Christian Litterscheid

Possible Superhardness of CrB4

Chromium tetraboride [orthorhombic, space group Pnnm (No. 58), a = 474.65(9) pm, b = 548.0(1) pm, c = 286.81(5) pm, and R value (all data) = 0.041], formerly described in space group Immm, was found not to be superhard, despite several theory-based prognoses. CrB(4) shows an almost temperature-independent paramagnetism, consistent with low-spin Cr(I) in a metallic compound. Conductivity measurements confirm the metallic character.

Crystal structure refinement and bonding patterns of CrB4: a boron-rich boride with a framework of tetrahedrally coordinated B atoms.

Crystals of chromium tetraboride, a recently proposed candidate superhard material, have been grown for the first time to allow for a first structure refinement of the compound [orthorhombic, space group Immm (No. 71), a = 474.82(8) pm, b = 548.56(8) pm, and c = 287.17(4) pm, R value (all data) = 0.018]. The previously proposed structure model is confirmed, and accurate interatomic distances are presented for the first time. First-principles electronic structure calculations emphasize the unique framework of three-dimensionally linked B atoms that are tetrahedrally coordinated and carry a slightly negative charge. All B-B bonding is of the 2-center 2-electron type. CrB(4) is metallic with a pseudogap at the Fermi level.

Solid solution between lithium-rich yttrium and europium molybdate as new efficient red-emitting phosphors

Li3.5Y1.5(MoO4)4 was synthesized in the form of phase-pure crystals. It forms a solid solution with Li3.5Eu1.5(MoO4)4. Single crystals obtained from Li2MoO4 fluxes had edge lengths of up to 0.5 mm. The crystal structures of Li3.5(Y1−xEux)1.5(MoO4)4 (x = 0, 0.1, 0.25, 0.5, 0.75 and 1) were determined in the triclinic crystal system (e.g. P, no. 2, Z = 1; Li3.5Y1.5(MoO4)4: a = 5.1875(2) A, b = 6.6380(2) A, c = 10.2731(4) A, α = 100.082(3)°, β = 100.257(2)° and γ = 111.943(2)°). All the compounds are isostructural and crystallize with a structure related to the scheelite-type structure with mixed occupancy of one cation position, while the two others are occupied by Li ions exclusively. Thermal analyses reveal stability in air up to 995 K for Li3.5Y1.5(MoO4)4; the decomposition temperature decreases with an increase in Eu-content. Spectroscopic properties (emission and excitation) were investigated in the context of the search for new thermographic phosphors. Excitation at 395 nm leads to strong red emission at 613 nm. Features of the emission spectra suggest the potential of Li3.5(Y1−xEux)1.5(MoO4)4 as red phosphor candidates for light emitting diodes. Their luminescence properties at high temperatures were also investigated.

Peierls‐Distorted Monoclinic MnB4 with a MnMn Bond

Tetraborides of chromium and manganese exhibit an unusual boron-atom framework that resembles the hypothetical tetragonal diamond. They are believed to be very hard. Single crystals of MnB4 have now been grown. The compound crystallizes in the monoclinic crystal system (space group P21 /c) with a structure that has four crystallographically independent boron-atom positions, as confirmed by (11) B MAS-NMR spectroscopy. An unexpected short distance between the Mn atoms suggests a double Mn-Mn bond and is caused by Peierls distortion. The structure was solved using group-subgroup-relationships. DFT calculations indicate Mn(I) centers and paramagnetism, as confirmed by magnetic measurements. The density of states shows a pseudo-band gap at the Fermi energy and semiconducting behavior was observed for MnB4 .

Manganese Tetraboride, MnB4: High‐Temperature Crystal Structure, p–n Transition, 55Mn NMR Spectroscopy, Solid Solutions, and Mechanical Properties

The structural and electronic properties of MnB4 were studied by high-temperature powder X-ray diffraction and measurements of the conductivity and Seebeck coefficient on spark-plasma-sintered samples. A transition from the room-temperature monoclinic structure (space group P2(1)/c) to a high-temperature orthorhombic structure (space group Pnnm) was observed at about 650 K. The material remained semiconducting after the transition, but its behavior changed from p-type to n-type. (55)Mn NMR measurements revealed an isotropic chemical shift of -1315 ppm, confirming an oxidation state of Mn close to I. Solid solutions of Cr(1-x)Mn(x)B4 (two phases in space groups Pnnm and P2(1)/c) were synthesized for the first time. In addition, nanoindentation studies yielded values of (496±26) and (25.3±1.7) GPa for the Youngs modulus and hardness, respectively, compared to values of 530 and 37 GPa obtained by DFT calculations.

Peierls-distorted monoclinic MnB(4) with a Mn-Mn bond.

Tetraborides of chromium and manganese exhibit an unusual boron-atom framework that resembles the hypothetical tetragonal diamond. They are believed to be very hard. Single crystals of MnB4 have now been grown. The compound crystallizes in the monoclinic crystal system (space group P21 /c) with a structure that has four crystallographically independent boron-atom positions, as confirmed by (11) B MAS-NMR spectroscopy. An unexpected short distance between the Mn atoms suggests a double Mn-Mn bond and is caused by Peierls distortion. The structure was solved using group-subgroup-relationships. DFT calculations indicate Mn(I) centers and paramagnetism, as confirmed by magnetic measurements. The density of states shows a pseudo-band gap at the Fermi energy and semiconducting behavior was observed for MnB4 .

Discovery of γ-MnP4 and the Polymorphism of Manganese Tetraphosphide

A new polymorph of MnP4 was prepared by reaction of the elements via chemical vapor transport with iodine as transporting agent. The crystal structure was refined using single-crystal diffraction data (space group Cc, no. 9, a = 5.1049(8) Å, b = 10.540(2) Å, c = 10.875(2) Å, β = 93.80(2)°). The phase is called γ-MnP4 as it is isostructural with γ-FeP4. It is the fourth reported binary polymorph in the MnP4 system, all of which are stacking variants of nets built with manganese and phosphorus atoms. In γ-MnP4, there are two Mn-Mn distances (2.93 and 3.72 Å) arising from a Peierls-like distortion effectively forming Mn2 dumbbells in the structure. Magnetic and electrical conductivity measurements show diamagnetism and a small anisotropic band gap (100-200 meV) with significantly enhanced conductivity along the crystallographic a axis. Calculations of the electronic and vibrational (phonon) structures show the P-P and Mn-P bonds within the nets are mainly responsible for the stability of the phase. The similar bonding motifs of the polymorphs give rise to the existence of numerous dynamically stable variants. The calculated Helmholtz energy shows the polymorph formation to be closely tied to temperature with the 6-MnP4 structure favorable at low temperatures, the 2-MnP4 favorable between approximately 800 and 2000 K, and 8-MnP4 preferred at high temperatures.

Multiscale and luminescent, hollow microspheres for gas phase thermometry

Recently developed laser-based measurement techniques are used to image the temperatures and velocities in gas flows. They require new phosphor materials with an unprecedented combination of properties. A novel synthesis procedure is described here; it results in hierarchically structured, hollow microspheres of Eu3+-doped Y2O3, with unusual particle sizes and very good characteristics compared to full particles. Solution-based precipitation on polymer microballoons produces very stable and luminescent, ceramic materials of extremely low density. As a result of the – compared to established template-directed syntheses – reduced mass of polymer that is lost upon calcination, micron-sized particles are obtained with mesoporous walls, low defect concentrations, and nanoscale wall thicknesses. They can be produced with larger diameters (~25 µm) compared to known hollow spheres and exhibit an optimized flow behavior. Their temperature sensing properties and excellent fluidic follow-up behavior are shown by determining emission intensity ratios in a specially designed heating chamber. Emission spectroscopy and imaging, electron microscopy and X-ray diffraction results are presented for aerosolizable Y2O3 with an optimized dopant concentration (8%). Challenges in the field of thermofluids can be addressed by combined application of thermometry and particle image velocimetry with such hollow microparticles.

Peierls-Distorted Monoclinic MnB4with a MnMn Bond

Tetraborides of chromium and manganese exhibit an unusual boron-atom framework that resembles the hypothetical tetragonal diamond. They are believed to be very hard. Single crystals of MnB4 have now been grown. The compound crystallizes in the monoclinic crystal system (space group P21 /c) with a structure that has four crystallographically independent boron-atom positions, as confirmed by (11) B MAS-NMR spectroscopy. An unexpected short distance between the Mn atoms suggests a double Mn-Mn bond and is caused by Peierls distortion. The structure was solved using group-subgroup-relationships. DFT calculations indicate Mn(I) centers and paramagnetism, as confirmed by magnetic measurements. The density of states shows a pseudo-band gap at the Fermi energy and semiconducting behavior was observed for MnB4 .