Investigation of Planckian behavior in a high-conductivity oxide: PdCrO2.

The layered delafossite metal PdCrO[Formula: see text] is a natural heterostructure of highly conductive Pd layers Kondo coupled to localized spins in the adjacent Mott insulating CrO[Formula: see text] layers. At high temperatures, T, it has a T-linear resistivity which is not seen in the isostructural but nonmagnetic PdCoO[Formula: see text]. The strength of the Kondo coupling is known, as-grown crystals are extremely high purity and the Fermi surface is both very simple and experimentally known. It is therefore an ideal material platform in which to investigate "Planckian metal" physics. We do this by means of controlled introduction of point disorder, measurement of the thermal conductivity and Lorenz ratio, and studying the sources of its high-temperature entropy. The T-linear resistivity is seen to be due mainly to elastic scattering and to arise from a sum of several scattering mechanisms. Remarkably, this sum leads to a scattering rate within 10[Formula: see text] of the Planckian value of k[Formula: see text]T/[Formula: see text].

Metal Substitutions (M = Al, Ga, In; Sn, Ge; and Mn, Fe, Co) in ZnS: Sphalerite versus Wurtzite Formation.

A series of Zn1-xMxS polycrystalline samples were synthesized via a solid-state reaction in closed vessels to examine the solubility of foreign M cations within the wurtzite ZnS structure, employing quenching or slow cooling processes to favor specific polymorphs. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses revealed diverse structural behaviors across different cations. Group 13 elements (Al and Ga) formed solid solutions with a wurtzite structure, while In showed complex layer stacking defects. For 3d magnetic cations (Mn, Fe, and Co), a broad solubility range in the hexagonal structure was noted for Mn, whereas Fe and Co more readily formed cubic structures, with solubilities similar to Mn in the sphalerite form. Despite structural differences, magnetic susceptibilities and spin freezing temperatures for Fe and Co were comparable. Group 14 elements showed varied behaviors: Sn was insoluble in ZnS, as attested by unchanged unit cell parameters and surface crystallite Sn, whereas Ge only formed in the cubic phase with a solubility limit of x ≈ 0.2. The study discusses these variations in solubility and structure in terms of oxidation states, ionic-covalent radius, and coordination preferences in sulfides.

Redox Thermochemistry, Thermodynamics, and Solar Energy Conversion and Storage Capability of Some Double Perovskite Cobaltites.

The oxygen nonstoichiometry, δ, and oxidation enthalpy, ΔHox, of double perovskites RBaCo2O6-δ (R = Sm or Eu) were simultaneously measured depending on the temperature and oxygen partial pressure, pO2. Theoretical equations for ΔHox(T, δ) and pO2(T, δ) were derived from the defect structure model based on the oxygen exchange and cobalt disproportionation reactions. These equations were fitted independently to each of the experimental ΔHox(T, δ) and pO2(T, δ) data sets. The resulting enthalpies of defect reactions were found to be almost the same irrespective of the calculation method. In other words, the models, describing satisfactorily the data, can be used to calculate both compositional dependences and redox thermodynamics of RBaCo2O6-δ (R = Sm or Eu). In addition, from the previously published data and the data presented here, trends were determined in the defect reaction thermodynamics of RBaCo2O6-δ (R = La, Pr, Nd, Sm, Eu, Gd, or Y). Drop calorimetric measurements were performed in air to obtain enthalpy increments for RBaCo2O6-δ (R = Sm or Eu) with variable oxygen content because the samples lost oxygen upon being heated in the calorimetric cell. As-obtained data were used to calculate the functional dependences of enthalpy increments of EuBaCo2O5.56 and SmBaCo2O5.6 with a constant oxygen content. In addition, as an example of practical application-oriented calculations for solar energy conversion and oxygen storage, the performances at equilibrium of RBaCo2O6-δ (R = Pr, Sm, Eu, or Gd) were evaluated and compared to those of SrFeO3-δ as a reference material.

QUANTITATIVE ANALYSIS OF CHORIOCAPILLARIS ALTERATIONS IN SWEPT-SOURCE OPTICAL COHERENCE TOMOGRAPHY ANGIOGRAPHY IN DIABETIC PATIENTS.

PURPOSE: To evaluate quantitative alterations of the choriocapillaris in swept-source optical coherence tomography angiography in diabetic patients. METHODS: We included normal patients and diabetic patients with and without diabetic retinopathy (DR), excluding patients with macular edema. Angiograms in 3 × 3 mm were acquired with Plexelite 9000 swept-source optical coherence tomography angiography. Choroidal flow voids were analyzed after removal of projection artifacts. The main evaluation was the correlation between choroidal flow voids area (FVA-CC) and DR stage. RESULTS: A total of 120 eyes of 72 patients were analyzed. There were 17 eyes from healthy subjects, 30 eyes without DR, 22 eyes with minimal nonproliferative DR, 30 eyes with moderate nonproliferative DR, 16 eyes with severe nonproliferative DR, and 5 eyes with proliferative DR (PDR). The percentage of FVA-CC for each group was, respectively, 10.9 ± 3.4%, 14.6 ± 4.8%, 17.6 ± 3.5%, 20.7 ± 5.9%, 19.9 ± 2.9%, and 26.6 ± 4.4%. FVA-CC and DR stage significantly correlated (P < 0.0001). FVA-CC was significantly increased in diabetic patients without DR compared with healthy subjects (P = 0.008). CONCLUSION: Diabetes is associated with quantifiable choriocapillaris alterations in swept-source optical coherence tomography angiography. These alterations precede clinical signs of DR and are correlated with DR stage.

Thermoelectric materials taking advantage of spin entropy: lessons from chalcogenides and oxides.

The interplay between charges and spins may influence the dynamics of the carriers and determine their thermoelectric properties. In that respect, magneto-thermoelectric power MTEP, i.e. the measurements of the Seebeck coefficient S under the application of an external magnetic field, is a powerful technique to reveal the role of magnetic moments on S. This is illustrated by different transition metal chalcogenides: CuCrTiS4 and CuMnTiS4 magnetic thiospinels, which are compared with magnetic oxides, Curie-Weiss (CW) paramagnetic misfit cobaltites, ruthenates, either ferromagnetic perovskite or Pauli paramagnet quadruple perovskites, and CuGa1-x Mn x Te2 chalcopyrite telluride and Bi1.99Cr0.01Te3 in which diluted magnetism is induced by 3%-Mn and 1%-Cr substitution, respectively. In the case of a ferromagnet (below TC) and CW paramagnetic materials, the increase of magnetization at low T when a magnetic field is applied is accompanied by a decrease of the entropy of the carriers and hence S decreases. This is consistent with the lack of MTEP in the Pauli paramagnetic quadruple perovskites. Also, no significant MTEP is observed in CuGa1-x Mn x Te2 and Bi1.99Cr0.01Te3, for which Kondo-type interaction between magnetic moments and carriers prevails. In contrast, spin glass CuCrTiS4 exhibits negative MTEP like in ferromagnetic ruthenates and paramagnetic misfit cobaltites. This investigation of some chalcogenides and oxides provides key ingredients to select magnetic materials for which S benefits from spin entropy.

Original Network of Zigzag Chains in the ß Polymorph of Fe2WO6: Crystal Structure and Magnetic Ordering.

The structural and physical properties of the ß polymorph of iron tungstate Fe2WO6 have been investigated by synchrotron and neutron diffraction vs temperature, combined with magnetization and dielectric properties measurements. The monoclinic P21/a crystal structure of ß-Fe2WO6 has been determined and consists of an original network of zigzag chains of FeO6 and WO6 octahedra sharing trans and skew edges, connected through corners into a 3D structure. Magnetization measurements indicate an antiferromagnetic transition at TN = 264 K, which corresponds to a ↑↑↓↓ nearly collinear ordering of iron moments inside sequences of four edge-sharing FeO6 octahedra, as determined by neutron diffraction. A canting of the moments out of the ac plane is observed below 150 K, leading to a noncollinear antiferromagnetic structure, the P21/a' magnetic space group remaining unchanged. These results are discussed in comparison with the crystal and magnetic structures of γ-Fe2WO6 and with the magnetic couplings in other iron tungstates and trirutile Fe2TeO6.

Excellent Semiconductors Based on Tetracenotetracene and Pentacenopentacene: From Stable Closed-Shell to Singlet Open-Shell.

Designing stable open-shell organic materials through the modifications of the π-topology of molecular organic semiconductors has recently attracted considerable attention. However, their uses as an active layer in organic field-effect transistors (OFETs) are very limited, and the obtained hole and electron charge mobilities are around 10-3 cm2 V-1 s-1. Herein, we disclose the synthesis of two peri-fused materials, so-called tetracenotetracene (TT) and pentacenopentacene (PP), which have low band gaps of 1.79 and 1.42 eV, respectively. Their ground state natures have been investigated by different experiments including steady state absorption, electron spin resonance, superconducting quantum interfering device, and variable-temperature NMR along with DFT calculations. TT and PP have closed-shell and singlet open-shell structures in their ground state, respectively, and possess high stability. Their biradical characteristics were found to be 0.50 and 0.64. The origin of the open-shell character of PP is related to the concomitant opening of two tetracenes with the recovering of two extra aromatic sextets and a small HOMO-LUMO energy gap (gap <1.5 eV). Thanks to the high stability, thin film OFET devices could be fabricated. In TG-BC configuration PP shows a remarkably high hole mobility of 1.4 cm2 V-1 s-1, while TT exhibits a hole mobility of 0.77 cm2 V-1 s-1. In the configuration of BG-TC, ambipolar behaviors for both were obtained with hole and electron mobilities of 0.21 and 0.01 cm2 V-1 s-1 for PP and 0.14 and 0.006 cm2 V-1 s-1 for TT.

Impact of the iron substitution on the thermoelectric properties of Co1- xFe xS2 ( x ≤ 0.30).

The strong interplay between magnetism and transport can tune the thermoelectric properties in chalcogenides and oxides. In the case of ferromagnetic CoS2 pyrite, it was previously shown that the power factor is large at room temperature, reaching 1 mW m-1 K-2 and abruptly increases for temperatures below the Curie transition ( TC), an increase potentially due to a magnonic effect on the Seebeck ( S) coefficient. The too large thermal conductivity approximately equal to 10.5 W m-1 K-1 at room temperature prevents this pyrite from being a good thermoelectric material. In this work, samples belonging to the Co1- xFe xS2 pyrite family ( x = 0, 0.15 and 0.30) have thus been investigated in order to modify the thermal properties by the introduction of disorder on the Co site. We show here that the thermal conductivity can indeed be reduced by such a substitution, but that this substitution predominantly induces a reduction of the electronic part of the thermal conductivity and not of the lattice part. Interestingly, the magnonic contribution to S below TC disappears as x increases, while at high T, S tends to a very similar value (close to -42 µV K-1) for all the samples investigated. This article is part of a discussion meeting issue 'Energy materials for a low carbon future'.

Topochemical Approach for Transition-Metal Exchange Assisted by Copper Extrusion: from Cu2FeBO5 to Fe3BO5.

All fields of today's technology are concerned with multifunctional materials, the subject of constantly expanding research. Among them, metal transition oxides occupy a strategic place because of the properties directly correlated with metal valence linked with oxygen stoichiometry. To enhance or induce new properties, knowledge of the relationships between the structural and physical characteristics is of prime importance, but a design at low scale also appears to be a powerful tool to increase the chemical reactivity and stabilize new compounds. Herein, an unexpected reaction is reported that associates the exchange of copper and iron in a 3D ludwigite lattice with the huge release of oxygen (14% by weight) at moderate temperature (<450 °C). Annealing of Cu2FeBO5 in a reducing atmosphere leads to the extrusion of copper and the formation of Fe3BO5, the micro/nanostructural state of which facilitates the partial Cu2FeBO5 recovery associated with the capture of oxygen in oxidizing conditions.

Structure and Electronic Properties of the Quasi-One-Dimensional Ba2Co1-xZnxS3 Series.

This work focuses on the structure and physical properties of the solid solution Ba2Co1-xZnxS3 (0 ≤ x ≤ 1), a family of quasi-one-dimensional sulfides with end members Ba2CoS3 and Ba2ZnS3. The structure of selected compounds with increasing Zn2+ content has been analyzed using neutron diffraction, transmission electron microscopy, and extended X-ray absorption fine structure, and the physical properties have been analyzed via magnetic susceptibility and resistivity measurements. The progressive substitution of the nonmagnetic Zn2+ cation for Co2+ rapidly destroys the antiferromagnetic transition present at 46 K in the quasi-one-dimensional Ba2CoS3, leading to paramagnetic behavior down to the lowest investigated temperature (5 K) for compounds with x > 0.25. For compounds with x ≥ 0.4, a pure Curie-Weiss regime is recovered around 300 K, yielding effective moments consistent with the g factor of the tetrahedrally coordinated Co2+ previously determined for Ba2CoS3. The substitution of Zn2+ for Co2+ also removes the metallic-like behavior of Ba2CoS3, causing an increase in the value of the resistivity with all the Ba2Co1-xZnxS3 compounds showing semiconducting behavior. The negative magnetoresistance of Ba2CoS3 is improved by the substitution of Zn2+ for Co2+, with values of -6% for Ba2Co0.75Zn0.25S3, -9% for Ba2Co0.5Zn0.5S3, and -8% for Ba2Co0.25Zn0.75S3. However, there does not seem to be a correlation between the values of resistivity and magnetoresistance and the content of Zn2+, leading to the hypothesis that transport properties may be linked more closely to extrinsic properties.

Unconventional aspects of electronic transport in delafossite oxides.

The electronic transport properties of the delafossite oxides [Formula: see text] are usually understood in terms of two well-separated entities, namely the triangular [Formula: see text] and ([Formula: see text] layers. Here, we review several cases among this extensive family of materials where the transport depends on the interlayer coupling and displays unconventional properties. We review the doped thermoelectrics based on [Formula: see text] and [Formula: see text], which show a high-temperature recovery of Fermi-liquid transport exponents, as well as the highly anisotropic metals [Formula: see text], [Formula: see text], and [Formula: see text], where the sheer simplicity of the Fermi surface leads to unconventional transport. We present some of the theoretical tools that have been used to investigate these transport properties and review what can and cannot be learned from the extensive set of electronic structure calculations that have been performed.

Magnetodielectric Effect in Crystals of the Noncentrosymmetric CaOFeS at Low Temperature.

Single crystals of the stoichiometric iron calcium oxysulfide CaOFeS have been grown by a solid-state reaction. Structural analysis of CaOFeS at room temperature by combining single-crystal X-ray diffraction data and transmission electron microscopy leads to a stoichiometric hexagonal noncentrosymmetric P63mc layered structure isostructural to CaOZnS. It is built from alternating layers made of FeOS3 tetrahedra sharing sulfur apexes and stacked with Ca(2+) planes. All Fe-O bonds are parallel to the stacking axis; this breaks the centrosymmetry, leading to a polar structure. The dielectric measurements reveal the existence of a magnetodielectric effect near 33 K in good agreement with the Neel temperature, as evidenced near 35 K by specific heat measurements reported by a different group.

Magnetization reversal study of Ni4-xZnxNb2O9compounds using Monte Carlo simulations.

The magnetization reversal (MR) of the layered Ni4-xZnxNb2O9ferrimagnetic compounds, withx=0,0.25,0.50and 0.75, is studied in this work using Monte Carlo (MC) simulations and mean field (MF) calculations. First, we analyze the parent compound to set the parameters of our simulations; testing together MC simulations, MF calculations, and MR experiments reported by Bollettaet al(2022J. Appl. Phys.132153901). Then using two different approaches we fit the MR curves of the series of compounds finding a quite good agreement between MC simulations and the experiments. According to these results, Zn substitutions change the relative contribution to the magnetization of the different layers. Here we present two possible hypotheses to explain this effect; one involving a heterogeneous distribution of Zn2+among the layers, and the other related to distortions of the NiO6octahedra.

Revisiting some chalcogenides for thermoelectricity.

Thermoelectric materials that are efficient well above ambient temperature are needed to convert waste-heat into electricity. Many thermoelectric oxides were investigated for this purpose, but their power factor (PF) values were too small (∼10-4 W m-1 K-2) to yield a satisfactory figure of merit zT. Changing the anions from O2- to S2- and then to Se2- is a way to increase the covalency. In this review, some examples of sulfides (binary Cr-S or derived from layered TiS2) and an example of selenides, AgCrSe2, have been selected to illustrate the characteristic features of their physical properties. The comparison of the only two semiconducting binary chromium sulfides and of a layered AgCrSe2 selenide shows that the PF values are also in the same order of magnitude as those of transition metal oxides. In contrast, the PF values of the layered sulfides TiS2 and Cu0.1TiS2 are higher, reaching ∼10-3 W m-1 K-2. Apparently the magnetism related to the Cr-S network is detrimental for the PF when compared to the d0 character of the Ti4+ based sulfides. Finally, the very low PF in AgCrSe2 (PF = 2.25 × 10-4 W m1 K-2 at 700 K) is compensated by a very low thermal conductivity (κ = 0.2 W m-1 K-1 from the measured Cp) leading to the highest zT value among the reviewed compounds (zT700K = 0.8). The existence of a glassy-like state for the Ag+ cations above 475 K is believed to be responsible for this result. This result demonstrates that the phonon engineering in open frameworks is a very interesting way to generate efficient thermoelectric materials.

Undoped Sr2MMoO6 Double Perovskite Molybdates (M = Ni, Mg, Fe) as Promising Anode Materials for Solid Oxide Fuel Cells.

The chemical design of new functional materials for solid oxide fuel cells (SOFCs) is of great interest as a means for overcoming the disadvantages of traditional materials. Redox stability, carbon deposition and sulfur poisoning of the anodes are positioned as the main processes that result in the degradation of SOFC performance. In this regard, double perovskite molybdates are possible alternatives to conventional Ni-based cermets. The present review provides the fundamental properties of four members: Sr2NiMoO6-δ, Sr2MgMoO6-δ, Sr2FeMoO6-δ and Sr2Fe1.5Mo0.5O6-δ. These properties vary greatly depending on the type and concentration of the 3d-element occupying the B-position of A2BB'O6. The main emphasis is devoted to: (i) the synthesis features of undoped double molybdates, (ii) their electrical conductivity and thermal behaviors in both oxidizing and reducing atmospheres, as well as (iii) their chemical compatibility with respect to other functional SOFC materials and components of gas atmospheres. The information provided can serve as the basis for the design of efficient fuel electrodes prepared from complex oxides with layered structures.

Increase in magnetoresistivity in Ba2CoS3 via Zn2+/Co2+ substitution.

We report an increase of negative magnetoresistivity from 1.7% to 9% in the Ba(2)Co(0.5)Zn(0.5)S(3) series (0

Sr2Fe1+xRe1-xO6 double perovskites: magnetoresistance and (magneto)thermopower.

Polycrystalline Sr2Fe1+xRe1-xO6 samples have been synthesized and structurally characterized by X-ray powder diffraction, transmission electron microscopy and X-ray absorption spectroscopy. Resistivity strongly increases with x, but a large and negative magnetoresistance persists up to x = 0.33. This is discussed considering the charge delocalization in iron and rhenium t2g orbitals.

Origin of Ising magnetism in Ca3Co2O6 unveiled by orbital imaging.

The one-dimensional cobaltate Ca[Formula: see text]Co[Formula: see text]O[Formula: see text] is an intriguing material having an unconventional magnetic structure, displaying quantum tunneling phenomena in its magnetization. Using a newly developed experimental method, [Formula: see text]-core-level non-resonant inelastic x-ray scattering ([Formula: see text]-NIXS), we were able to image the atomic Co [Formula: see text] orbital that is responsible for the Ising magnetism in this system. We can directly observe that corrections to the commonly accepted ideal prismatic trigonal crystal field scheme occur in Ca[Formula: see text]Co[Formula: see text]O[Formula: see text], and it is the complex [Formula: see text] orbital occupied by the sixth electron at the high-spin Co[Formula: see text] ([Formula: see text]) sites that generates the Ising-like behavior. The ability to directly relate the orbital occupation with the local crystal structure is essential to model the magnetic properties of this system.

CuFe2S3 as electrode material for Li-ion batteries.

Electrochemical performances of the isocubanite CuFe2S3 tested as electrode material for Li-ion batteries have been investigated. A first discharge capacity of 860 mA h g-1 shows a conversion process leading to Li2S, copper and iron nanoparticles. Interestingly, a reversible capacity of 560 mA h g-1 at 1.5 V is demonstrated with good cyclability up to 30 cycles.