Room-temperature modification of potassium oxyfluorotungstate, G2-K3WO3F3, has been prepared by low-temperature chemical route and single crystal growth. Wide optical transparency range of 0.3–9.4μm ...and forbidden band gap Eg=4.32eV have been obtained for G2-K3WO3F3 crystal. Meanwhile, its electronic structure has been calculated with the first-principles calculations. The good agreement between the theorectical and experimental results have been achieved. Furthermore, G2-K3WO3F3 is predicted to possess the relatively large nonlinear optical coefficients.
Using the cm-size K3WO3F3 crystal (left upper), the transmission spectrum (right upper) and XPS valence electronic states (left lower) were measured, agreed with the ab initio results (right lower). Display omitted
► The cm-size G2-K3WO3F3 single crystals are obtained. ► Optical absorption edge and transmission range are defined for G2-K3WO3F3 crystal. ► Crystal structures of all known K3WO3F3 polymorph modifications are determined. ► Experimental electronic structure is consistent with the first-principles result. ► G2-K3WO3F3 is predicted as a crystal with large NLO coefficients.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Three new alkaline earth metal complexes, Ca
2
(H
2
O)
8
(μ
2
-HTBA-O,O′)
2
(HTBA-O)
2
(1), Ca(H
2
O)
5
(HTBA-O)
2
·2H
2
O (2), and Sr(H
2
O)
4
(μ
2
-HTBA-O,S)
2
n
(3) (H
2
TBA = 2-thiobarbituric ...acid, C
4
H
4
N
2
O
2
S), were synthesized and characterized by FT-IR spectroscopy, TG-DSC, and single-crystal and powder X-ray diffraction analysis. The single-crystal X-ray diffraction data revealed that 1 and 2 are discrete structures, whereas 3 is a polymer. In 1 and 2, Ca
2+
is seven-coordinate and forms a monocapped trigonal prism. In 1, the prisms are pairwise connected with the assistance of two μ
2
-HTBA-O,O′
−
ligands. In 3, Sr
2+
is coordinated by four monodentate HTBA
−
via S or O donors and four waters, with the formation of a distorted square antiprism. The antiprisms are connected by μ
2
-O,S bridging HTBA
−
. Hydrogen bonding involving coordinated water and π-π interactions plays an important role in construction of the supramolecular 3-D structures in 1-3. Infrared spectroscopic data supported the structural data. The thermal stability of 1-3 decreases in the order 1 > 2 > 3. Dehydration of 1-3 was a multi-step process, followed by exothermic oxidative degradation of the 2-thiobarbiturate moiety between 290 and 800 °C.
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BFBNIB, DOBA, GIS, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, UILJ, UKNU, UL, UM, UPUK
•Fe3O4 nanoparticles modified with Ag were synthesized with thermal decomposition method.•Nanoparticles morphology and size do not depend on Ag concentration.•The Ag effect on nanoparticles magnetic ...properties was studied.•Strong influence of Ag on visible magnetic circular dichroism was revealed and discussed.
Effect of Ag inclusions on magnetic properties and magnetic circular dichroism (MCD) of Fe3O4 nanoparticles (NPs) in the mixed system of Fe3O4 and Ag NPs in dependence on the relative concentration of the components is presented. The samples were synthesized by the thermal decomposition of the mixture of constant concentration of Fe(NO3)3·9H2O and varied concentration of AgNO3. The synthesized powdered samples consisted of Fe3O4 and Ag NPs located very close with each other, and in the most cases the Fe3O4 NPs were bordered with the Ag nanocrystals. The Ag introducing in the samples does not effect, practically, in the Fe3O4 NPs morphology and size distribution. At the same time, Ag NPs in the powdered samples cause a decrease in the Fe3O4 NPs magnetization and shift of the blocking temperature to lower temperatures, both approximately proportional to the Ag concentration. Most significant changes are revealed in the MCD spectra in the energy region of 1.2–2.2 eV. We have discussed the influence of the Ag NPs on the MCD spectra features in terms of the charge-transfer electron transitions.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The effect of the size of Bi
2
Fe
4
O
9
and BiFeO
3
nanoparticles on the magnetoelectric interaction in the Bi
2
Fe
4
O
9
/BiFeO
3
composite with a percentage ratio of 67/33 has been studied. The ...electrostriction and electric polarization on electric and magnetic field in wide temperature range has been measured. The hysteresis of the polarization and
I‒V
characteristics has been found. Temperature ranges with activation and hopping types of conductivity have been found. The mechanism of electric polarization and the crossover temperature from dipole polarization to migration polarization at 260 K have been established. Linear and quadratic contributions to the magnetoelectric effect have been found. Below 120 K the linear contribution is an order of magnitude greater than the quadratic contribution and above 240 K the quadratic contribution to the ME effect prevails. Models have been proposed to explain the enhancement of the magnetoelectric effect as a result of the migration polarization in mullite and linear magnetoelectric effect in bismuth ferrite. The correlation of temperatures of the extremum of the temperature coefficient of the electrical resistance and the magnetic phase transition in mullite at 260 K indicates a polaron-type conductivity and a strong electron‒phonon interaction. A change in the sign of the electrostriction coefficient upon heating and the compression temperature of the composite in an electric field was found.
Graphical Abstract
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
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•RFeTi2O7 behave as insulating spin glasses (SG) combining 3d and 4f elements.•Disorder in the Fe sublattice is driving the SG behavior modulated by the R presence.•R3+ single ion ...anisotropy increases SG temperature and the coercive field.•Uniaxial anisotropy of R3+ slows down spin dynamics and reduces spin fluctuations.•Increase in the SG temperature correlates with the anisotropic RFe exchange interaction.
Zirconolite oxides R3+Fe3+Ti2O7 (R rare earth element) are known to exhibit spin glass behaviour at low temperatures. Here we present a detailed study of these compounds for R = Eu, Gd, Dy, Ho, and Er, together with reviewed previous measurements on Sm, Tb, Tm, Yb and Lu, with the scope of determining the role played by the rare earth on their magnetic properties. They have been investigated using X-ray powder diffraction, and further characterized by magnetization, frequency dependent ac susceptibility and heat capacity measurements. RFeTi2O7 compounds are all isostructural showing orthorhombic structure, space group Pcnb at 300 K. Disorder of the magnetic ions in the RFeTi2O7 lattice induces spin glass behaviour at low temperatures, mainly due to the Fe sublattice. We show that magnetic rare earth ions participate in the spin glass state tuning its properties. The single ion anisotropy of the R3+ ions, excluding exchange interaction with other magnetic ions, has been calculated by ab initio methods, and expressed in terms of the g tensor of the ground doublet or quasi-doublet in Kramers (Sm, Dy, Er, Yb) and non-Kramers (Tb, Ho) ions, respectively, in an effective spin S* = 1/2 model. In the case of R with a singlet ground state (Eu, Tm) or a multiplet state (Gd), the ion is isotropic. We show that the relative increase in the spin-glass temperature ΔTSGR/TSGFe with respect to the LuFeTi2O7, where Lu is non-magnetic, correlates qualitatively with the product of the ratio gz/gJ (R = Tb, Dy, Ho, and Er), or g⊥/gJ (R = Sm), times the ratio of exchange interactions J~R,FeJFe,Fe determined from the paramagnetic room temperature susceptibility measurements. Besides, for increasing anisotropy the spin glass transition dynamics slows down to values typical of cluster glass. The coercive field below the transition is increased in the same trend. This paper explains the effect of the R-Fe exchange interaction and R single ion anisotropy on the spin-glass behaviour of these compounds.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
85 RM
3
(BO
3
)
4
(R is the rare-earth element (Y, La–Lu) and M = Al, Sc, Cr, Fe, or Ga) compounds with the huntite structure have been analyzed. The analysis of the structures has made it possible ...to determine critical atomic displacements during the phase transition
R
32 ↔
P
3
1
21 and establish how these critical displacements can be controlled by varying the ionic radii. A tolerance factor has been derived and its threshold value below which the structure is stable in the
R
32 phase and above it, in the distorted
P
3
1
21 phase, has been found. The formula has been tested on more than 30 huntite-family compounds and good agreement has been obtained. Therefore, it can be used with confidence to predict new compounds. At the moment, the tolerance factor has allowed us to establish previously unknown regularities in huntites.
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DOBA, EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, IZUM, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, SIK, UILJ, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
The features of electronic structure of La0.7Sr0.3MnO3, Pr0.8Sr0.2MnO3, and Pr0.6Sr0.4MnO3 polycrystalline films of different thickness have been investigated using magnetic circular dichroism (MCD) ...in the range of 1.1–4.2 eV. The temperature behavior of the samples electrical resistance were also has been studied. It was found that films with high Sr content (0.3 and 0.4) act as high-temperature semiconductors, while the maximum in the temperature dependences of resistivity these films indicates the transition of the samples to the metallic state at some temperature TM-S, which is different for different sample thickness. The films with the lower Sr content (0.2) act as insulators in the used temperature range. The MCD spectra have been decomposed to the Gaussian-shaped lines, and the temperature dependence of intensity of each line has been analyzed in comparison with temperature dependence of the films magnetization and with their electric conductivity type. Different temperature behavior of the intensity of four specified Gaussian-lines was revealed for semiconductor films. In the case of insulating Pr0.8Sr0.2MnO3 samples, the intensity of three specified Gaussian lines changes with the temperature in the same way as the magnetization changed. It was established that the lanthanide (La, Pr) type does not affect the MCD spectra shape for the films with the same electrical conductivity type. Besides, the correlation between the MCD data of the films and their conductivity type was revealed. Due to the detailed analysis of the specified Gaussian lines with taking into account the well-known in the literature absorption bands, lying outside the studied spectral region, the MCD bands for the studied manganite films have been identified with electronic transitions of a different nature.
•La0.7Sr0.3MnO3, Pr0.8Sr0.2MnO3, and Pr0.6Sr0.4MnO3 films act as objects of research.•Magnetic circular dichroism (MCD) and electrical resistance of the films are studied.•Lanthanide type does not affect the MCD spectra shape for the films with the same electrical conductivity type.•MCD band of the positive sign near 2.3–2.4 eV is typical for the metallic films only.•Revealed MCD bands are identified with electronic transitions of a different nature.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Core-shell FexOy@C nanoparticles (NPs) modified with Ag were studied with x-ray diffraction, transmission electron microscopy, energy dispersive elemental mapping, Mössbauer spectroscopy, static ...magnetic measurements, and optical magnetic circular dichroism (MCD). FexOy@C NPs synthesized by the pyrolysis process of the mixture of Fe(NO3)3 · 9H2O with oleylamine and oleic acid were added to a heated mixture of oleylamine and AgNO3 in different concentrations. The final product was a mixture of iron oxide crystalline NPs in an amorphous carbon shell and Ag crystalline NPs. The iron oxide NPs were presented by two magnetic phases with extremely close crystal structures: Fe3O4 and γ-Fe2O3. Ag is shown to form crystalline NPs located very close to the iron oxide NPs. An assumption is made about the formation of hybrid FexOy@C-Ag NPs. Correlations were obtained between the Ag concentration in the fabricated samples, their magnetic properties and the MCD spectrum shape. Introducing Ag led to a approximately linear decrease of the NPs saturation magnetization depending upon the Ag concentration, it also resulted into the MCD spectrum shift to the lower light wave energies. MCD was also studied for the Fe3O4@C NPs synthesized earlier with the same one-step process using different heat treatment temperatures, and MCD spectra were compared for two series of NPs. A possible contribution of the surface plasmon excitation in Ag NPs to the MCD spectrum of the FexOy@C-Ag NPs is discussed.
•The Cu2−XSe-Sb2Se3 system phase diagram was revisited and reconstructed.•The samples of CuSbSe2 and Cu3SbSe3 annealed at 450 °C 4320 h are single-phase.•Cu3SbSe3 and CuSbSe2 melt incongruently, ...ΔН(Cu3SbSe3) = 67.6 J/g ΔН(CuSbSe2) = 85.1 J/g.•CuSb3Se5 is formed at 445 °C, ΔНf = 21.5 J/g, and decomposes at 527 °C, ΔНd = 36.7 J/g.•Thermal expansion anisotropy for CuSbSe2 and Sb2Se3 is similar to As2S3 and AsS.
The phase diagram of the Cu2−XSe-Sb2Se3 system is revisited to clarify ambiguity/disagreement in previously reported data. Ternary Cu3SbSe3 and CuSbSe2 compounds were obtained. In order to confirm that the phases have been identified correctly, crystal structures were solved, and the energy band gaps measured. For the sample containing 75 mol% Sb2Se3 and 25 mol% Cu1.995Se the temperature range of the stability of the high-temperature CuSb3Se5 phase was determined for the first time. This phase is formed at 445 °С, decomposes following a peritectic reaction at 527 °С, and can be quenched. A high-temperature X-ray diffraction study of a sample containing 75 mol% Sb2Se3 and 25 mol% Cu2Se allowed us to measure the thermal expansion of the CuSbSe2 and Sb2Se3 phases present in the sample. The anisotropy of thermal expansion of CuSbSe2 is similar to that of As2S3 (orpiment); thermal expansion of Sb2Se3 is similar to that of AsS (realgar). The 6 balance equations of the invariant phase transformations involving all the ternary compounds existing in the Cu2−XSe-Sb2Se3 system were suggested for the first time. The temperature and the enthalpies of all these transformations were measured. A phase diagram of the Cu2−XSe-Sb2Se3 system was found for the first time in all the range of concentrations at temperatures from ambient to the complete melting. This diagram takes into consideration the phase equilibria that involve all the ternary compounds that are possible in this system. The liquidus of the Cu2−XSe-Sb2Se3 system was calculated according to Redlich-Kister equation; it agrees with the experimental data within 1–17 °С.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Intense search for new nonlinear optical crystals for the mid-infrared region is in progress, and Li-containing quaternary chalcogenides are expected to improve transparency range, stability, ...phase-matching conditions, and other parameters in comparison with commercially available AgGaS2, AgGaSe2, and ZnGeP2. Single crystals of Li2In2GeSe6 up to 8 mm in size were obtained by the Bridgman–Stockbarger growth technique, and their high quality was confirmed by exciton luminescence. A monoclinic structure and direct band-to-band electronic transitions were established, and the thermal expansion was shown to be virtually isotropic. Defect-related absorption and luminescence were revealed, and the way to lower them was suggested. The electronic structure, density of states, and some optical properties were calculated from the first principles for Li2In2GeSe6. The calculated nonlinear coefficients and rather large birefringence indicate a strong phase-matching ability. These investigations demonstrate that Li2In2GeSe6 is a promising mid-infrared nonlinear optical crystal.
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