Surface and bulk components of electrical conductivity in the (presumably special topological) Kondo insulator SmB6 at lowest temperatures

Samarium hexaboride (SmB6) has recently been considered to be a topological Kondo insulator (TKI), the first strongly correlated electron system to exhibit topological surface conduction states. In this contribution, results of electrical resistivity measurements between 80 K and 0.08 K of various SmB6 single crystalline samples are presented, analyzed and discussed. The received results imply that the residual conductivity of SmB6 below about 4 K is of non-activated (metallic-like) nature. It is shown that this metallic-like behavior can be attributed both to surface (2D) conduction states, as may be expected in case of a topological insulator, as well as to the highly correlated many-body (3D) bulk ground state which is formed within the gap of this compound. From this it follows that in SmB6, where surface conductivity states are clearly present, there is in parallel also a bulk contribution to residual electrical conductivity originating from the strongly correlated electron system with valence fluctuations. This raises the question whether SmB6 does not form a new / special type of topological insulator in which in the energy gap besides the surface conduction states, there is also a conducting narrow in-gap band originating from the bulk strongly correlated electron system.Comment: 9 pages, 5 figure

Insights into a Defective Potassium Sulfido Cobaltate: Giant Magnetic Exchange Bias, Ionic Conductivity, and Electrical Permittivity

The novel potassium sulfido cobaltate, K2[Co3S4] is introduced, with 25% vacancies of the cobalt positions within a layered anionic sublattice. The impedance and dielectric investigations indicate a remarkable ionic conductivity of 21.4 mS cm−1 at room temperature, which is in the range of highest ever reported values for potassium-ions, as well as a high electrical permittivity of 2650 at 1 kHz, respectively. Magnetometry results indicate an antiferromagnetic structure with giant intrinsic exchange bias fields of 0.432 and 0.161 T at 3 and 20 K respectively, potentially induced by a combination of the interfacial effect of combined magnetic anionic and nonmagnetic cationic sublattices, as well as partial spin canting. The stability of the exchange bias behavior is confirmed by a training effect of less than 18% upon 10 hysteresis cycles. The semiconductivity of the material is determined, both experimentally and theoretically, with a bandgap energy of 1.68 eV. The findings render this material as a promising candidate for both, active electrode material in potassium-ion batteries, and for spintronic applications

Structural, Electronic, and Magnetic Curiosities of an Unprecedented Chromate (II)

The ternary sulfido chromate (II), K2[Cr3S4], was synthesized through a straightforward solid-state method as the first alkali metal chalcogenido chromate with the formal oxidation state +2, which was verified by X-ray absorption spectroscopy. Single-crystal diffraction analysis reveals the chromium ions to be coordinated by sulfur in two geometric arrangements: square planar and square pyramidal. Both environments are unusual for transition metal complexes with a d4 electron configuration. Structural distortions from the ideal arrangement are present in both coordination environments. Measurement of the magnetic moment indicates a value of 3.60 μB per chromium ion, which appears at first glance to contradict the standard ligand field theory. Quantum chemical calculations suggest high-spin states for both coordination geometries with a spin delocalization due to Cr–Cr interactions, leading to an intermediate-spin state with magnetic moment values very close to the experimental results, and attributing the structural distortions as the first example of the Jahn–Teller active d4 system with nonoctahedral coordination geometries. The optical, dielectric, and impedance measurement results indicate the potential as a synergic insulator, capacitor, and high-dielectric-constant material

Phosphonate Metal–Organic Frameworks: A Novel Family of Semiconductors

Herein, the first semiconducting and magnetic phosphonate metal–organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner‐sharing copper dimers. The solid‐state UV–vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)‐calculated bandgap of 1.77 eV. Single‐crystal conductivity measurements for different orientations of the individual crystals yield a range of conductances from 10−3 to 103 S m−1 at room temperature, pointing to the directional nature of the electrical conductivity in TUB75. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors.TU Berlin, Open-Access-Mittel - 202

Large-scale synthesis of mixed valence K3_3[Fe2_2S4_4] with high dielectric and ferrimagnetic characteristics

High yields of phase-pure K(3)[Fe(2)S(4)] are obtained using a fast, straight-forward, and efficient synthetic technique starting from the binary precursors K(2)S and FeS, and elemental sulphur. The compound indicates soft ferrimagnetic characteristics with magnetization of 15.23 A m(2) kg(−1) at 300 K due to the mixed valence of Fe(II)/Fe(III). Sintering at different temperatures allows the manipulation of the microstructure as well as the ratio of grains to grain boundaries. This results in a variation of dielectric and impedance properties. Samples sintered at 923 K demonstrate a dielectric constant (κ) of around 1750 at 1 kHz, which lies within the range of well-known high-κ dielectric materials, and an ionic conductivity of 4 × 10(−2) mS cm(−1) at room temperature. The compound has an optical band gap of around 2.0 eV, in agreement with tailored quantum chemical calculations. These results highlight its potential as a material comprising non-toxic and abundant elements for electronic and magnetic applications

Large Exchange Bias, High Dielectric Constant, and Outstanding Ionic Conductivity in a Single‐Phase Spin Glass

The multigram synthesis of K2[Fe3S4] starting from K2S and FeS is presented, and its electronic and magnetic properties are investigated. The title compound obtains a defect variant of the K[Fe2Se2] structure type. Dielectric and impedance measurements indicate a dielectric constant of 1120 at 1 kHz and an outstanding ionic conductivity of 24.37 mS cm–1 at 295 K, which is in the range of the highest reported value for potential solid‐state electrolytes for potassium‐ion batteries. The Seebeck coefficient of the n‐type conductor amounts to −60 µV K−1 at 973 K. The mismatch of the measured electrical resistivity and the predicted metal‐like band structure by periodic quantum chemical calculations indicates Mott insulating behavior. Magnetometry demonstrates temperature‐dependent, large exchange bias fields of 35 mT, as a consequence of the coexistence of spin glass and antiferromagnetic orderings due to the iron vacancies in the lattice. In addition, the decreasing training effects of 34% in the exchange bias are identified at temperatures lower than 20 K. These results demonstrate the critical role of iron vacancies in tuning the electronic and magnetic properties and a multifunctional material from abundant and accessible elements

Intramolecular crossover from unconventional diamagnetism to paramagnetism of palladium ions probed by soft X-ray magnetic circular dichroism

The case of palladium(II) ions in molecular polyoxopalladates highlights the importance of accounting not only for nearest neighbour atoms or ions in order to understand, model or predict magnetic characteristics. Here, using site-specific soft X-ray magnetic circular dichroism (XMCD), the effects of different bond lengths, delocalization of 4d electrons, and 4d spin-orbit coupling on the electronic and magnetic properties are investigated and three different states identified: Conventional diamagnetism in a square-planar O4 coordination environment, paramagnetism caused by four additional out-of-plane oxygen anions, and an unusual diamagnetic state in the diamagnetic/paramagnetic crossover region modified by significant mixing of states and facilitated by the substantial 4d spin-orbit coupling. The two diamagnetic states can be distinguished by characteristic XMCD fine structures, thereby overcoming the common limitation of XMCD to ferro-/ferrimagnetic and paramagnetic materials in external magnetic fields. The qualitative interpretation of the results is corroborated by simulations based on charge transfer multiplet calculations and density functional theory results

A 3D Cu‐Naphthalene‐Phosphonate Metal–Organic Framework with Ultra‐High Electrical Conductivity

A conductive phosphonate metal–organic framework (MOF), [{Cu(H2O)}(2,6‐NDPA)0.5] (NDPA = naphthalenediphosphonic acid), which contains a 2D inorganic building unit (IBU) comprised of a continuous edge‐sharing sheet of copper phosphonate polyhedra is reported. The 2D IBUs are connected to each other via polyaromatic 2,6‐NDPA's, forming a 3D pillared‐layered MOF structure. This MOF, known as TUB40, has a narrow band gap of 1.42 eV, a record high average electrical conductance of 2 × 102 S m−1 at room temperature based on single‐crystal conductivity measurements, and an electrical conductance of 142 S m−1 based on a pellet measurement. Density functional theory (DFT) calculations reveal that the conductivity is due to an excitation from the highest occupied molecular orbital on the naphthalene‐building unit to the lowest unoccupied molecular orbital on the copper atoms. Temperature‐dependent magnetization measurements show that the copper atoms are antiferromagnetically coupled at very low temperatures, which is also confirmed by the DFT calculations. Due to its high conductance and thermal/chemical stability, TUB40 may prove useful as an electrode material in supercapacitors.TU Berlin, Open-Access-Mittel – 202

Phosphonate Metal-Organic Frameworks: A Novel Family of Semiconductors

Herein is reported the first semiconducting and magnetic phosphonate metal-organic framework (MOF), TUB75, which contains a one-dimensional inorganic building unit composed of a zig-zag chain of corner-sharing copper dimers. The solid-state UV-Vis spectrum of TUB75 reveals the existence of a narrow band gap of 1.4 eV, which agrees well with the 1.77 eV one obtained from DFT calculations. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors. </p