ferromagnetic superconductor Eu(Fe0.75Ru0.25)2As2.

Eu(Fe0.75Ru0.25)2As2is an intriguing system with unusual coexistence of superconductivity and ferromagnetism, providing a unique platform to study the nature of such coexistence. To establish a magnetic phase diagram, time-domain synchrotron Mössbauer experiments in151Eu have been performed on a single crystalline Eu(Fe0.75Ru0.25)2As2sample under hydrostatic pressures and at low temperatures. Upon compression the magnetic ordering temperature increases sharply from 20 K at ambient pressure, reaching ∼49 K at 10.1 GPa. With further compression, the magnetic order is suppressed and eventually collapses. Isomer shift values from Mössbauer measurements and x-ray absorption spectroscopy data at EuL3edge show that pressure drives Eu ions to a homogeneous intermediate valence state with mean valence of ∼2.4 at 27.4 GPa, possibly responsible for the suppression of magnetism. Synchrotron powder x-ray diffraction experiment reveals a tetragonal to collapsed-tetragonal structural transition around 5 GPa, a lower transition pressure than in the parent compound. These results provide guidance to further work investigating the interplay of superconductivity and magnetism.

Structural, Electronic, and Physical Properties of a New Layered Cr-Based Oxyarsenide Sr2Cr2AsO3.

We report synthesis, crystal structure, and physical properties of Sr2Cr2AsO3. The new compound crystallizes in a Sr2GaO3CuS-type structure with two distinct Cr sites, Cr(1) in the perovskite-like block layers of "Sr3Cr2O6" and Cr(2) in the ThCr2Si2-type layers of "SrCr2As2". An inter-block-layer charge transfer is explicitly evidenced, which dopes electrons in the CrO2 planes and simultaneously dopes holes into the CrAs layers. Measurements of electrical resistivity, magnetization, and specific heat, in combination with density-functional theoretical calculations, indicate that the title material is an antiferromagnetic metal. The Cr(2) magnetic moments in the CrAs layers order at 420 K, while the Cr(1) spins in the CrO2 planes show quasi-two-dimensional magnetism with long-range ordering below 80 K. Both Néel temperatures are significantly reduced, compared with those of the cousin material Sr2Cr3As2O2, probably due to the intrinsic charge-carrier doping. Complex re-entrant magnetic transitions with a huge magnetic hysteresis were observed at low temperatures.

High-Frequency ac Susceptibility of Iron-Based Superconductors.

A microwave technique suitable for investigating the AC magnetic susceptibility of small samples in the GHz frequency range is presented. The method-which is based on the use of a coplanar waveguide resonator, within the resonator perturbation approach-allows one to obtain the absolute value of the complex susceptibility, from which the penetration depth and the superfluid density can be determined. We report on the characterization of several iron-based superconducting systems, belonging to the 11, 122, 1144, and 12442 families. In particular, we show the effect of different kinds of doping for the 122 family, and the effect of proton irradiation in a 122 compound. Finally, the paradigmatic case of the magnetic superconductor EuP-122 is discussed, since it shows the emergence of both superconducting and ferromagnetic transitions, marked by clear features in both the real and imaginary parts of the AC susceptibility.

Commensurate Stacking Phase Transitions in an Intercalated Transition Metal Dichalcogenide.

Intercalation and stacking-order modulation are two active ways in manipulating the interlayer interaction of transition metal dichalcogenides (TMDCs), which lead to a variety of emergent phases and allow for engineering material properties. Herein, the growth of Pb-intercalated TMDCs-Pb(Ta1+x Se2 )2 , the first 124-phase, is reported. Pb(Ta1+x Se2 )2 exhibits a unique two-step first-order structural phase transition at around 230 K. The transitions are solely associated with the stacking degree of freedom, evolving from a high-temperature (high-T) phase with ABC stacking and R3m symmetry to an intermediate phase with AB stacking and P3m1, and finally to a low-temperature (low-T) phase again with R3msymmetry, but with ACB stacking. Each step involves a rigid slide of building blocks by a vector [1/3, 2/3, 0]. Intriguingly, gigantic lattice contractions occur at the transitions on warming. At low-T, bulk superconductivity with Tc  ≈ 1.8 K is observed. The underlying physics of the structural phase transitions are discussed from first-principle calculations. The symmetry analysis reveals topological nodal lines in the band structure. The results demonstrate the possibility of realizing higher-order metal-intercalated phases of TMDCs and advance the knowledge of polymorphic transitions, and may inspire stacking-order engineering in TMDCs and beyond.

Possible Evidence for Berezinskii-Kosterlitz-Thouless Transition in Ba(Fe0.914Co0.086)2As2 Crystals.

In this study, we measure the in-plane transport properties of high-quality Ba(Fe0.914Co0.086)2As2 single crystals. Signatures of vortex unbinding Berezinskii-Kosterlitz-Thouless (BKT) transition are shown from both the conventional approach and the Fisher-Fisher-Huse dynamic scaling analysis, in which a characteristic Nelson-Kosterlitz jump is demonstrated. We also observe a non-Hall transverse signal exactly at the superconducting transition, which is explained in terms of guided motion of unbound vortices.

Iron-based magnetic superconductorsAEuFe4As4(A=Rb, Cs): natural superconductor-ferromagnet hybrids.

Superconductivity (SC) and ferromagnetism (FM) are normally antagonistic, and their coexistence in a single crystalline material appears to be very rare. Over a decade ago, the iron-based pnictides of doped EuFe2As2were found to render such a coexistence, primarily because of the Fe-3dmulti-orbitals which simultaneously satisfy the superconducting pairing and the ferromagnetic exchange interaction among Eu local spins. In 2016, the discovery of the iron-based superconductorsAEuFe4As4(A= Rb, Cs) provided an additional and complementary material basis for the study of the coexistence and the interplay between SC and FM. The two sibling compounds, which can be viewed as an intergrowth or a hybrid betweenAFe2As2and EuFe2As2, show SC in the FeAs bilayers atTc= 35-37 K and magnetic ordering atTm∼ 15 K in the sandwiched Eu2+-ion sheets. BelowTm, the Eu2+spins align ferromagnetically within each Eu plane, making the system as a natural atomic-thick superconductor-ferromagnet superlattice. This paper reviews the main research progress in the emerging topic during the past five years. An outlook for the future research opportunities is also presented.

Associations of urinary phenolic environmental estrogens exposure with blood glucose levels and gestational diabetes mellitus in Chinese pregnant women.

BACKGROUND: Endocrine-disrupting chemicals (EDCs) are considered to be related to diabetes, but studies of the association between phenolic EDCs and gestational diabetes mellitus (GDM) are limited. OBJECTIVES: To assess associations of maternal urinary bisphenol A (BPA), nonylphenol (NP), and 2-tert-octylphenol (2-t-OP) with GDM occurrence. METHODS: A cross-sectional study was performed among 390 Chinese women at 24-28 weeks of gestation. GDM was diagnosed with a 2-h 75-g oral glucose tolerance test (OGTT). BPA, NP, and 2-t-OP concentrations were determined in urine samples. Linear and logistic regression tests evaluated associations of BPA, NP, and 2-t-OP with blood glucose levels and GDM prevalence. RESULTS: The 2-t-OP concentrations in GDM patients were significantly higher than in non-GDM women with median values of 2.23 µg/g Cr and 1.79 µg/g Cr, respectively. No significant difference was observed in BPA and NP. Urinary 2-t-OP was positively associated with blood glucose levels after adjustment for several confounding factors and urinary BPA and NP. Higher 2-t-OP levels were associated with higher odds of GDM (OR: 5.78; 95% CI: 2.04, 16.37), whereas higher NP levels were associated with lower odds (OR: 0.22; 95% CI: 0.05, 0.85) in the adjusted models. In addition, compared to the first quartile of 2-t-OP, the adjusted odds ratios (ORs) and 95% confidence intervals (95% CIs) for GDM in the second, third, and fourth quartiles were 2.81 (1.23, 6.42), 3.01 (1.30, 6.93), and 5.49 (2.24, 13.46), respectively. CONCLUSION: Our study indicates that, for the first time to our knowledge, exposure to 2-t-OP is associated with a higher risk of GDM. However, higher NP exposure is associated with lower GDM risk. Further studies are necessary to affirm the associations of 2-t-OP and NP with GDM, and to elucidate the causality of these findings.

A new Majorana platform in an Fe-As bilayer superconductor.

Iron-chalcogenide superconductors have emerged as a promising Majorana platform for topological quantum computation. By combining topological band and superconductivity in a single material, they provide significant advantage to realize isolated Majorana zero modes. However, iron-chalcogenide superconductors, especially Fe(Te,Se), suffer from strong inhomogeneity which may hamper their practical application. In addition, some iron-pnictide superconductors have been demonstrated to have topological surface states, yet no Majorana zero mode has been observed inside their vortices, raising a question of universality about this new Majorana platform. In this work, through angle-resolved photoemission spectroscopy and scanning tunneling microscopy/spectroscopy measurement, we identify Dirac surface states and Majorana zero modes, respectively, for the first time in an iron-pnictide superconductor, CaKFe4As4. More strikingly, the multiple vortex bound states with integer-quantization sequences can be accurately reproduced by our model calculation, firmly establishing Majorana nature of the zero mode.

ThMnPnN (Pn = P, As): Synthesis, Structure, and Chemical Pressure Effects.

Mn-based ZrCuSiAs-type pnictides ThMnPnN (Pn = P, As) containing PbO-type Th2N2 layers were synthesized. The crystal and magnetic structures are determined using X-ray and neutron powder diffraction. While neutron diffraction indicates a C-type antiferromagnetic state at 300 K, the temperature dependence of the magnetic susceptibility shows cusps at 36 and 52 K respectively for ThMnPN and ThMnAsN. The susceptibility cusps are ascribed to a spontaneous antiferromagnetic-to-antiferromagnetic transition for Mn2+ moments, which is observed for the first time in Mn-based ZrCuSiAs-type compounds. In addition, measurements of the resistivity and specific heat suggest an abnormal increase in the density of states at the Fermi energy. The result is discussed in terms of the internal chemical pressure effect.

Superconductivity and magnetism in RbEu(Fe1-x Co x )4As4.

We studied the cobalt-doping effect on superconductivity and magnetism in a hole self-doped RbEuFe4As4 magnetic superconductor which shows superconductivity at [Formula: see text] 36.5 K and Eu2+ -spin ordering at [Formula: see text] 15 K. The Co solubility limit in RbEu(Fe1-x Co x )4As4 achieves x = 0.21 for the solid-state reaction at 880 °C. With increasing x, [Formula: see text] decreases gradually, and superconductivity eventually disappears at [Formula: see text]. A spin-density-wave transition at [Formula: see text] 35-40 K is recovered for [Formula: see text], which can be understood in terms of the hole-depletion and the disorder effects. On the other hand, [Formula: see text] remains unchanged despite the Co doping and, consequently, an intriguing superconducting ferromagnet without Meissner state is realized in the range of 0.125 [Formula: see text] 0.155. Our results indicate that the Eu2+ spins essentially decouple with superconductivity over a wide doping range, making the coexistence of superconductivity and ferromagnetism possible in the 1144-type system.

Degradation of gas-phase o-xylene via combined non-thermal plasma and Fe doped LaMnO3 catalysts: Byproduct control.

A series of Fe doped LaMnO3 catalysts were prepared to control the production of byproducts such as O3, N2O, and CO, during the degradation of volatile organic compounds with a non-thermal plasma. Eliminating these potentially toxic byproducts will make non-thermal plasma technologies applicable for a wider range of commercial applications. The modified LaMnO3 catalysts are combined in NTP-catalysis reactor with optimal configuration. Experimental results show that doping Fe on LaMnO3 catalysts can not only enhance the oxidation of o-xylene, but also lower the emission levels of byproducts. LaMn0.9Fe0.1O3 catalyst shows the best catalytic activity among the formulations tested herein. In addition to the strong mineralization of 88.1 %, the catalyst has the highest performance for o-xylene conversion (91.3 %), O3 inhibition efficiency (84.9 %), and N2O inhibition efficiency (61.2 %) due to the strong concentration of active oxygen species on the surface of the catalyst. Moreover, the high reducibility of Fe3+ demonstrated with H2-TPR (hydrogen temperature-programed reduction) further enhances the removal of O3 by oxygen species exchange between Mn3+/Mn4+ and Fe2+/Fe3+.