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The effect of doping of the TiCoSb compound (MgAgAs structure type) by Mo atoms on the features of the structural characteristics and behavior of the electrokinetic, energetic and magnetic properties of the Ti1-xMoxCoSb semiconducting solid solution (х = 0 - 0.06) in the temperature interval 80 - 400 K was studied. It was shown that including of Mo atoms (rМо= 0.140 nm) in the ToCoSb structure by substitution of Ti atoms (rТі= 0.146 нм) in 4a position is accompanied with non-monotonous variation of the lattice parameter values а(х), indicating unpredictable structural changes. Based on analysis of the variation of the electric resistivity values, thermopower coefficient, magnetic susceptibility and energetic characteristics, it was concluded that simultaneous generation in the crystal of the structural defects of the donor and acceptor nature (donor-acceptor pairs), which generate corresponding energy levels in the band gap of semiconductor and determine its electrical conductivity.

The isothermal section of the phase diagram of the Er–Cr–Ge ternary system was constructed at 1070 K over the whole concentration range using X-ray diffractometry, metallography and electron microprobe analysis (EPMA). At the temperature of investigation the interaction of components in the Er–Cr–Ge system is characterized by the formation of two ternary compounds: ErCr6Ge6 (MgFe6Ge6-type, space group P6/mmm, Pearson symbol hP13; a = 5.15149(3), c = 8.26250(7) Ǻ; RBragg = 0.0493, RF = 0.0574) and ErCr1-xGe2 (CeNiSi2-type, space group Cmcm, Pearson symbol oS16, a = 4.10271(5), b = 15.6652(1), c = 3.99017(4) Ǻ; RBragg = 0.0473, RF = 0.0433). For the ErCr1-xGe2 compound, the homogeneity region was determined (ErCr0.28-0.38Ge2, a = 4.10271 (5)-4.1418 (9), b = 15.6652 (1)-15.7581(4), c = 3.99017 (4)-3.9291(1) Ǻ).

Single crystals of trizirconium nickel heptaantimonide were synthesized from the constituent elements by arc-melting. The compound crystallizes in a unique structure type and belongs to the family of two-layer structures. All crystallographically unique atoms (3 × Zr, 1 × Ni and 7 × Sb) are located at sites with m symmetry. The structure contains `Zr2Ni2Sb5' and `Zr4Sb9' fragments and might be described as a new ZrSb2 derivative with a high Sb content.

Interaction between the components in the Ho-Fe-Sn ternary system was studied using X-ray diffractometry, metallography and electron microprobe analysis. Isothermal section of the phase diagram was constructed at 670 K over the whole concentration range. Component interaction in the Ho-Fe-Sn system at 670 K results in the existence of one ternary compound HoFe6Sn6 which crystallizes in the YCo6Ge6 structure type (space group P6/mmm, a=0.53797(2), c= 0.44446(2) nm). The interstitial-type solid solution HoFexSn2 (up to 8 at.% Fe) based on the HoSn2 (ZrSi2-type structure) binary compound was found. Solubility of Sn in the HoFe2 binary (MgCu2 structure type) extends up to 5 at. %.

The travelling solvent floating zone (TSFZ) growth of Eu-substituted LSCO (La1.81−xEuxSr0.19CuO4, with nominal x = 0 ÷ 0.4) single crystals was systematically explored for the first time. The substitution of La with Eu considerably decreased the decomposition temperature. Optimal growth parameters were found to be: oxygen pressure 9.0–9.5 bars; Eu-free CuO-poor solvent (66 mol% CuO) with a molar ratio of La2O3:SrCO3:CuO = 4:4.5:16.5 and growth rate 0.6 mm/hour. The obtained single crystals were characterized with optical polarized microscopy, X-ray diffraction and energy-dispersive X-ray spectroscopy analysis. The solubility of Eu in LSCO appeared to be limited to x~0.36–0.38 under the used conditions. The substitution of La3+ with smaller Eu3+ ions led to a structural transition from tetragonal with space group I4/mmm for La1.81Sr0.19CuO4 (x = 0) to orthorhombic with space group Fmmm for La1.81−xSr0.19EuxCuO4 (x = 0.2, 0.3, 0.4), and to a substantial shrinking of the c-axis from 13.2446 Å (x = 0.0) to 13.1257 Å (x = 0.4). Such structural changes were accompanied by a dramatic decrease in the superconducting critical temperature, Tc, from 29.5 K for x = 0 to 13.8 K for 0.2. For x ≥ 0.3, no superconductivity was detected down to 4 K.

The interaction of the components in the Gd-Mn-Sn ternary system was studied using the methods of X-ray and microstructure analyses, in the whole concentration range. The phase diagrams of the Gd-Mn-Sn system were constructed at 873 and 673 K. At both temperature of investigation the Gd-Mn-Sn system is characterized by existence of two ternary compounds: GdMn6Sn6 (MgFe6Ge6 structure type, space group P6/mmm) and Gd4Mn4Sn7 (Zr4Co4Ge7 structure type, space group I4/mmm). The formation of the interstitial solid solution GdMnхSn2 based on GdSn2 (ZrSi2-type) binary compound was found up to 10 at. % Mn at 873 K and 673 K. The existence of the substitutional solid solution based on GdMn2 (MgCu2-type) was observed up to 5 at.% Sn and 3 at. % Sn at 873 K and 673 K, respectively. Key words: intermetallics, ternary system, phase equilibria, crystal structure, solid solution.

The mechanism of simultaneous generation of donor-acceptor pairs in ZrNiSn1-xGax semiconductor solid solution is established. The modeled distribution of atoms in the crystal lattice of ZrNiSn1-xGax showed that the speed of movement of Fermi level εF, obtained from the band structure calculations is in agreement with experimental extracted from lnρ(1/T) dependencies. It is shown that with substitution of Sn (5s25p2) with Ga (4s24p1) atoms in 4b crystallographic site both acceptor and donor (vacancies in 4b site) defects are generated. Keywords: crystal and electronic structures, conductivity, thermopower coefficient.

The features of structural, energy state and electrokinetic characteristics were investigated for Hf1 xTmxNiSn solid solution in the range: T = 80 - 400 K, x = 0 - 0.40. It was confirmed partly disorder crystal structure of HfNiSn compound as a result of occupation in the 4a crystallographic site of Hf (5d26s2) atoms by Ni (3d84s2) ones up to ~ 1 % that generates in the crystal structural defects of donor nature. It was shown that introduction of Tm atoms ordered crystal structure (“healing” of structural defects). It was established mechanisms of simultaneous generation of structural defects as acceptors by substitution of Hf (5d26s2) by Tm (4f135d06s2) atoms, and the donor nature defects as a result of the appearance of vacancies in the Sn (4b) atoms sites, which determines the mechanisms of conductivity for Hf1-xTmxNiSn. Keywords: crystal and electronic structures, conductivity, thermopower coefficient.

The features of structural, energy state and kinetic characteristics of the p-GdNiSb and p-LuNiSb semiconductors were investigated in the temperature range T = 4.2-400 K. As example, in p-LuNiSb, the generating of structural acceptor defects as a result of the emergence of vacancies upto 6 % in the 4c positions of Ni (3d84s2) atoms and partial, up to 1.35 %, substitution of Ni (4c) atoms by Lu (5d16s2) ones was shown. Keywords: crystal structure, electronic structure, electrical conductivity, thermopower.

The features of structural, energy state and electrokinetic characteristics were investigated for Hf1-xErxNiSn solid solution in the range: T = 80 – 400 K, x = 0 - 0.10. It was confirmed partly disorder crystal structure of HfNiSn compound as a result of occupation in the 4a crystallographic site of Hf (5d26s2) atoms by Ni (3d84s2) ones up to ~ 1 % that generates in the crystal structural defects of donor nature. It was shown that introduction of Er atoms ordered crystal structure (“healing” of structural defects). It was established mechanisms of simultaneous generation of structural defects as acceptors by substitution of Hf (5d26s2) by Er (4f125d06s2) atoms, and the donor nature defects as a result of the appearance of vacancies in the Sn (4b) atoms sites, which determines the mechanisms of conductivity for Hf1-xErxNiSn.Keywords: crystal and electronic structures, conductivity, thermopower coefficient.

The peculiarities of the crystal and electronic structure of V1-xTixFeSb, х = 0 – 0,20, semiconductor solid solution were investigated. The mechanism of generation of structural defects of acceptor and donor nature is described. In particular the nature of donors in n-VFeSb was established (“a priori doping”) as a result of presence ofvacancies in Sb atomic site (4b). The obtained result lays in the basis of the technology for obtaining thermoelectric materials based on n-VFeSb with maximal efficiency of thermal to electrical energy conversion. Keywords: semiconductor, electrical conduction, electronic structure.

Due to the novel properties of both 2D materials and rare-earth elements, developing 2D rare-earth nanomaterials has a growing interest in research. To produce the most efficient rare-earth nanosheets, it is essential to find out the correlation between chemical composition, atomic structure and luminescent properties of individual sheets. In this study, 2D nanosheets exfoliated from Pr 3+ -doped KCa 2 Nb 3 O 10 particles with different Pr concentrations were investigated. Energy dispersive X-ray spectroscopy analysis indicates that the nanosheets contain Ca, Nb and O and a varying Pr content between 0.9 and 1.8 at%. K was completely removed after exfoliation. The crystal structure is monoclinic as in the bulk. The thinnest nanosheets are 3 nm corresponding to one triple perovskite-type layer with Nb on the B sites and Ca on the A sites, surrounded by charge compensating TBA + molecules. Thicker nanosheets of 12 nm thickness (and above) were observed too by transmission electron microscopy with the same chemical composition. This indicates that several perovskite-type triple layers remain stacked similar to the bulk. Luminescent properties of individual 2D nanosheets were studied using a cathodoluminescence spectrometer revealing additional transitions in the visible region in comparison to the spectra of different bulk phases., (© 2023. The Author(s).)

The nature of metal in the isomorphous flexible metal-organic frameworks is often reported to influence flexibility and responsivity. A prominent example of such behaviour is the DUT-8( M ) family ([ M 2 (2,6-ndc) 2 (dabco)] n , 2,6-ndc = 2,6-naphthalene dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane), where the isostructural compounds with Ni, Zn, Co, and Cu in the paddle wheel cluster are known. The macro-sized crystals of Ni, Co, and Zn based compounds transform to the closed pore (cp) phase under desolvation and show typical gate opening behaviour upon adsorption. The choice of metal, in this case, allows the adjustment of switching kinetics, selectivity in adsorption, and gate-opening pressures. The submicron-sized crystals of of Ni, Co, and Zn based compounds remain in the open pore (op) phase after desolvation. In this contribution, we demonstrate that the presence of Cu in the paddle wheel leads to fundamentally different flexible behaviour. The DUT-8(Cu) desolvation does not lead to the formation of the cp phase, independent of the particle size regime. However, according to in situ powder diffraction analysis, the desolvated, macro-sized crystals of DUT-8(Cu)_op show breathing upon adsorption of CO 2 at 195 K. The submicron-sized particles show rigid, nonresponsive behaviour.

Atom order in the crystal structures of Yb2Cu2-xMg (x = 0.17; Mo2FeB2-type; P4/mbm; a = 0.75592(2) nm; c = 0.40282(1) nm) and Yb9+xCuMg4-x (x = 0.034; Hf9Mo4B-type; P63/mmc; a = 1.0169(5) nm; c = 1.0290(5) nm) was determined from powder and X-ray single-crystal counter data analyses supported by electron probe microanalyses. Among the group of the so-called κ-phases, Yb9+xCuMg4-x is the first representative formed by a lanthanoid element. The structure of this κ-phase can be viewed as a typical network of corner-connected empty Yb6-octahedra, which encompass Yb6Mg6-icosahedra (filled by a mix of Mg/Yb atoms) and Yb6-trigonal prisms centered by Cu atoms to complete the three-dimensional metal framework. From another point of view, the same structure is considered as built from infinite polyicosahedral columns of Yb9Mg4 composition with Cu atoms located in trigonal prismatic interstices, highlighting similarities with other Yb-rich Yb-Cu-Mg phases. Density functional theory (DFT) calculations classify Yb9CuMg4 as a polar intermetallic. Metallic-like behavior is inferred from the Sommerfeld constant, γ = 49.2 mJ/mol·K(2), derived from the electronic density of states, calculated at the Fermi level. DFT integration of the f-density of states indicates almost completely filled f-states, revealing 13.6 and 13.7 electrons in the valence band for Yb1 and Yb2 atoms, respectively, close to the Yb(2+) ground state ((1)S0) for both Yb atoms. Magnetic susceptibility data recorded on the same compound are consistent with a nonmagnetic divalent Yb(2+) state. Temperature-dependent heat capacity data display a metallic behavior characterized by a small Sommerfeld constant γ = 64.8 mJ/mol·K(2) and a rather low Debye temperature ΘD = 140 K as typical for soft materials.

X-ray single crystal (XSC) and powder diffraction data (XPD) were used to elucidate the crystal structure of a new refractory silicon boride Ta7Si2(Si(x)B(1-x))2 (x = 0.12). Tetragonal Ta7Si2(Si(x)B(1-x))2 (space group P4/mbm; a = 0.62219(2) nm, c = 0.83283(3) nm) with B atoms randomly sharing the 4g site with Si atoms is isotypic with the boride structure of (Re,Co)7B4. The architecture of the structure of Ta7Si2(Si(x)B(1-x))2 combines layers of three-capped triangular metal prisms (Si,B)[Ta(6+2)(Si,B)] alternating with double layers of two-capped Si[Ta(8+1)Si] Archimedian metal antiprisms. Consequently, the metal framework contains (B/Si) pairs and Si-Si dumbbells. These two types of coordination figures around the nonmetal atoms are typical for the system-inherent structures of Ta2B (or Ta2Si) and Ta3B2. DFT calculations showed strong B(Si)-B(Si) and Si-Si bonding and represent Ta7Si2(Si(x)B(1-x))2 as a covalent-ionic compound. This bonding behavior is reflected in the high hardness value of 1750 HV. The Sommerfeld constant, γ = 7.58 mJ/mol K(2), as derived from the electronic density of states, calculated at the Fermi level, suggests typical metallic behavior.

Single crystals of trizirconium nickel hepta-anti-monide were synthesized from the constituent elements by arc-melting. The compound crystallizes in a unique structure type and belongs to the family of two-layer structures. All crystallographically unique atoms (3 × Zr, 1 × Ni and 7 × Sb) are located at sites with m symmetry. The structure contains 'Zr(2)Ni(2)Sb(5)' and 'Zr(4)Sb(9)' fragments and might be described as a new ZrSb(2) derivative with a high Sb content.

Single crystals of didysprosium heptanickel tritin were synthesized from the constituent elements by arc-melting. Two of the five Ni atoms are at general sites and all other atoms are at sites with either twofold or m symmetry. The structure contains 'DyNi(5)Sn' and 'DyNi(2)Sn(2)' fragments and represents a new member of the CaCu(5) series of intermetallics.