By first-principles calculations, we present a doping-dependent phase diagram of LaO{\it M}As ({\it M}=V--Cu) family. It is characterized as antiferromagnetic semiconductor around LaOMnAs side and ferromagnetic metal around LaOCoAs. Both LaOFeAs and LaONiAs, where superconductivity were discovered, are located at the borderline of magnetic phases. Extensive Fermi surface analysis suggests that the observed superconductivity is of electron-type in its origin. We discuss possible pairing mechanisms in the context of competing ferromagnetic phases found in this work and the ferromagnetic spin fluctuations.
We report the synthesis and characterization of antimony doped oxypnictide superconductor, LaO0.8F0.2FeAs1-xSbx (x = 0.05 and 0.10). The parent compound LaOFeAs with fluorine doping exhibits superconductivity at maximum transition temperature ~ 28.5 K [11]. Here we partially substitute As by Sb (LaO0.8F0.2FeAs1-xSbx) and observe enhancement of the transition temperature to 30.1 K. This is the only instance so far where Tc increases with doping in the conducting layer (FeAs) and this leads to the highest transition temperature in any La-based oxypnictide. XRD and EDAX measurements confirm phase…
The layered compound LaOBiSSe was successfully synthesized by a two-step solid-state reaction method, which is isostructural with the quaternary compound LaOBiS2 indicated by the powder X-ray diffraction characterization, and the crystal lattice parameters are slightly expanded by the substitution of Se atoms. Electrical transport measurement shows that LaOBiSSe exhibits semiconducting behavior similar with the parent compound LaOBiS2, while by F-doping the samples can be much more easily turned to be metallic and superconducting at low temperature with a small amount of F. Under the optimal c…
Theoretical calculations under the scheme of WIEN2k computer package had been performed on the pristine compound LaOFeAs, as well as on LaO1-xFxFeAs. One factor crucial to the manifestation of superconductivity seems to be fluorine doping; hence we search for its effect. Paying close attention to Fe d-orbitals upon doping of F by O, at first, Fe d-orbitals have dz2 symmetry, changing gradually to something akin to dx2-y2 which seems more prone to conductivity than the former one. This issue agree with the accepted results happened in the copper-based high-temperature superconductors.
Raman spectra have been measured on iron-based quaternary CeO$_{1-x}$F$_x$FeAs and LaO$_{1-x}$F$_x$FeAs with varying fluorine doping at room temperatures. A group analysis has been made to clarify the optical modes. Based on the first principle calculations, the observed phonon modes can be assigned accordingly. In LaO$_{1-x}$F$_x$FeAs, the E$_g$ and A$_{1g}$ modes related to the vibrations of La, are suppressed with increasing F doping. However F doping only has a small effect on the E$_g$ and A$_{1g}$ modes of Fe and As. The Raman modes of La and As are absent in rare-earth substituted CeO$_…
Using state-of-the-art first-principles calculations we have elucidated the complex magnetic and structural dependence of LaOFeAs upon doping. Our key findings are that (i) doping results in an orthorhombic ground state and (ii) there is a commensurate to incommensurate transition in the magnetic structure between $x=0.025$ and $x=0.04$. Our calculations further imply that in this system magnetic order persists up to the onset of superconductivity at the critical doping of $x=0.05$. Finally, our investigations of the undoped parent compound reveal an unusually pronounced dependence of the magn…
Ferromagnetism and superconductivity are in most cases adverse. However, recent experiments reveal that they coexist at interfaces of LaAlO3 and SrTiO3. We analyze the magnetic state within density functional theory and provide evidence that magnetism is not an intrinsic property of the two-dimensional electron liquid at the interface. We demonstrate that the robust ferromagnetic state is induced by the oxygen vacancies in SrTiO3- or in the LaAlO3-layer. This allows for the notion that areas with increased density of oxygen vacancies produce ferromagnetic puddles and account for the previous o…
A recent experiment reported the first rare-earth binary oxide superconductor LaO ($T_c $ $\sim$ 5 K) with a rock-salt structure [K. Kaminaga et al., J. Am. Chem. Soc. 140, 6754 (2018)]. Correspondingly, the underlying superconducting mechanism in LaO needs theoretical elucidation. Based on first-principles calculations on the electronic structure, lattice dynamics, and electron-phonon coupling of LaO, we show that the superconducting pairing in LaO belongs to the conventional Bardeen-Cooper-Schrieffer (BCS) type. Remarkably, the electrons and phonons of the heavy La atoms, instead of those of…
The Fermi surfaces (FS) of LaOFeAs (in $k_z$=0 plane) consist of two hole-type circles around $Γ$ point, which do not touch each other, and two electron-type co-centered ellipses around M point, which are degenerate along the M-X line. By first-principles calculations, here we show that additional degeneracy exists for the two electron-type FS, and the crucial role of F-doping and pressure is to enhance this orbital degeneracy. It is suggested that the inter-orbital fluctuation is the key point to understand the unconventional superconductivity in these materials.
By means of first-principles calculations? we have probed the peculiarities of the elecrtonic band structure and Fermi surface for the recently discovered layered superconductor LaO0.5F0.5BiSi2 in comparison with the parent phase LaOBiO2. The electronic factors prpmoting the transition of LaOBiS2 upon fluorine doping to superconducting state: inter-layer charge transfer, the evolution of the Fermi surface, and the dependence of the near-Fermi densities of states on x for LaO1-xFxBiS2 are evaluated and discussed in comparison with the available experiments.
Using state-of-the-art first-principles calculations we study the magnetic behaviour of CeOFeAs. We find the Ce layer moments oriented perpendicular to those of the Fe layers. An analysis of incommensurate magnetic structures reveals that the Ce-Ce magnetic coupling is rather weak with, however, a strong Fe-Ce coupling. Comparison of the origin of the tetragonal to orthorhombic structural distortion in CeOFeAs and LaOFeAs show marked differences; in CeOFeAs the distortion is stabilized by a lowering of spectral weight at the Fermi level, while in LaOFeAs by a reduction in magnetic frustration.…
We constructed an effective tight-binding model with five Cr $3d$ orbitals for LaOCrAs according to first-principles calculations. Basing on this model, we investigated possible superconductivity induced by correlations in doped LaOCrAs using the functional renormalization group (FRG). We find that there are two domes of superconductivity in electron-doped LaOCrAs. With increasing electron doping, the ground state of the system evolves from G-type antiferromagnetism in the parent compound to an incipient $s_\pm$-wave superconducting phase dominated by electron bands derived from the $d_{3z^2-r…
Neutron scattering measurements have been performed on polycrystalline samples of the newly discovered layered superconductor LaO$_{0.5}$F$_{0.5}$BiS$_{2}$, and its nonsuperconducting parent compound LaOBiS$_{2}$. The crystal structures and vibrational modes have been examined. Upon F-doping, while the lattice contracts significantly along $c$ and expands slightly along $a$, the buckling of the BiS$_2$ plane remains almost the same. In the inelastic measurements, a large difference in the high energy phonon modes was observed upon F substitution. Alternatively, the low energy modes remain almo…
Within the framework of density functional theory we investigate the nature of magnetism in various families of Fe-based superconductors. (i) We show that magnetization of stripe-type antiferromagnetic order always becomes stronger when As is substituted by Sb in LaOFeAs, BaFe$_2$As$_2$ and LiFeAs. By calculating Pauli susceptibilities, we attribute the magnetization increase obtained after replacing As by Sb to the enhancement of an instability at $(π,π)$. This points to a strong connection between Fermi surface nesting and magnetism, which supports the theory of the itinerant nature of magne…
The competition of magnetic order and superconductivity is a key element in the physics of all unconventional superconductors, e.g. in high-transition-temperature cuprates 1, heavy fermions 2 and organic superconductors3. Here superconductivity is often found close to a quantum critical point where long-range antiferromagnetic order is gradually suppressed as a function of a control parameter, e.g. charge carrier doping or pressure. It is believed that dynamic spin fluctuations associated with this quantum critical behaviour are crucial for the mechanism of superconductivity. Recently high-tem…
We report a strategy to induce superconductivity in the BiS$_2$-based compound LaOBiS$_2$. Instead of substituting F for O, we increase the charge-carrier density (electron dope) via substitution of tetravalent Th$^{+4}$, Hf$^{+4}$, Zr$^{+4}$, and Ti$^{+4}$ for trivalent La$^{+3}$. It is found that both the LaOBiS$_2$ and ThOBiS$_2$ parent compounds are bad metals and that superconductivity is induced by electron doping with \emph{T$_c$} values of up to 2.85 K. The superconducting and normal states were characterized by electrical resistivity, magnetic susceptibility, and heat capacity measure…
We investigated the recently found superconductor LaO_{1-x}F_xFeAs by X-ray absorption spectroscopy (XAS). From a comparison of the O K-edge with LDA calculations we find good agreement and are able to explain the structure and changes of the spectra with electron doping. An important result from this edge is a limitation of the Hubbard U to values not significantly larger than 1 eV. From experimental Fe L_2,3-edge spectra and charge transfer multiplet calculations we gain further information on important physical values such as hopping parameters, the charge transfer energy Delta, and the on-…
We have prepared the newly discovered Fe-based superconducting material $\rm LaO_{1-x}F_xFeAs$ ($0\leq x\leq 0.2$) in polycrystalline form and have investigated the samples by means of structural, thermodynamic and transport measurements. Our investigations reveal a non superconducting phase at $0\leq x\lesssim0.04$ which for $x=0$ is characterized by a structural transition towards an orthorhombic distortion at $T_s\approx 160$ K and antiferromagnetic spin order at $T_N\approx138$ K. Both transitions lead to strong anomalies in various transport properties as well as in magnetization and in s…
Structural, electronic, and magnetic properties of undoped and aliovalent-ion (Ca, F)-doped LaOFeP, which undergo superconducting transitions at transition temperatures (Tc) 4-7 K [Kamihara et al, J. Am. Chem. Soc. 128, 10012, (2006)], were investigated. Tc of the samples varied from 2.4 to 5.5 K in the undoped samples, and was increased up to ~7 K by Ca- and F-doping. The Tc increases are correlated with a decrease in the lattice volume. LaOFeP exhibits paramagnetism in the normal conducting state. Photoemission spectroscopy combined with first-principle band calculations clarified that Fe 3d…
We studied the pressure effects on the electronic and structural properties of LaOFeAs by first-principles calculations. For the anti-ferromagnetic (AFM) phase with stripe- like aligned Fe spins, the electronic density of states at the Fermi level (N (EF)) slightly descends first with increasing applied pressure, then bounces up with further increasing pressure (or decreasing volume), and reaches its maximum at ~ 29.2 GPa with the volume ~ 80% of the ambient pressure value (V0). At this volume (V = 0.8V0), the LaOFeAs crystal undergoes a structural phase transition from the orthorhombic struct…
Resistivities of single-crystalline as well as poly-crystalline samples of CeOBiS2 without fluorine doping were measured at temperatures down to 0.13 K, and were compared with those of poly-crystalline LaOBiS2 and PrOBiS2. Both poly-crystalline and single-crystalline CeOBiS2 exhibited zero resistivity below 1.2 K while poly-crystalline LaOBiS2 and PrOBiS2 did not show zero resistivity down to 0.13 K. Superconducting transition temperature of CeOBiS2 was reduced by increasing the applied current density. The superconductivity of CeOBiS2 without chemical doping is likely triggered by the carrier…
The significantly enhanced superconducting transition temperature ($T_c$) of an FeSe monolayer on SrTiO$_3$(001) substrate has attracted extensive attention in recent years. Here, based on first-principles electronic structure calculations, we propose another candidate substrate LaO(001) for the epitaxial growth of FeSe monolayer to realize superconductivity. Our calculations show that for the optimal adsorption structure of FeSe monolayer on LaO(001), the stripe antiferromagnetic state and the dimer antiferromagnetic state are almost energetically degenerate, indicating the existence of stron…
We report the synthesizing and characterization of the hole doped Ni-based superconductor ($La_{1-x}Sr_{x})ONiAs$. By substituting La with Sr, the superconducting transition temperature $T_c$ is increased from 2.75 K of the parent phase $LaONiAs$ to 3.7 K at the doping levels x= 0.1 - 0.2. The curve $T_c$ versus hole concentration shows a symmetric behavior as the electron doped samples $La(O_{1-x}F_{x})NiAs$. The normal state resistivity in Ni-based samples shows a good metallic behavior and reveals the absence of an anomaly which appears in the Fe-based system at about 150 K, suggesting that…
Condensed matter systems that simultaneously exhibit superconductivity and ferromagnetism are rare due the antagonistic relationship between conventional spin-singlet superconductivity and ferromagnetic order. In materials in which superconductivity and magnetic order is known to coexist (such as some heavy-fermion materials), the superconductivity is thought to be of an unconventional nature. Recently, the conducting gas that lives at the interface between the perovskite band insulators LaAlO$_3$ (LAO) and SrTiO$_3$ (STO) has also been shown to host both superconductivity and magnetism. Most …
The two-dimensional electron gas at the crystalline LaAlO$_{3}$/SrTiO$_{3}$ (c-LAO/STO) interface has sparked large interest due to its exotic properties including an intriguing gate-tunable superconducting phase. While there is growing evidence of pronounced spatial inhomogeneity in the conductivity at STO-based interfaces, the consequences for superconductivity remain largely unknown. We study interfaces based on amorphous LAO top layers grown at room temperature (a-LAO/STO) and demonstrate a superconducting phase similar to c-LAO/STO, however, with a gate-tunable critical temperature of $46…
We investigated the magnetic properties of (La$_{1-x}$Ba$_{x}$)(Zn$_{1-x}$Mn$_{x}$)AsO with $x$ varying from 0.005 to 0.05 at an external magnetic field of 1000 Oe. For doping levels of $x$ $\leq$ 0.01, the system remains paramagnetic down to the lowest measurable temperature of 2 K. Only when the doping level increases to $x$ = 0.02 does the ferromagnetic ordering appear. Our analysis indicates that antiferromagnetic exchange interactions dominate for $x$ $\leq$ 0.01, as shown by the negative Weiss temperature fitted from the magnetization data. The Weiss temperature becomes positive, i.e., f…
We report the discovery of a new diluted magnetic semiconductor, Li(Zn,Mn)P, in which charge and spin are introduced independently via lithium off-stoichiometry and the isovalent substitution of Mn2+ for Zn2+, respectively. Isostructural to (Ga,Mn)As, Li(Zn,Mn)P was found to be a p-type ferromagnetic semiconductor with excess Lithium providing charge doping. First principles calculations indicate that excess Li is favored to partially occupy the Zn site, leading to hole doping. Ferromagnetism is mediated in semiconducting samples of relative low mobile carriers with a small coercive force, ind…
Here we report the successful synthesis of a spin- & charge-decoupled diluted magnetic semiconductor (Ca,Na)(Zn,Mn)2As2, crystallizing into the hexagonal CaAl2Si2 structure. The compound shows a ferromagnetic transition with a Curie temperature up to 33 K with 10% Na doping, which gives rise to carrier density of np~10^20 cm^-3. The new DMS is a soft magnetic material with HC<400 Oe. The anomalous Hall effect is observed below the ferromagnetic ordering temperature. With increasing Mn doping, ferromagnetic order is accompanied by an interaction between the local spin and mobile charge, giving …
In order to explore the possibility of tuning superconducting and ferromagnetic transitions by Cu doping (for Ru) in GdSr2RuCu2O8, we have carried out synthesis and characterization of GdSr2Ru{1-x}Cu{2+x)O8 (x = 0, 0.05, 0.1, 0.2) and studied their physical properties. Coexistence of superconductivity and ferromagnetism is observed in all the Cu doped samples studied here. The zero field susceptibility data suggests formation of a spontaneous vortex phase. Cu doping decreases the ferromagnetic Curie temperature, whereas the superconducting transition temperature increases until an optimal conc…
We report the effects of Ce substitution on structural, electronic, and magnetic properties of layered bismuth-chalcogenide La1-xCexOBiSSe (x = 0-0.9), which are newly obtained in this study. Metallic conductivity was observed for x > 0.1 because of electron carriers induced by mixed valence of Ce ions, as revealed by bond valence sum calculation and magnetization measurements. Zero resistivity and clear diamagnetic susceptibility were obtained for x = 0.2-0.6, indicating the emergence of bulk superconductivity in these compounds. Dome-shaped superconductivity phase diagram with the highest tr…
Exotic superconductivity in the doped Kitaev quantum spin liquid
Institute for Solid State Physics, University of Tokyo（东京大学固体物理研究所）；Department of Applied Science, Graduate School of Sciences and Technology for Innovation, Yamaguchi University（山口大学理工学综合研究科应用科学系）
Neutron scattering has been used to study the nature of the ferromagnetic transition in single crystals of La_0.7Ca_0.3MnO_3 and La_0.8Ca_0.2MnO_3, and polycrystalline samples of La_0.67Ca_0.33MnO_3 and La_5/8Ca_3/8MnO_3 where the naturally occurring O-16 can be replaced with the O-18 isotope. Small angle neutron scattering on the x=0.3 single crystal reveals a discontinuous change in the scattering at the Curie temperature for wave vectors below ~0.065 A^-1. Strong relaxation effects are observed for this domain scattering, for the magnetic order parameter, and for the quasielastic scattering…
We report a complete multicomponent mean-field-theory for the coexistence and competition of charge ordering (CO), antiferromagnetic (AFM) and ferromagnetic (FM) spin ordering in the presence of a uniform magnetic field. Doping the AFM or CO state always generates a ferromagnetic component. Itinerant FM, AFM and CO, necessarily coexist and compete in a particle-hole asymmetric system. Melting of large AFM-CO orders by small magnetic fields and the related phenomenon of Colossal Magnetoresistance (CMR) may arise whenever the CO and AFM order parameters have similar magnitude and momentum struct…
Following the discovery of superconductivity in an iron-based arsenide LaO1-xFxFeAs with a superconducting transition temperature (Tc) of 26 K[1], Tc was pushed up surprisingly to above 40 K by either applying pressure[2] or replacing La with Sm[3], Ce[4], Nd[5] and Pr[6]. The maximum Tc has climbed to 55 K, observed in SmO1-xFxFeAs[7, 8] and SmFeAsO1-x[9]. The value of Tc was found to increase with decreasing lattice parameters in LnFeAsO1-xFx (Ln stands for the lanthanide elements) at an apparently optimal doping level. However, the F- doping in GdFeAsO is particularly difficult[10,11] due t…
The doping of charge carriers into the CuO2 planes of copper oxide Mott insulators causes a gradual destruction of antiferromagnetism and the emergence of high-temperature superconductivity. Optimal superconductivity is achieved at a doping concentration p beyond which further increases in doping cause a weakening and eventual disappearance of superconductivity. A potential explanation for this demise is that ferromagnetic fluctuations compete with superconductivity in the overdoped regime. In this case a ferromagnetic phase at very low temperatures is predicted to exist beyond the doping conc…
The discovery of about 50 K superconductivity in the tetragonal Fe-based pnictides has stimulated the search for superconductivity in a wide class of materials with similar structure. Copper forms compounds isostructural to LaOFeAs. Single phase BiOCuS can be prepared by a solid state reaction at temperature lower than 500 C from a mixture of Bi2O3, Bi2S3 and Cu2S. The samples have been characterized by means of EDX analysis, X-ray diffraction, magnetic and electrical measurements. The cell parameters are a = 3.8708 A, c = 8.565 A. Charge carrier doping can be realized either by F substitution…
Heterostructuring as Gateway to Electron Doping of Nickelate Superconductors
Northwest University（西北大学）；University of Hyogo（兵库大学）；Kyushu Institute of Technology（九州工业大学）；Soochow University（苏州大学）；Universität Würzburg（维尔茨堡大学）；Southeast University（东南大学）；University of Science and Technology of China（中国科学技术大学）；TU Wien（维也纳工业大学）
We have investigated the crystal structure and physical properties of LaO1-xFxBiSSe to reveal the intrinsic superconductivity phase diagram of the BiCh2-based layered compound family. From synchrotron X-ray diffraction and Rietveld refinements with anisotropic displacement parameters, we clearly found that the in-plane disorder in the BiSSe layer was fully suppressed for all x. In LaO1-xFxBiSSe, metallic conductivity and superconductivity are suddenly induced by electron doping even at x = 0.05 and 0.1 with a monoclinic structure. In addition, x (F concentration) dependence of the transition t…
Based on the first-principles calculations, we have investigated the geometry, binding properties, density of states and band structures of the novel superconductor LaFe1-xCoxAsO and its parent compounds with the ZrCuSiAs structure. We demonstrate that La-O bond and TM-As (TM=Fe or Co) bond are both strongly covalent, while the LaO and TMAs layers have an almost ionic interaction through the Bader charge analysis. Partial substitution of iron with cobalt modify the Fermi level from a steep edge to a flat slope, which explains why in this system Co doping suppresses the spin density wave (SDW) …
