Rb(Zn,Cu)4As3 as a New High-Efficiency Thermoelectric Material.

The thermoelectric performance of RbZn4-xCuxAs3 crystallized in the KCu4S3-type structure was investigated. Samples were synthesized via solid-state reactions, followed by hot pressing. Hole carriers were doped by substituting Zn with Cu until x = 0.02, resulting in an increase of the power factor from 0.049 to 0.52 mW/mK2 at T = 797 K. The lattice thermal conductivity was substantially low, with a value of 1.61 W/mK at T = 312 K, independent of doping. This can be attributed to the large vibration of the Rb atoms, as demonstrated by the neutron diffraction analysis. The maximum dimensionless figure of merit, ZT, was 0.53 at T = 797 K, representing the highest value for the 143-Zintl compounds. The result indicated that the 143-Zintl compounds could be a new class of high-performance thermoelectric materials.

Calorimetric evidence for two phase transitions in Ba1-xKxFe2As2 with fermion pairing and quadrupling states.

Materials that break multiple symmetries allow the formation of four-fermion condensates above the superconducting critical temperature (Tc). Such states can be stabilized by phase fluctuations. Recently, a fermionic quadrupling condensate that breaks the Z2 time-reversal symmetry was reported in Ba1-xKxFe2As2. A phase transition to the new state of matter should be accompanied by a specific heat anomaly at the critical temperature where Z2 time-reversal symmetry is broken ([Formula: see text]). Here, we report on detecting two anomalies in the specific heat of Ba1-xKxFe2As2 at zero magnetic field. The anomaly at the higher temperature is accompanied by the appearance of a spontaneous Nernst effect, indicating the breakdown of Z2 symmetry. The second anomaly at the lower temperature coincides with the transition to a zero-resistance state, indicating the onset of superconductivity. Our data provide the first example of the appearance of a specific heat anomaly above the superconducting phase transition associated with the broken time-reversal symmetry due to the formation of the novel fermion order.

Superconducting vortices carrying a temperature-dependent fraction of the flux quantum.

Magnetic field penetrates type-II bulk superconductors by forming quantum vortices that enclose a magnetic flux equal to the magnetic flux quantum. The flux quantum is a universal quantity that depends only on fundamental constants. In this study, we investigated isolated vortices in the hole-overdoped Ba1-xKxFe2As2 (x = 0.77) by using scanning superconducting quantum interference device (SQUID) magnetometry. In many locations, we observed objects that carried only part of a flux quantum, with a magnitude that varied continuously with temperature. We demonstrated mobility and manipulability of these objects and interpreted them as quantum vortices with nonuniversally quantized (fractional) magnetic flux whose magnitude is determined by the temperature-dependent parameters of a multicomponent superconductor.

Mechanical Compatibility between Mg3(Sb,Bi)2 and MgAgSb in Thermoelectric Modules.

Thermoelectric (TE) modules are exposed to temperature gradients and repeated thermal cycles during their operation; therefore, mechanically robust n- and p-type legs are required to ensure their structural integrity. The difference in the coefficients of thermal expansion (CTEs) of the two legs of a TE module can cause stress buildup and the deterioration of performance with frequent thermal cycles. Recently, n-type Mg3Sb2 and p-type MgAgSb have become two promising components of low-temperature TE modules because of to their high TE performance, nontoxicity, and abundance. However, the CTEs of n-Mg3Sb2 and p-MgAgSb differ by approximately 10%. Furthermore, the oxidation resistances of these materials at increased temperatures are unclear. This work manipulates the thermal expansion of Mg3Sb2 by alloying it with Mg3Bi2. The addition of Bi to Mg3Sb2 reduces the coefficient of linear thermal expansion from 22.6 × 10-6 to 21.2 × 10-6 K-1 for Mg3Sb1.5Bi0.5, which is in excellent agreement with that of MgAgSb (21 × 10-6 K-1). Furthermore, thermogravimetric data indicate that both Mg3Sb1.5Bi0.5 and MgAgSb are stable in air and Ar at temperatures below ∼570 K. The results suggest the compatibility and robustness of Mg3Sb1.5Bi0.5 and MgAgSb as a pair of thermoelectric legs for low-temperature TE modules.

Thermoelectric Properties of (Ba,K)Zn2As2 Crystallized in the ThCr2Si2-type Structure.

The compound Ba1-xKxZn2As2 has a low-temperature phase (α-phase) crystallized in the α-BaCu2S2-type structure and a high-temperature phase (ß-phase) crystallized in the ThCr2Si2-type structure. We successfully obtained the ß-phase at room temperature as a metastable state by quenching from above the structural phase transition. This allowed us to determine the thermoelectric properties of the ß-phase from room to high temperature in the range of 0.00 ≤ x ≤ 0.10. The lattice thermal conductivity is quite low, with a value less than 1 W/mK at 773 K, independent of x. The effective suppression may be due to lattice instability in the underdoped region and to randomness in the overdoped region. The maximum dimensionless figure-of-merit ZT was 0.30 at 773 K for x = 0.03 with the power factor of 0.61 mW/mK2, which is relatively high for a ThCr2Si2-type structure. The results demonstrate the effectiveness of quenching for obtaining a low lattice thermal conductivity, thus providing a new method for attaining high thermoelectric performance.

Superconductivity in a New 1144-Type Family of (La,Na)AFe4As4 (A = Rb or Cs).

We discovered novel Fe-based superconductors (FeSCs) (La,Na)AFe4As4, where A = Rb or Cs, and characterized their superconducting properties. (La,Na)AFe4As4 is a so-called 1144-type compound with a tetragonal unit cell classified into space group P4/mmm (no. 123). The lattice constants are a = 3.861(1) Å and c = 13.26(1) Å for (La,Na)RbFe4As4 and a = 3.880(1) Å and c = 13.60(1) Å for (La,Na)CsFe4As4. The Rietveld refinement results on the powder X-ray diffraction suggest that the La/Na ratio is rather fixed as La:Na = 0.44(5):0.56(5). The electrical resistivity and magnetic susceptibility show superconducting transition at 25.5 K for (La,Na)RbFe4As4 and 24.0 K for (La,Na)CsFe4As4. The superconducting transition temperature (Tc) of (La,Na)AFe4As4 is comparable with that of 122-type (La,Na)Fe2As2 and lower than that of typical 122-type or 1144-type FeSCs by more than 10 K. The possible reasons for lower Tc are discussed in terms of the structural modification, carrier concentration, and chemical disorder.

Antiferroic electronic structure in the nonmagnetic superconducting state of the iron-based superconductors.

A major problem in the field of high-transition temperature (Tc) superconductivity is the identification of the electronic instabilities near superconductivity. It is known that the iron-based superconductors exhibit antiferromagnetic order, which competes with the superconductivity. However, in the nonmagnetic state, there are many aspects of the electronic instabilities that remain unclarified, as represented by the orbital instability and several in-plane anisotropic physical properties. We report a new aspect of the electronic state of the optimally doped iron-based superconductors by using high-energy resolution angle-resolved photoemission spectroscopy. We find spectral evidence for the folded electronic structure suggestive of an antiferroic electronic instability, coexisting with the superconductivity in the nonmagnetic state of Ba1-x K x Fe2As2. We further establish a phase diagram showing that the antiferroic electronic structure persists in a large portion of the nonmagnetic phase covering the superconducting dome. These results motivate consideration of a key unknown electronic instability, which is necessary for the achievement of high-Tc superconductivity in the iron-based superconductors.

Thermoelectric Properties of As-Based Zintl Compounds Ba1-xKxZn2As2.

As-based Zintl compounds Ba1-xKxZn2As2 were prepared by solid-state reaction followed by hot pressing. Ba1-xKxZn2As2 (x ≤ 0.02) crystallizes in the α-BaCu2S2-type structure (space group Pnma) upon cooling from 900 °C, whereas it crystallizes in the ThCr2Si2-type structure (space group I4/mmm) for x ≥ 0.04. The lattice thermal conductivities are almost equivalent for both crystal structures with relatively low values of 0.8-1.1 W/mK at 773 K. The values are comparable to those of Sb-based Zintl compounds, though Ba1-xKxZn2As2 consists of As atoms, which are lighter than Sb atoms. The electrical resistivity and Seebeck coefficient decreases with increasing x, indicating successful hole doping by K substitution. The dimensionless figure-of-merit ZT is 0.67 at 900 K for x = 0.02, opening a new class of thermoelectric materials with the As-based 122 Zintl compounds.

New-Structure-Type Fe-Based Superconductors: CaAFe4As4 (A = K, Rb, Cs) and SrAFe4As4 (A = Rb, Cs).

Fe-based superconductors have attracted research interest because of their rich structural variety, which is due to their layered crystal structures. Here we report the new-structure-type Fe-based superconductors CaAFe4As4 (A = K, Rb, Cs) and SrAFe4As4 (A = Rb, Cs), which can be regarded as hybrid phases between AeFe2As2 (Ae = Ca, Sr) and AFe2As2. Unlike solid solutions such as (Ba(1-x)K(x))Fe2As2 and (Sr(1-x)Na(x))Fe2As2, Ae and A do not occupy crystallographically equivalent sites because of the large differences between their ionic radii. Rather, the Ae and A layers are inserted alternately between the Fe2As2 layers in the c-axis direction in AeAFe4As4 (AeA1144). The ordering of the Ae and A layers causes a change in the space group from I4/mmm to P4/mmm, which is clearly apparent in powder X-ray diffraction patterns. AeA1144 is the first known structure of this type among not only Fe-based superconductors but also other materials. AeA1144 is formed as a line compound, and therefore, each AeA1144 has its own superconducting transition temperature of approximately 31-36 K.

Effect of doping on the magnetostructural ordered phase of iron arsenides: a comparative study of the resistivity anisotropy in doped BaFe2As2 with doping into three different sites.

To unravel the role of doping in iron-based superconductors, we investigated the in-plane resistivity of BaFe(2)As(2) doped at one of the three different lattice sites, Ba(Fe(1-x)Co(x))(2)As(2), BaFe(2)(As(1-x)P(x))(2), and Ba(1-x)K(x)Fe(2)As(2), focusing on the doping effect in the low-temperature antiferromagnetic/orthorhombic (AFO) phase. A major role of doping in the high-temperature paramagnetic/tetragonal (PT) phase is known to change the Fermi surface by supplying charge carriers or exerting chemical pressure. In the AFO phase, we found a clear correlation between the magnitude of the residual resistivity and the resistivity anisotropy. This indicates that the resistivity anisotropy originates from anisotropic impurity scattering due to dopant atoms. The magnitude of the residual resistivity was also found to be a parameter controlling the suppression rate of the AFO ordering temperature. Therefore, the dominant role of doping in the AFO phase is to introduce disorder to the system, distinct from that in the PT phase.

Disappearance of superconductivity in the solid solution between (Ca4Al2O6)(Fe2As2) and (Ca4Al2O6)(Fe2P2) superconductors.

The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

Cyclotron resonance and mass enhancement by electron correlation in KFe2As2.

Cyclotron resonance (CR) measurements for the Fe-based superconductor KFe(2)As(2) are performed. One signal for CR is observed, and is attributed to the two-dimensional α Fermi surface at the Γ point. We found a large discrepancy in the effective masses of CR [(3.4±0.05)m(e) (m(e) is the free-electron mass)] and de Haas-van Alphen results, a direct evidence of mass enhancement due to electronic correlation. A comparison of the CR and de Haas-van Alphen results shows that both intra- and interband electronic correlations contribute to the mass enhancement in KFe(2)As(2).

Complete Fermi surface in BaFe2As2 observed via Shubnikov-de Haas oscillation measurements on detwinned single crystals.

We show that the Fermi surface (FS) in the antiferromagnetic phase of BaFe(2)As(2) is composed of one hole and two electron pockets, all of which are three dimensional and closed, in sharp contrast to the FS observed by angle-resolved photoemission spectroscopy. Considerations on the carrier compensation and Sommerfeld coefficient rule out existence of unobserved FS pockets of significant sizes. A standard band structure calculation reasonably accounts for the observed FS, despite the overestimated ordered moment. The mass enhancement, the ratio of the effective mass to the band mass, is 2-3.

Emergence of superconductivity in "32522" structure of (Ca3Al2O(5-y))(Fe2Pn2) (Pn = As and P).

Using a high-pressure technique, we have successfully synthesized (Ca(3)Al(2)O(5-y))(Fe(2)Pn(2)) (Pn = As and P), the first iron-based superconductors with the perovskite-based "32522" structure to be reported. The transition temperature (T(c)) is 30.2 K for Pn = As and 16.6 K for Pn = P. The emergence of superconductivity is ascribed to the small tetragonal a-axis lattice constant of the materials. From these results, an empirical relationship is established between the a-axis lattice constant and T(c) in iron-based superconductors, which offers a practical guideline for exploring new superconductors with higher T(c).

Absence of an appreciable iron isotope effect on the transition temperature of the optimally doped SmFeAsO(1-y) Superconductor.

We report the iron (Fe) isotope effect on the transition temperature (T(c)) in oxygen-deficient SmFeAsO(1-y), a 50-K-class, Fe-based superconductor. For the optimally doped samples with T(c) = 54 K, a change of the average atomic mass of Fe (M(Fe)) causes a negligibly small shift in T(c), with the Fe isotope coefficient (α(Fe)) as small as -0.024 ± 0.015 (where α(Fe)=-d lnT(c)/dlnM(Fe)). This result contrasts with the finite, inverse isotope shift observed in optimally doped (Ba,K)Fe2As2, indicating that the contribution of the electron-phonon interaction markedly differs between these two Fe-based high-T(c) superconductors.

Inverse iron isotope effect on the transition temperature of the (Ba,K)Fe2As2 superconductor.

We report that the (Ba,K)Fe(2)As(2) superconductor (transition temperature, T(c) approximately 38 K) has an inverse iron isotope coefficient alpha(Fe) = -0.18(3) (where T(c) approximately M(-alphaFe) and M is the iron isotope mass); i.e., the sample containing the large iron isotope mass depicts a higher T(c). Systematic inverse shifts in T(c) were clearly observed between the samples using three types of Fe isotopes ((54)Fe, natural Fe, and (57)Fe). This indicates the first evidence of the inverse isotope effect in high-T(c) superconductors. This anomalous mass dependence on T(c) implies an exotic coupling mechanism in Fe-based superconductors.