Search

We report bulk magnetization measurements and spatially resolved measurements of magnetic domains inCo3Sn2S2single crystals. The results indicate that a previously reported magnetic anomaly around 130 K is due to an anomalous domain wall depinning upon cooling. Our measurements also reveal a hysteresis between field-cooled-cooling and field-cooled-warming magnetization curves acquired under a constant magnetic field below 300 Oe. This observation rules out the possibility that the anomaly stems from a second-order phase transition. Our results further suggest that changes in the shape of hysteresis loops from 5 to 170 K are caused by an unusual temperature-dependent domain nucleation field that changes sign around 130 K. The Kerr rotation images of the magnetic domains confirm that the domain walls depin between 120 and 140 K., (© 2022 IOP Publishing Ltd.)

A new type-I clathrate, Ba 8 Cu 14 Ge 6 P 26 , was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba 8 Cu 14 Ge 6 P 26 crystallizes in the cubic space group Pm 3 n (no. 223). Ba 8 Cu 14 Ge 6 P 26 is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba 8 Cu 14 Ge 6 P 26 were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba 8 Cu 14 Ge 6 P 26 is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m -1 K -1 at 812 K. The thermoelectric figure of merit, ZT , for a slice of the Bridgman-grown crystal of Ba 8 Cu 14 Ge 6 P 26 approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm -1 K -2 . The thermoelectric efficiency of Ba 8 Cu 14 Ge 6 P 26 is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700-850 K temperature region, including all tetrel-free clathrates. Ba 8 Cu 14 Ge 6 P 26 expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba 8 Cu 14 Ge 6 P 26 a strong candidate as a novel and efficient thermoelectric material.

Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A non-magnetic piston-cylinder pressure cell is presented for solution-state NMR spectroscopy at geochemical pressures. The probe has been calibrated up to 20 kbar using in situ ruby fluorescence and allows for the measurement of pressure dependencies of a wide variety of NMR-active nuclei with as little as 10 μL of sample in a microcoil. Initial (11)B NMR spectroscopy of the H3BO3-catechol equilibria reveals a large pressure-driven exchange rate and a negative pressure-dependent activation volume, reflecting increased solvation and electrostriction upon boron-catecholate formation. The inexpensive probe design doubles the current pressure range available for solution NMR spectroscopy and is particularly important to advance the field of aqueous geochemistry., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The heavy electron Kondo liquid is an emergent state of condensed matter that displays universal behavior independent of material details. Properties of the heavy electron liquid are best probed by NMR Knight shift measurements, which provide a direct measure of the behavior of the heavy electron liquid that emerges below the Kondo lattice coherence temperature as the lattice of local moments hybridizes with the background conduction electrons. Because the transfer of spectral weight between the localized and itinerant electronic degrees of freedom is gradual, the Kondo liquid typically coexists with the local moment component until the material orders at low temperatures. The two-fluid formula captures this behavior in a broad range of materials in the paramagnetic state. In order to investigate two-fluid behavior and the onset and physical origin of different long range ordered ground states in heavy electron materials, we have extended Knight shift measurements to URu(2)Si(2), CeIrIn(5), and CeRhIn(5). In CeRhIn(5) we find that the antiferromagnetic order is preceded by a relocalization of the Kondo liquid, providing independent evidence for a local moment origin of antiferromagnetism. In URu(2)Si(2) the hidden order is shown to emerge directly from the Kondo liquid and so is not associated with local moment physics. Our results imply that the nature of the ground state is strongly coupled with the hybridization in the Kondo lattice in agreement with phase diagram proposed by Yang and Pines.

Single-crystalline samples of a new Zintl compound, Eu(3)Ga(2)P(4), have been synthesized by a Ga-flux method. Eu(3)Ga(2)P(4) is found to crystallize in a monoclinic unit cell, space group C2/c, isostructural to Ca(3)Al(2)As(4). The structure is composed of a pair of edge-shared GaP(4) tetrahedra, which link by corner-sharing to form Ga(2)P(4) two-dimensional layers, separated by Eu(2+) ions. Magnetic susceptibility showed a Curie-Weiss behavior with an effective magnetic moment consistent with the value for Eu(2+) magnetic ions. Below 15 K, ferromagnetic ordering was observed and the saturation magnetic moment was 6.6 μ(B). Electrical resistivity measurements on a single crystal showed semiconducting behavior. Resistivity in the temperature range between 280 and 300 K was fit by an activation model with an energy gap of 0.552(2) eV. The temperature dependence of the resistivity is better described by the variable-range-hopping model for a three-dimensional conductivity, suggesting that Eu-P bonds are involved in the conductivity. A large magnetoresistance, up to -30%, is observed with a magnetic field H = 2 T at T = 100 K, suggesting strong coupling of carriers with the Eu(2+) magnetic moment.

Magnetic susceptibility, magnetization, specific heat, and electrical resistivity studies on single crystals of Ce4Pt12Sn25 reveal an antiferromagnetic transition at T(N) = 0.19 K, which develops from a paramagnetic state with a very large specific heat coefficient (C/T) of 14 J mol(-1) K(-2)-Ce just above T(N). On the basis of its crystal structure and these measurements, we argue that a weak magnetic exchange interaction in Ce4Pt12Sn25 is responsible for its low ordering temperature and a negligible Kondo-derived contribution to physical properties above T(N). The anomalous enhancement of specific heat above T(N) is suggested to be related, in part, to weak geometric frustration of f-moments in this compound.

The Zintl phase Yb(14)MnSb(11) was successfully doped with Ge utilizing a tin flux technique. The stoichiometry was determined by microprobe analysis to be Yb(13.99(14))Mn(1.05(5))Sb(10.89(16))Ge(0.06(3)). This was the maximum amount of Ge that could be incorporated into the structure via flux synthesis regardless of the amount included in the reaction. Single crystal X-ray diffraction could not unambiguously determine the site occupancy for Ge. Bond lengths varied by about 1% or less, compared with the undoped structure, suggesting that the small amount of Ge dopant does not significantly perturb the structure. Differential scanning calorimetry/thermogravimetry (DSC/TG) show that the doped compound's melting point is greater than 1200 K. The electrical resistivity and magnetism are virtually unchanged from the parent material, suggesting that Yb is present as Yb(2+) and that the Ge dopant has little effect on the magnetic structure. At 900 K the resistivity and Seebeck coefficient decrease resulting in a zT of 0.45 at 1100 K, significantly lower than the undoped compound.

Single crystals of the new Zintl phases AIn2P2 [A = Ca (calcium indium phosphide), Sr (strontium indium phosphide) and Ba (barium indium phosphide)] have been synthesized from a reactive indium flux. CaIn2P2 and SrIn2P2 are isostructural with EuIn2P2 and crystallize in the space group P63/mmc. The alkaline earth cations A are located at a site with 3m symmetry; In and P are located at sites with 3m symmetry. The structure type consists of layers of A2+ cations separated by [In2P2]2- anions that contain [In2P6] eclipsed ethane-like units that are further connected by shared P atoms. This yields a double layer of six-membered rings in which the In-In bonds are parallel to the c axis and to one another. BaIn2P2 crystallizes in a new structure type in the space group P2(1)/m with Z = 4, with all atoms residing on sites of mirror symmetry. The structure contains layers of Ba2+ cations separated by [In2P2]2- layers of staggered [In2P6] units that form a mixture of four-, five- and six-membered rings. As a consequence of this more complicated layered structure, both the steric and electronic requirements of the large Ba2+ cation are met.

Large, high quality single crystals of a new Zintl phase, EuIn(2)As(2), have been synthesized from a reactive indium flux. EuIn(2)As(2) is isostructural to the recently reported phase EuIn(2)P(2), and it is only the second reported member of the group of compounds with formula AM(2)X(2) (A = alkali, alkaline earth, or rare earth cation; M = transition or post-transition metal; and X = Group 14 or 15 element) that crystallizes in the hexagonal space group P6(3)/mmc (a = 4.2067(3) A, c = 17.889(2) A and Z = 2). The structure type contains layers of A(2+) cations separated by [M(2)X(2)](2-) layers along the crystallographic c-axis. Crystals of the title compound were mounted for magnetic measurements, with the crystallographic c-axis oriented either parallel or perpendicular to the direction of the applied field. The collective magnetization versus temperature and field data indicate two magnetic exchange interactions near 16 K, one involving Eu(2+)...Eu(2+) intralayer coupling and the other involving Eu(2+)...Eu(2+) coupling between layers. EuIn(2)As(2) is metallic and magnetoresistive, as is the isostructural phosphide, and both compounds have coincident resistivity and magnetic ordering transitions, consistent with the observation of colossal magnetoresistance. Negative colossal magnetoresistance (MR = {[rho(H) - rho(0)]/rho(H)} x 100%) of up to -143% (at T = 17.5 K, H = 5 T) is observed for EuIn(2)As(2), approximately half of that observed for the more resistive phosphide, which has a higher magnetic ordering temperature and local moment coupling strength.

The heat capacities of Gd(2)Zr(2)O(7) and Gd(2)Hf(2)O(7) both show sharp peaks in the vicinity of 0.77 K, consistent with the existence of long range magnetic order. They are superimposed in both cases on broader maxima centered at approximately 1 K, presumably due to short range spin correlations. Both compounds exhibit antiferromagnetic interactions, with Weiss constants of approximately -7 K. Comparisons are made to earlier results for the isomorphic compounds Gd(2)Ti(2)O(7) and Gd(2)Sn(2)O(7).

A new rare earth metal Zintl phase, Eu(3)In(2)P(4), was synthesized by utilizing a metal flux method. The compound crystallizes in the orthorhombic space group Pnnm with the cell parameters a = 16.097(3) A, b = 6.6992(13) A, c = 4.2712(9) A, and Z = 2 (T = 90(2) K, R1 = 0.0159, wR2 = 0.0418 for all data). It is isostructural to Sr(3)In(2)P(4). The structure consists of tetrahedral dimers, [In(2)P(2)P(4/2)](6-), that form a one-dimensional chain along the c axis. Three europium atoms interact via a Eu-Eu distance of 3.7401(6) A to form a straight line triplet. Single-crystal magnetic measurements show anisotropy at 30 K and a magnetic transition at 14.5 K. High-temperature data give a positive Weiss constant, which suggests ferromagnetism, while the shape of susceptibility curves (chi vs T) suggests antiferromagnetism. Heat capacity shows a magnetic transition at 14.5 K that is suppressed with field. This compound is a semiconductor according to the temperature-dependent resistivity measurements with a room-temperature resistivity of 0.005(1) Omega m and E(g) = 0.452(4) eV. It shows negative magnetoresistance below the magnetic ordering temperature. The maximum magnetoresistance (Deltarho/rho(H)) is 30% at 2 K with H = 5 T.

Eu3InP3 has been prepared as large single crystals with an indium flux reaction. The structure of the new compound is isotypic to Sr3InP3 and crystallizes in the orthorhombic space group Pnma with unit cell dimensions of a = 12.6517(15) A, b = 4.2683(5) A, and c = 13.5643(14) A (Z = 4, T = 140 K, R1 = 0.0404, wR2 = 0.0971 for all data). The structure consists of one-dimensional chains of corner-shared distorted [InP2P2/2]6- tetrahedra separated by rows of Eu2+ ions. Two of the three crystallographically distinct europium sites have a short Eu(1)-Eu(2) distance of 3.5954(7) A, which yields Eu-Eu dimers. The Eu-P bond distances range from 2.974(2) to 3.166(2) A. The temperature dependence of the conductivity indicates that Eu3InP3 is a small band gap semiconductor. Both magnetization and Eu-151 Mossbauer spectral measurements indicate that the europium in Eu3InP3 is divalent and that at least two magnetic transitions occur. Magnetization studies reveal magnetic transitions at 14, 10.4, and approximately 5 K. These transitions are also observed in heat capacity studies of Eu3InP3. The Mossbauer spectra indicate that the two europium sites are ordered at 12 K and that all three europium sites are ordered at 8 K.

A new transition-metal-containing Zintl compound, Eu(10)Mn(6)Sb(13), was prepared by a high-temperature Sn-flux synthesis. The structure was determined by single-crystal X-ray diffraction. Eu(10)Mn(6)Sb(13) crystallizes in the monoclinic space group C2/m with a = 15.1791(6) A, b = 19.1919(7) A, c = 12.2679(4) A, beta = 108.078(1)*, Z = 4 (R1 = 0.0410, wR2 = 0.0920), and T = 90(2) K. The structure of Eu(10)Mn(6)Sb(13) is composed of double layers of Mn-centered tetrahedra separated by Eu(2+) cations. The double layers are composed of edge- and corner-sharing Mn-centered tetrahedra which form cavities occupied by Eu(2+) cations and [Sb(2)](4-) dumbbells. Linear [Sb(3)](5-) trimers bridging two tetrahedra across the cavity are also present. Bulk susceptibility data indicate paramagnetic behavior with a ferromagnetic component present below 60 K. Temperature-dependent electrical resistivity measurements show semiconducting behavior above 60 K (E(a)() = 0.115(2) eV), a large and unusually sharp maximum in the resistivity at approximately 40 K, and metallic behavior below 40 K. (151)Eu Mössbauer spectra confirm that the europium is divalent with an average isomer shift of -11.2(1) mm/s at 100 K; the spectra obtained below 40 K reveal magnetic ordering of six of the seven europium sublattices and, at 4.2 K, complete ordering of the seven europium sublattices.

Treatment of M[N(SiMe(3))(2)](2) (M = Mn, Fe, Co) with various bulky beta-diketimines afforded a variety of new three-coordinate complexes which were characterized by UV-vis, (1)H NMR and IR spectroscopy, magnetic measurements, and X-ray crystallography. Reaction of the beta-diketimine H(Dipp)NC(Me)CHC(Me)N(Dipp) (Dipp(2)N(wedge)NH; Dipp = C(6)H(3)-2,6-Pr(i)(2)) with M[N(SiMe(3))(2)](2) (M = Mn or Co) gave Dipp(2)N(wedge)NMN(SiMe(3))(2) (M = Mn, 1; Co, 3) while the reaction of Fe[N(SiMe(3))(2)](2) with Ar(2)N(wedge)NH (Ar = Dipp, C(6)F(5), Mes, C(6)H(3)-2,6-Me(2), or C(6)H(3)-2,6-Cl(2)) afforded the series of iron complexes Ar(2)N(wedge)NFe[N(SiMe(3))(2)] (Ar = Dipp, 2a; C(6)F(5), 2b; Mes, 2c; C(6)H(3)-2,6-Me(2), 2d; C(6)H(3)-2,6-Cl(2), 2e). This represents a new synthetic route to beta-diketiminate complexes of these metals. The four-coordinate bis-beta-diketiminate complex Fe[N(wedge)N(C(6)F(5))(2)](2), 4, was also isolated as a byproduct from the synthesis of 2b. Direct reaction of the Dipp(2)N(wedge)NLi with CoCl(2) gave the "ate" salt Dipp(2)N(wedge)NCoCl(2)Li(THF)(2), 5, in which the lithium chloride has formed a complex with Dipp(2)N(wedge)NCoCl through chloride bridging. The Fe(III) species Dipp(2)N(wedge)NFeCl(2), 6, was obtained cleanly from the reaction of FeCl(3) with Dipp(2)N(wedge)NLi. Magnetic measurements showed that all the complexes have a high spin configuration. The different substituents in the series of iron complexes 2a-e allowed assignment of their paramagnetically shifted (1)H NMR spectra. The X-ray crystal structures 1-2d and 3 showed that they have a distorted three-coordinate planar configuration at the metals whereas complexes 4-6 have highly distorted four-coordinate geometries.