We report the design, synthesis, structure, and properties of two complex layered phosphide nitrides, $Ak$Th$_2$Mn$_4$P$_4$N$_2$ ($Ak$ = Rb, Cs), which contain anti-fluorite-type [Mn$_2$P$_2$] bilayers separated by fluorite-type [Th2N2] layers as a r
esult of the intergrowth between AkMn$_2$P$_2$ and ThMnPN. The new compounds are featured with an intrinsic hole doping associated with the interlayer charge transfer and a built-in chemical pressure from the [Th$_2$N$_2$] layers, both of which are reflected by the changes in the lattice and the atomic position of phosphorus. The measurements of magnetic susceptibility, electrical resistivity, and specific heat indicate existence of local moments as well as itinerant electrons in relation with d-p hybridizations. The expected dominant antiferromagnetic interactions with enhanced d-p hybridizations were demonstrated by the first-principles calculations only when additional Coulomb repulsions are included. The density of states at the Fermi level derived from the specific-heat analysis are 3.5 and 7.5 times of the calculated ones for Ak = Rb and Cs, respectively, suggesting strong electron correlations in the title compounds.
Strongly correlated electrons in layered perovskite structures have been the birthplace of high-temperature superconductivity, spin liquid, and quantum criticality. Specifically, the cuprate materials with layered structures made of corner sharing sq
uare planar CuO$_4$ units have been intensely studied due to their Mott insulating grounds state which leads to high-temperature superconductivity upon doping. Identifying new compounds with similar lattice and electronic structures has become a challenge in solid state chemistry. Here, we report the hydrothermal crystal growth of a new copper tellurite sulfate Cu$_3$(TeO$_4$)(SO$_4$)$cdot$H$_2$O, a promising alternative to layered perovskites. The orthorhombic phase (space group $Pnma$) is made of corrugated layers of corner-sharing CuO$_4$ square-planar units that are edge-shared with TeO$_4$ units. The layers are linked by slabs of corner-sharing CuO$_4$ and SO$_4$. Using both the bond valence sum analysis and magnetization data, we find purely Cu$^{2+}$ ions within the layers, but a mixed valence of Cu$^{2+}$/Cu${^+}$ between the layers. Cu$_3$(TeO$_4$)(SO$_4$)$cdot$H$_2$O undergoes an antiferromagnetic transition at $T_N$=67 K marked by a peak in the magnetic susceptibility. Upon further cooling, a spin-canting transition occurs at $T^{star}$=12 K evidenced by a kink in the heat capacity. The spin-canting transition is explained based on a $J_1$-$J_2$ model of magnetic interactions, which is consistent with the slightly different in-plane super-exchange paths. We present Cu$_3$(TeO$_4$)(SO$_4$)$cdot$H$_2$O as a promising platform for the future doping and strain experiments that could tune the Mott insulating ground state into superconducting or spin liquid states.
Materials with strong magnetoresistive responses are the backbone of spintronic technology, magnetic sensors, and hard drives. Among them, manganese oxides with a mixed valence and a cubic perovskite structure stand out due to their colossal magnetor
esistance (CMR). A double exchange interaction underlies the CMR in manganates, whereby charge transport is enhanced when the spins on neighboring Mn3+ and Mn4+ ions are parallel. Prior efforts to find different materials or mechanisms for CMR resulted in a much smaller effect. Here we show an enormous CMR at low temperatures in EuCd2P2 without manganese, oxygen, mixed valence, or cubic perovskite structure. EuCd2P2 has a layered trigonal lattice and exhibits antiferromagnetic ordering at 11 K. The magnitude of CMR (104 percent) in as-grown crystals of EuCd2P2 rivals the magnitude in optimized thin films of manganates. Our magnetization, transport, and synchrotron X-ray data suggest that strong magnetic fluctuations are responsible for this phenomenon. The realization of CMR at low temperatures without heterovalency leads to a new regime for materials and technologies related to antiferromagnetic spintronics.
Recently, An electron-doped 12442-type iron-based superconductor BaTh$_2$Fe$_4$As$_4$(N$_{0.7}$O$_{0.3}$)$_2$ has been successfully synthesized with high-temperature solid-state reactions on basis of a structural design. The inter-block-layer charge
transfer between the constituent units of BaFe$_2$As$_2$ and ThFeAsN$_{0.7}$O$_{0.3}$ was found to be essential to stabilize the target compound. Dominant electron-type conduction and bulk superconducting transition at ~22 K were demonstrated.
CsCa$_2$Fe$_4$As$_4$F$_2$ is a newly discovered iron-based superconductor with $T_mathrm{c}sim$ 30 K containing double Fe$_2$As$_2$ layers that are separated by insulating Ca$_2$F$_2$ spacer layers. Here we report the transport and magnetization meas
urements on CsCa$_2$Fe$_4$As$_4$F$_2$ single crystals grown for the first time using the self flux of CsAs. We observed a huge resistivity anisotropy $rho_c(T)/rho_{ab}(T)$, which increases with decreasing temperature, from 750 at 300 K to 3150 at 32 K. The $rho_c(T)$ data exhibit a non-metallic behavior above $sim$140 K, suggesting an incoherent electronic state at high temperatures due to the dimension crossover. The superconducting onset transition temperature in $rho_{ab}$ is 0.7 K higher than that in $rho_c$, suggesting two-dimensional (2D) superconducting fluctuations. The lower and upper critical fields also show an exceptional anisotropy among iron-based superconductors. The $H_{c1}^bot(T)$ data are well fitted using the model with two $s$-wave-like superconducting gaps, $Delta_1(0)=6.75$ meV and $Delta_2(0)=2.32$ meV. The inter-plane coherence length $xi_c(0)$ is $3.6$ AA, remarkably smaller than the distance between conducting layers (8.6 AA), consolidating the 2D nature in the title material.
ThFeAsN$_{1-x}$O$_x$ ($0leq xleq0.6$) system with heavy electron doping has been studied by the measurements of X-ray diffraction, electrical resistivity, magnetic susceptibility and specific heat. The non-doped compound exhibits superconductivity at
$T_mathrm{c}^mathrm{onset}=30$ K, which is possibly due to an internal uniaxial chemical pressure that is manifested by the extremely small value of As height with respect to the Fe plane. With the oxygen substitution, the $T_mathrm{c}$ value decreases rapidly to below 2 K for $0.1leq xleq0.2$, and surprisingly, superconductivity re-appears in the range of $0.25leq xleq0.5$ with a maximum $T_mathrm{c}^mathrm{onset}$ of 17.5 K at $x=0.3$. For the normal-state resistivity, while the samples in intermediate non-superconducting interval exhibit Fermi liquid behavior, those in other regions show a non-Fermi-liquid behavior. The specific heat jump for the superconducting sample of $x=0.4$ is $Delta C/(gamma T_mathrm{c})=0.89$, which is discussed in terms of anisotropic superconducting gap. The peculiar phase diagram in ThFeAsN$_{1-x}$O$_x$ presents additional ingredients for understanding the superconducting mechanism in iron-based superconductors.
We have synthesized 10 new iron oxyarsenides, K$Ln_2$Fe$_4$As$_4$O$_2$ ($Ln$ = Gd, Tb, Dy, and Ho) and Cs$Ln_2$Fe$_4$As$_4$O$_2$ ($Ln$ = Nd, Sm, Gd, Tb, Dy, and Ho), with the aid of lattice-match [between $A$Fe$_2$As$_2$ ($A$ = K and Cs) and $Ln$FeAs
O] approach. The resultant compounds possess hole-doped conducting double FeAs layers, [$A$Fe$_4$As$_4$]$^{2-}$, that are separated by the insulating [$Ln_2$O$_2$]$^{2+}$ slabs. Measurements of electrical resistivity and dc magnetic susceptibility demonstrate bulk superconductivity at $T_mathrm{c}$ = 33 - 37 K. We find that $T_mathrm{c}$ correlates with the axis ratio $c/a$ for all 12442-type superconductors discovered. Also, $T_mathrm{c}$ tends to increase with the lattice mismatch, implying a role of lattice instability for the enhancement of superconductivity.
We have synthesized four iron-based oxyarsenide superconductors Rb$Ln_2$Fe$_4$As$_4$O$_2$ ($Ln$ = Sm, Tb, Dy and Ho) resulting from the intergrowth of RbFe$_2$As$_2$ and $Ln$FeAsO. It is found that the lattice match between RbFe$_2$As$_2$ and $Ln$FeA
sO is crucial for the phase formation. The structural intergrowth leads to double asymmetric Fe$_2$As$_2$ layers that are separated by insulating $Ln_2$O$_2$ slabs. Consequently, the materials are intrinsically doped at a level of 0.25 holes/Fe-atom and, bulk superconductivity emerges at $T_mathrm{c}$ = 35.8, 34.7, 34.3 and 33.8 K, respectively, for $Ln$ = Sm, Tb, Dy and Ho. Investigation on the correlation between crystal structure and $T_mathrm{c}$ suggests that interlayer couplings may play an additional role for optimization of superconductivity.
We have synthesized two iron fluo-arsenides $A$Ca$_2$Fe$_4$As$_4$F$_2$ with $A$ = Rb and Cs, analogous to the newly discovered superconductor KCa$_2$Fe$_4$As$_4$F$_2$. The quinary inorganic compounds crystallize in a body-centered tetragonal lattice
with space group I4/mmm, which contain double Fe$_2$As$_2$ layers that are separated by insulating Ca$_2$F$_2$ layers. Our electrical and magnetic measurements on the polycrystalline samples demonstrate that the new materials undergo superconducting transitions at Tc = 30.5 K and 28.2 K, respectively, without extrinsic doping. The correlations between Tc and structural parameters are discussed.
We report synthesis, crystal structure and physical properties of a quinary iron-arsenide fluoride KCa$_2$Fe$_4$As$_4$F$_2$. The new compound crystallizes in a body-centered tetragonal lattice (with space group $I4/mmm$, $a$ = 3.8684(2) {AA}, c = 31.
007(1) {AA}, and $Z$ = 2), which contains double Fe$_2$As$_2$ conducting layers separated by insulating Ca$_2$F$_2$ layers. Our measurements of electrical resistivity, dc magnetic susceptibility and heat capacity demonstrate bulk superconductivity at 33 K in KCa$_2$Fe$_4$As$_4$F$_2$.
