Electronic properties of single-crystalline FeO.

We synthesized single and polycrystals of iron oxide with an unconventional FeO stoichiometry under high-pressure high-temperature (HP-HT) conditions. The crystals of FeO had a CaFeO-type structure composed of linear chains of iron with octahedral and trigonal-prismatic oxygen coordinations. We investigated the electronic properties of this mixed-valence oxide using several experimental techniques, including measurements of electrical resistivity, the Hall effect, magnetoresistance, and thermoelectric power (Seebeck coefficient), X-ray absorption near edge spectroscopy (XANES), reflectance and absorption spectroscopy, and single-crystal X-ray diffraction.

Novel Class of Rhenium Borides Based on Hexagonal Boron Networks Interconnected by Short B Dumbbells.

Transition metal borides are known due to their attractive mechanical, electronic, refractive, and other properties. A new class of rhenium borides was identified by synchrotron single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells between 26 and 75 GPa. Recoverable to ambient conditions, compounds rhenium triboride (ReB) and rhenium tetraboride (ReB) consist of close-packed single layers of rhenium atoms alternating with boron networks built from puckered hexagonal layers, which link short bonded (∼1.

Verwey-Type Charge Ordering and Site-Selective Mott Transition in FeO under Pressure.

The metal-insulator transition driven by electronic correlations is one of the most fundamental concepts in condensed matter. In mixed-valence compounds, this transition is often accompanied by charge ordering (CO), resulting in the emergence of complex phases and unusual behaviors. The famous example is the archetypal mixed-valence mineral magnetite, FeO, exhibiting a complex charge-ordering below the Verwey transition, whose nature has been a subject of long-time debates.

Giant Room-Temperature Power Factor in p-Type Thermoelectric SnSe under High Pressure.

Materials that can efficiently convert heat into electricity are widely utilized in energy conversion technologies. The existing thermoelectrics demonstrate rather limited performance characteristics at room temperature, and hence, alternative materials and approaches are very much in demand. Here, it is experimentally shown that manipulating an applied stress can greatly improve a thermoelectric power factor of layered p-type SnSe single crystals up to ≈180 µW K cm at room temperature.

Structural Diversity of Magnetite and Products of Its Decomposition at Extreme Conditions.

Magnetite, FeO, is the oldest known magnetic mineral and archetypal mixed-valence oxide. Despite its recognized role in deep Earth processes, the behavior of magnetite at extreme high-pressure high-temperature (HPHT) conditions remains insufficiently studied. Here, we report on single-crystal synchrotron X-ray diffraction experiments up to ∼80 GPa and 5000 K in diamond anvil cells, which reveal two previously unknown FeO polymorphs, γ-FeO with the orthorhombic YbS-type structure and δ-FeO with the modified ThP-type structure.

Structural Stability and Properties of Marokite-Type γ-MnO.

We synthesized single crystals of marokite (CaMnO)-type orthorhombic manganese (II,III) oxide, γ-MnO, in a multianvil apparatus at pressures of 10-24 GPa. The magnetic, electronic, and optical properties of the crystals were investigated at ambient pressure. It was found that γ-MnO is a semiconductor with an indirect band gap of 0.

Synthesis of Ilmenite-type ε-MnO and Its Properties.

In contrast to the corundum-type AX structure, which has only one crystallographic site available for trivalent cations (e.g., in hematite), the closely related ABX ilmenite-type structure comprises two different octahedrally coordinated positions that are usually filled with differently charged ions (e.

Author Correction: Discovery of FeO: a new iron oxide with a complex monoclinic structure.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

A Room-Temperature Verwey-type Transition in Iron Oxide, Fe O.

Functional oxides whose physicochemical properties may be reversibly changed at standard conditions are potential candidates for the use in next-generation nanoelectronic devices. To date, vanadium dioxide (VO ) is the only known simple transition-metal oxide that demonstrates a near-room-temperature metal-insulator transition that may be used in such appliances. In this work, we synthesized and investigated the crystals of a novel mixed-valent iron oxide with an unconventional Fe O stoichiometry.

Pressure tuning of charge ordering in iron oxide.

A Verwey-type charge-ordering transition in magnetite at 120 K leads to the formation of linear units of three iron ions with one shared electron, called trimerons. The recently-discovered iron pentoxide (FeO) comprising mixed-valent iron cations at octahedral chains, demonstrates another unusual charge-ordering transition at 150 K involving competing formation of iron trimerons and dimerons. Here, we experimentally show that applied pressure can tune the charge-ordering pattern in FeO and strongly affect the ordering temperature.

Structural and Magnetic Transitions in CaCoVO Perovskite at Extreme Conditions.

We investigated the structural, vibrational, magnetic, and electronic properties of the recently synthesized CaCoVO double perovskite with the high-spin (HS) Co ions in a square-planar oxygen coordination at extreme conditions of high pressures and low temperatures. The single-crystal X-ray diffraction and Raman spectroscopy studies up to 60 GPa showed a conservation of its cubic crystal structure but indicated a crossover near 30 GPa. Above 30 GPa, we observed both an abnormally high "compressibility" of the Co-O bonds in the square-planar oxygen coordination and a huge anisotropic displacement of HS-Co ions in the direction perpendicular to the oxygen planes.

Dramatic Changes in Thermoelectric Power of Germanium under Pressure: Printing n-p Junctions by Applied Stress.

Controlled tuning the electrical, optical, magnetic, mechanical and other characteristics of the leading semiconducting materials is one of the primary technological challenges. Here, we demonstrate that the electronic transport properties of conventional single-crystalline wafers of germanium may be dramatically tuned by application of moderate pressures. We investigated the thermoelectric power (Seebeck coefficient) of p- and n-type germanium under high pressure to 20 GPa.

Tuning the electronic and vibrational properties of SnPSe and PbPS crystals and their metallization under high pressure.

External stimuli enabling either a continuous tuning or an abrupt switching of the basic properties of materials that are utilized in various industrial appliances could significantly extend their range of use. The key characteristics of semiconductors are basically linked to their electronic and optical properties. In this study, we experimentally demonstrated that two kindred wide-band-gap semiconductors, ferroelectric SnPSe and paraelectric PbPS, which are commonly used in optical technologies, have remarkably different and unusual responses in their electronic band structures to applied moderate pressures.

Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure.

Iron oxides are fundamentally important compounds for basic and applied sciences as well as in numerous industrial applications. In this work we report the synthesis and investigation of a new binary iron oxide with the hitherto unknown stoichiometry of Fe7O9. This new oxide was synthesized at high-pressure high-temperature (HP-HT) conditions, and its black single crystals were successfully recovered at ambient conditions.

Charge-ordering transition in iron oxide Fe4O5 involving competing dimer and trimer formation.

Phase transitions that occur in materials, driven, for instance, by changes in temperature or pressure, can dramatically change the materials' properties. Discovering new types of transitions and understanding their mechanisms is important not only from a fundamental perspective, but also for practical applications. Here we investigate a recently discovered Fe4O5 that adopts an orthorhombic CaFe3O5-type crystal structure that features linear chains of Fe ions.

A hard oxide semiconductor with a direct and narrow bandgap and switchable p-n electrical conduction.

An oxide semiconductor (perovskite-type Mn2 O3 ) is reported which has a narrow and direct bandgap of 0.45 eV and a high Vickers hardness of 15 GPa. All the known materials with similar electronic band structures (e.

Crystal structure and thermal expansion of Mn(1-x)Fe(x)Ge.

A series of temperature-dependent single-crystal and powder diffraction experiments has been carried out using synchrotron radiation in order to characterize the monogermanides of Mn, Fe and their solid solutions. The MnGe single crystal is found to be enantiopure and we report the absolute structure determination. The thermal expansion, parametrized with the Debye model, is discussed from the temperature-dependent powder diffraction measurements for Mn(1-x)Fe(x)Ge (x = 0, 0.

New antiferromagnetic perovskite CaCo3V4O12 prepared at high-pressure and high-temperature conditions.

A new perovskite, CaCo(2+)3V(4+)4O12, has been synthesized at high-pressure and high-temperature (HP-HT) conditions. The properties of this perovskite were examined by a range of techniques. CaCo3V4O12 was found to adopt a double-perovskite cubic lattice [a = 7.

Anomalous compression and new high-pressure phases of vanadium sesquioxide, V2O3.

We report results of a powder x-ray diffraction (XRD) study of vanadium sesquioxide, V2O3, under pressurization in a neon pressure-transmitting medium up to 57 GPa. We have established a bulk modulus value for corundum-type V2O3 of B0 = 150 GPa at B' = 4. This bulk modulus value is the lowest among those known for the corundum-type-structured oxides, e.

Structural stability of a golden semiconducting orthorhombic polymorph of Ti2O3 under high pressures and high temperatures.

An orthorhombic polymorph of titanium oxide (Ti(2)O(3)) has been synthesized at high pressure-high temperature (HP-HT) conditions. It has been refined in the Pnma space group and the Th(2)S(3) structural type with the unit cell parameters as follows: a = 7.8248(6) Å, b = 2.

Is the Verwey transition in Fe(3)O(4) magnetite driven by a Peierls distortion?

In this viewpoint article we analyse recent crucial structural, optical and transport experiments on Fe(3)O(4) magnetite across the Verwey transition at T(V)∼120-125 K. We find that all the relevant experimental data are consistent with a model of a Peierls distortion in the cubic spinel lattice, and likewise, some of them evidence against the original and still distributed hypothesis of the long range charge ordering origin of the Verwey transition. An estimated Peierls transition temperature (T(P)) is comparable with T(V).