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  1. Free, publicly-accessible full text available February 5, 2025
  2. Abstract

    A computational search for stable structures among both α and β phases of ternary ATB4borides (A= Mg, Ca, Sr, Ba, Al, Ga, and Zn,Tis3dor4dtransition elements) has been performed. We found that α-ATB4compounds withA= Mg, Ca, Al, andT = V, Cr, Mn, Fe, Ni, and Co form a family of structurally stable or almost stable materials. These systems are metallic in non-magnetic states and characterized by the formation of the localized molecular-like state of3dtransition metal atom dimers, which leads to the appearance of numerous Van Hove singularities in the electronic spectrum. The closeness of such singularities to the Fermi level can be easily tuned by electron doping. For the atoms in the middle of the3drow (Cr, Mn, and Fe), these singularities led to magnetic instabilities and magnetic ground states with a weakly metallic or semiconducting nature. Such states appear as non-trivial coexistence of the different spin ladders formed by magnetic dimers of3delements. These magnetic states can be characterized as an analog of the spin glass state. Experimental attempts to produce MgFeB4and associated challenges are discussed, and promising directions for further synthetic studies are formulated.

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  3. Noncentrosymmetric (NCS) silicon phosphides have recently shown promise as nonlinear optical materials due to the balance of strong second harmonic generation (SHG) activity and large laser damage threshold (LDT) values. While arsenides of electropositive metals, such as Ba, Mg, Zn, and Cd were explored, no NLO properties for transition metal tetrel arsenides have yet been reported. IrSi 3 As 3 is a novel compound, isostructural to IrSi 3 P 3 , which allows a direct investigation on the impact of the heavier pnictogen on structural and optical properties. The direct bandgap is reduced from 1.8 eV for IrSi 3 P 3 to 1.55 eV for IrSi 3 As 3 . Unlike many NLO chalcogenides, IrSi 3 As 3 has a small bandgap without compromising the balance between SHG signal and high LDT values. IrSi 3 As 3 was found to outperform both its phosphide analogue IrSi 3 P 3 , as well as the state-of-the-art infrared SHG standard AgGaS 2 (AGS) in SHG activity and the LDT. 
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    Free, publicly-accessible full text available June 6, 2024
  4. Free, publicly-accessible full text available July 25, 2024
  5. The solvothermal synthetic exploration of the Bi–S–halogen phase space resulted in the synthesis of two bismuth sulfohalides with common structural motifs. Bi 13 S 18 I 2 was confirmed to have the previously reported composition and crystal structure. In contrast, the bromide analogue was shown to have a formula of neither Bi 19 S 27 Br 3 nor Bi 13 S 18 Br 2 , in contrast to the previous reports. The composition, refined from single crystal X-ray diffraction and confirmed by elemental analysis, high-resolution powder X-ray diffraction, and total scattering, is close to Bi 13 S 17 Br 3 due to the partial S/Br substitution in the framework. Bi 13 S 18 I 2 and Bi 13 S 17 Br 3 are n -type semiconductors with similar optical bandgaps of ∼0.9 eV but different charge and heat transport properties. Due to the framework S/Br disorder, Bi 13 S 17 Br 3 exhibits lower thermal and electrical conductivities than the iodine-containing analogue. The high Seebeck coefficients and ultralow thermal conductivities indicate that the reported bismuth sulfohalides are promising platforms to develop novel thermoelectric materials. 
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  6. A facile and universal route for synthesizing transition metal borides has been developed by reaction of boron triiodide (BI 3 ) with elemental transition metals. This method employs relatively low synthesis temperatures to afford single-phase samples of various binary and ternary metal borides, such as Fe 2 B, Co 2 B, Ni 3 B, TiB 2 , VB 2 , CrB 2 , and Ni 2 CoB. This synthesis protocol can be utilized for the topotactic transformation of metal shapes into their respective borides, as exemplified by transformation of Ni foam to Ni 3 B foam. In situ powder X-ray diffraction studies of the Ni–BI 3 system showed that the crystalline nickel borides, Ni 4 B 3 and Ni 2 B, start to form at temperatures as low as 700 K and 877 K, respectively, which is significantly lower than the typical synthesis temperatures required to produce these borides. Ni 3 B synthesized by this method was tested as a supporting material for oxygen evolution reaction (OER) in acidic media. Composite electrocatalysts of IrO 2 /Ni 3 B with only 50% of IrO 2 exhibit current densities and stability similar to pure IrO 2 at mass loadings lower than 0.5 mg cm −2 , indicating Ni 3 B could be a promising supporting material for acidic OER. 
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