Crystals, magnetic and electronic properties of a new ThCr2Si2-type BaMn2Bi2 and K-doped compositions

This is a report on the new 122 ternary transition-metal pnictide of BaMn2Bi2, which is crystallized from bismuth flux. BaMn2Bi2 adopts ThCr2Si2-type structure (I4/mmm) with a = 4.4902(3) {\AA} and c = 14.687(1) {\AA}; it is antiferromagnetic with anisotropic magnetic susceptibility and semiconducting with a band gap of Eg = 6 meV. Heat capacity result confirms the insulating ground state in BaMn2Bi2 with the electronic residual Sommerfeld coefficient of {\gamma} ~ 0. The high temperature magnetization results show that magnetic ordering temperature is TN ~ 400 K. Hole-doping in BaMn2Bi2 via potassium in Ba1-xKxMn2Bi2 results in metallic behavior for x = 0.10(1), 0.32(1) and 0.36(1). With K-doping, more magnetically anisotropic behavior is observed. Although there is a downturn in electrical resistivity and low-field magnetization data below 4 K in > 30%-doped crystals, there is no sign of zero resistance or diamagnetism. This manuscript is a report on new materials of BaMn2Bi2 and Ba1-xKxMn2Bi2 (0 < x < 0.4). Results from powder X-ray diffraction, anisotropic temperature- and field-dependent magnetization, temperature-and field-dependent electrical resistivity, and heat capacity are presented

Local inhomogeneity and filamentary superconductivity in Pr-doped CaFe2_{2}As2_{2}

We use multi-scale techniques to determine the extent of local inhomogeneity and superconductivity in Ca$_{0.86}$Pr$_{0.14}$Fe$_{2}$As$_{2}$ single crystal. The inhomogeneity is manifested as a spatial variation of praseodymium concentration, local density of states, and superconducting order parameter. We show that the high-$T_{c}$ superconductivity emerges from clover-like defects associated with Pr dopants. The highest $T_{c}$ is observed in both the tetragonal and collapsed tetragonal phases, and its filamentary nature is a consequence of non-uniform Pr distribution that develops localized, isolated superconducting regions within the crystals.Comment: Accepted for publication in Phys. Rev. Lett. (January 6, 2014

Magnetic structure and spin excitations in BaMn2Bi2

We present a single crystal neutron scattering study of BaMn2Bi2, a recently synthesized material with the same ThCr2Si2-type structure found in several Fe-based unconventional superconducting materials. We show long range magnetic order, in the form of a G-type antiferromagnetic structure, to exist up to 390 K with an indication of a structural transition at 100 K. Utilizing inelastic neutron scattering we observe a spin-gap of 16meV, with spin-waves extending up to 55 meV. We find these magnetic excitations to be well fit to a J1-J2-Jc Heisenberg model and present values for the exchange interactions. The spin wave spectrum appears to be unchanged by the 100 K structural phase transition

Fermi-Surface Reconstruction and Complex Phase Equilibria in CaFe2_{2}As2_{2}

Fermi-surface topology governs the relationship between magnetism and superconductivity in iron-based materials. Using low-temperature transport, angle-resolved photoemission, and x-ray diffraction we show unambiguous evidence of large Fermi surface reconstruction in CaFe$_{2}$As$_{2}$ at magnetic spin-density-wave and nonmagnetic collapsed-tetragonal ($cT$) transitions. For the $cT$ transition, the change in the Fermi surface topology has a different character with no contribution from the hole part of the Fermi surface. In addition, the results suggest that the pressure effect in CaFe$_{2}$As$_{2}$ is mainly leading to a rigid-band-like change of the valence electronic structure. We discuss these results and their implications for magnetism and superconductivity in this material.Comment: Accepted for publication in Phys. Rev. Lett. (April 3, 2014

Direct spectroscopic evidence for completely filled Cu 3d3d shell in BaCu2_2As2_2 and α\alpha-BaCu2_2Sb2_2

We use angle-resolved photoemission spectroscopy to extract the band dispersion and the Fermi surface of BaCu$_2$As$_2$ and $\alpha$-BaCu$_2$Sb$_2$. While the Cu $3d$ bands in both materials are located around 3.5 eV below the Fermi level, the low-energy photoemission intensity mainly comes from As $4p$ states, suggesting a completely filled Cu $3d$ shell. The splitting of the As $3d$ core levels and the lack of pronounced three-dimensionality in the measured band structure of BaCu$_2$As$_2$ indicate a surface state likely induced by the cleavage of this material in the collapsed tetragonal phase, which is consistent with our observation of a Cu$^{+1}$ oxydation state. However, the observation of Cu states at similar energy in $\alpha$-BaCu$_2$Sb$_2$ without the pnictide-pnictide interlayer bonding characteristic of the collapsed tetragonal phase suggests that the short interlayer distance in BaCu$_2$As$_2$ follows from the stability of the Cu$^{+1}$ rather than the other way around. Our results confirm the prediction that BaCu$_2$As$_2$ is an $sp$ metal with weak electronic correlations.Comment: 6 pages, 4 figure

Temperature-composition Phase Diagrams for Ba1-xSrxFe2As2 and Ba0.5Sr0.5(Fe1-yCoy)2As2

Single crystals of mixed alkaline earth metal iron arsenide materials of Ba1-xSrxFe2As2 and Ba0.5Sr0.5(Fe1-yCoy)2As2 are synthesized via the self-flux method. Ba1-xSrxFe2As2 display spin-density wave features (TN) at temperatures intermediate to the parent materials, x = 0 and 1, with TN(x) following an approximately linear trend. Cobalt doping of the 1 to 1 Ba:Sr mixture, Ba0.5Sr0.5(Fe1-yCoy)2As2, results in a superconducting dome with maximum transition temperature of TC = 19 K at y = 0.092, close to the maximum transition temperatures observed in unmixed A(Fe1-yCoy)2As2; however, an annealed crystal with y = 0.141 showed a TC increase from 11 to 16 K with a decrease in Sommerfeld coefficient from 2.58(2) to 0.63(2) mJ/(K2 mol atom). For the underdoped y = 0.053, neutron diffraction results give evidence that TN and structural transition (To) are linked at 78 K, with anomalies observed in magnetization, resistivity and heat capacity data, while a superconducting transition at TC ~ 6 K is seen in resistivity and heat capacity data. Scanning tunneling microscopy measurements for y = 0.073 give Dynes broadening factor of 1.15 and a superconducting gap of 2.37 meV with evidence of surface inhomogeneity.Comment: Submitted to PR

Absence of structural transition in TM0.5IrTe2 (TM=Mn, Fe, Co, Ni)

TM-doped IrTe2(TM=Mn, Fe, Co, Ni) compounds were synthesized by solid state reaction. Single crystal x-ray diffraction experiments indicate that part of the doped TM ions (TM=Fe, Co, and Ni) substitute for Ir, and the rest intercalate into the octahedral interstitial sites located in between IrTe2 layers. Due to the lattice mismatch between MnTe2 and IrTe2, Mn has limited solubility in IrTe2 lattice. The trigonal structure is stable in the whole temperature range 1.80<T<300K for all doped compositions. No long range magnetic order or superconductivity was observed in any doped compositions above 1.80K. A spin glass behavior below 10K was observed in Fe-doped IrTe2 from the temperature dependence of magnetization, electrical resistivity, and specific heat. The low temperature specific heat data suggest the electron density of states is enhanced in Fe- and Co-doped compositions but reduced in Ni-doped IrTe2. With the 3d transition metal doping the trigonal a-lattice parameters increases but the c-lattice parameter decreases. Detailed analysis of the single crystal x-ray diffraction data shows that interlayer Te-Te distance increases despite a reduced c-lattice. The importance of the Te-Te, Te-Ir, and Ir-Ir bonding is discussed.Comment: 8 pages, 7 figure

Complex structures of different CaFe2_{2}As2_{2} samples

The interplay between magnetism and crystal structures in three CaFe$_{2}$As$_{2}$ samples is studied. For the nonmagnetic quenched crystals, different crystalline domains with varying lattice parameters are found, and three phases (orthorhombic, tetragonal, and collapsed tetragonal) coexist between T$_{S}$ = 95 K and 45 K. Annealing of the quenched crystals at 350{\deg}C leads to a strain relief through a large (~1.3 %) expansion of the c-parameter and a small (~0.2 %) contraction of the a-parameter, and to local ~0.2 {\AA} displacements at the atomic-level. This annealing procedure results in the most homogeneous crystals for which the antiferromagnetic and orthorhombic phase transitions occur at T$_{N}$/T$_{S}$ = 168(1) K. In the 700{\deg}C-annealed crystal, an intermediate strain regime takes place, with tetragonal and orthorhombic structural phases coexisting between 80 to 120 K. The origin of such strong shifts in the transition temperatures are tied to structural parameters. Importantly, with annealing, an increase in the Fe-As length leads to more localized Fe electrons and higher local magnetic moments on Fe ions. Synergistic contribution of other structural parameters, including a decrease in the Fe-Fe distance, and a dramatic increase of the c-parameter, which enhances the Fermi surface nesting in CaFe$_{2}$As$_{2}$, are also discussed.Comment: 5 pages main text, 5 figures and 6 pages Supporting Informatio

Spin Glass and Semiconducting Behavior in 1D BaFe2-{\delta}Se3 Crystals

We investigate the physical properties and electronic structure of BaFe2-{\delta}Se3 crystals, which were grown out of tellurium flux. The crystal structure of the compound, an iron-deficient derivative of the ThCr2Si2-type, is built upon edge-shared FeSe4 tetrahedra fused into double chains. The semiconducting BaFe2-{\delta}Se3 with {\delta} \approx 0.2 ({\rho}295K = 0.18 {\Omega}\cdotcm and Eg = 0.30 eV) does not order magnetically, however there is evidence for short-range magnetic correlations of spin glass type (Tf \approx 50 K) in magnetization, heat capacity and neutron diffraction results. A one-third substitution of selenium with sulfur leads to a slightly higher electrical conductivity ({\rho}295K = 0.11 {\Omega}\cdotcm and Eg = 0.22 eV) and a lower spin glass freezing temperature (Tf \approx 15 K), corroborating with higher electrical conductivity reported for BaFe2S3. According to the electronic structure calculations, BaFe2Se3 can be considered as a one-dimensional ladder structure with a weak interchain coupling.Comment: 17 pages, 9 figure

Crystal, magnetic, and electronic structures, and properties of new BaMnPnF (Pn = As, Sb, Bi)

New fluoropnictides BaMnPnF with Pn = As, Sb, Bi, are synthesized by stoichiometric reaction of elements with BaF\_2. The compounds crystallize in the tetragonal P4/nmm (No. 129, Z = 2) space group, with the ZrCuSiAs-type structure, as indicated by single crystal and powder X-ray diffraction results. Electrical resistivity results indicate that Pn = As, Sb, and Bi are semiconductors with band gaps of E\_g = 0.73 eV, E\_g = 0.48 eV and E\_g = 0.003 eV, respectively. Powder neutron diffraction reveals a G-type antiferromagnetic order below T\_N = 338(1) K for Pn = As, and below T\_N = 272(1) K for Pn = Sb. Magnetic susceptibility increases with temperature above 100 K for all the materials. Density functional calculations also find semiconducting antiferromagnetic compounds with strong in-plane and weaker out-of-plane exchange coupling that may result in non-Curie Weiss behavior above T\_N. There is strong covalency between Mn and pnictogen elements. The ordered magnetic moments are 3.65(5) {\mu}B/Mn for Pn = As, and 3.66(3) {\mu}B/Mn for Pn = Sb at 4 K, as refined from neutron diffraction experiments.Comment: Accepted for publication in Scientific Report