Synthesis, structure, and properties of EuErCuS3

Русейкина, А. В.; Solovyov, Leonid A.; Chernyshev, V. A.; Aleksandrovsky, A.S.; Андреев, О. В.; Krylova, S. N.; Крылов, А. С.; Великанов, Д. А.; Мolokeev, Maxim S.; Maximov, Nikolai G.; Grigoriev, Maxim V.; Garmonov, Alexander A.; Matigorov, Alexey V.

doi:10.1016/j.jallcom.2019.07.059

Cited by 16 publications

(21 citation statements)

References 43 publications

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“…In compounds EuLnCuS3, the europium ion is Eu 2+ [11,68,71]. An insignificant structural difference also anticipates a similarity of charges in EuLnCuX3 (X = S, Se).…”

Section: Elastic Propertiesmentioning

confidence: 95%

“…Unfortunately, contrarily to the corresponding sulfide analogues [9,11], we faced problems collecting Raman spectra for some of the reported selenides, and our numerous attempts failed. This can be explained by the narrower bandgap and sequent high absorption at the wavelengths of excitation and of the scattered Raman signal.…”

Section: Eutbcuse3 Structural Type Eu2cus3mentioning

confidence: 99%

“…Nowadays, the copper-containing chalcogenides are of particular interest and in the limelight of many studies, the reason being their thermal, electrical and optical properties, which make them promising materials for infrared (IR) and nonlinear optics [1,2], photocatalysis, photoelectric energy and proton conductivity [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. Development of electronic technologies opened prospects for the copper containing selenides as one of the most promising absorbers in thin film photovoltaic cells and high-performance thermoelectric materials [19,20].…”

Section: Introductionmentioning

confidence: 99%

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Quaternary Selenides EuLnCuSe3: Synthesis, Structures, Properties and In Silico Studies

Grigoriev

Solovyov

Русейкина

et al. 2022

IJMS

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In this work, we report on the synthesis, in-depth crystal structure studies as well as optical and magnetic properties of newly synthesized heterometallic quaternary selenides of the Eu+2Ln+3Cu+1Se3 composition. Crystal structures of the obtained compounds were refined by the derivative difference minimization (DDM) method from the powder X-ray diffraction data. The structures are found to belong to orthorhombic space groups Pnma (structure type Ba2MnS3 for EuLaCuSe3 and structure type Eu2CuS3 for EuLnCuSe3, where Ln = Sm, Gd, Tb, Dy, Ho and Y) and Cmcm (structure type KZrCuS3 for EuLnCuSe3, where Ln = Tm, Yb and Lu). Space groups Pnma and Cmcm were delimited based on the tolerance factor t’, and vibrational spectroscopy additionally confirmed the formation of three structural types. With a decrease in the ionic radius of Ln3+ in the reported structures, the distortion of the (LnCuSe3) layers decreases, and a gradual formation of the more symmetric structure occurs in the sequence Ba2MnS3 → Eu2CuS3 → KZrCuS3. According to magnetic studies, compounds EuLnCuSe3 (Ln = Tb, Dy, Ho and Tm) each exhibit ferrimagnetic properties with transition temperatures ranging from 4.7 to 6.3 K. A negative magnetization effect is observed for compound EuHoCuSe3 at temperatures below 4.8 K. The magnetic properties of the discussed selenides and isostructural sulfides were compared. The direct optical band gaps for EuLnCuSe3, subtracted from the corresponding diffuse reflectance spectra, were found to be 1.87–2.09 eV. Deviation between experimental and calculated band gaps is ascribed to lower d states of Eu2+ in the crystal field of EuLnCuSe3, while anomalous narrowing of the band gap of EuYbCuSe3 is explained by the low-lying charge-transfer state. Ab initio calculations of the crystal structures, elastic properties and phonon spectra of the reported compounds were performed.

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“…In compounds EuLnCuS3, the europium ion is Eu 2+ [11,68,71]. An insignificant structural difference also anticipates a similarity of charges in EuLnCuX3 (X = S, Se).…”

Section: Elastic Propertiesmentioning

confidence: 95%

Section: Eutbcuse3 Structural Type Eu2cus3mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Quaternary Selenides EuLnCuSe3: Synthesis, Structures, Properties and In Silico Studies

Grigoriev

Solovyov

Русейкина

et al. 2022

IJMS

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“…Complex sulfides EuLnCuS 3 crystallize in ST Ba 2 MnS 3 SG Pnma (Nd), ST KZrCuS 3 SG Cmcm (Sm, Gd, Er). The optical band gap of EuErCuS 3 is 1.934 eV [22]. Ferromagnets are EuNdCuS 3 and EuSmCuS 3 with magnetic phase transition temperatures of 3.1 K and 3.1 K, respectively [23].…”

Section: Introductionmentioning

confidence: 99%

“…Ferromagnets are EuNdCuS 3 and EuSmCuS 3 with magnetic phase transition temperatures of 3.1 K and 3.1 K, respectively [23]. Ferrimagnets are EuGdCuS 3 (Tc = 5.2 K) [16] and EuErCuS 3 (Tc = 4.8 K) [22]. Above the temperatures of magnetic transitions, the compounds exhibit paramagnetic properties [16,23].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Properties of EuLnCuSe3 (Ln = Nd, Sm, Gd, Er)

et al. 2021

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EuLnCuSe3 (Ln = Nd, Sm, Gd, Er), due to their complex composition, should be considered new materials with the ability to purposefully change the properties. Samples of the EuLnCuSe3 were prepared using Cu, rare earth metal, Se (99.99%) by the ampoule method. The samples were obtained by the crystallization from a melt and annealed at temperatures 1073 and 1273 K. The EuErCuSe3 crystal structure was established using the single-crystal particle. EuErCuSe3 crystallizes in the orthorhombic system, space group Cmcm, KCuZrS3 structure type, with cell parameters a = 4.0555 (3), b = 13.3570 (9), and c = 10.4602 (7) Å, V = 566.62 (6) Å3. In structure EuErCuSe3, erbium ions are coordinated by selenium ions in the octahedral polyhedron, copper ions are in the tetrahedral coordination, europium ions are between copper and erbium polyhedra layers and are coordinated by selenium ions as two-cap trigonal prisms. The optical band gap is 1.79 eV. At 4.7 K, a transition from the ferrimagnetic state to the paramagnetic state was detected in EuErCuSe3. At 85 and 293 K, the compound is in a paramagnetic state. According to XRPD data, EuLnCuSe3 (Ln = Nd, Sm, Gd) compounds have a Pnma orthorhombic space group of the Eu2CuS3 structure type. For EuSmCuSe3, a = 10.75704 (15) Å, b = 4.11120 (5) Å, c = 13.37778 (22) Å. In the series of EuLnCuSe3 compounds, the optical band gap increases 1.58 eV (Nd), 1.58 eV (Sm), 1.72 eV (Gd), 1.79 eV (Er), the microhardness of the 205 (Nd), 210 (Sm), 225 (Gd) 235 ± 4 HV (Er) phases increases, and the thermal stability of the phases increases significantly. According to the measurement data of differential scanning calorimetry, the EuNdCuSe3 decomposes, according to the solid-phase reaction T = 1296 K, ΔH = 8.2 ± 0.8 kJ/mol. EuSmCuSe3 melts incongruently T = 1449 K, ΔH = 18.8 ± 1.9 kJ/mol. For the EuGdCuSe3, two (Tα↔β = 1494 K, ΔHα↔β = 14.8 kJ/mol, Tβ↔γ = 1530 K, ΔHβ↔γ = 4.8 kJ/mol) and for EuErCuSe3 three polymorphic transitions (Tα↔β = 1561 K, ΔHα↔β = 30.3 kJ/mol, Tβ↔γ = 1579 K, ΔHβ↔γ = 4.4 kJ/mol, and Tγ↔δ = 1600 K, ΔHγ↔δ = 10.1 kJ/mol). The compounds melt incongruently at the temperature of 1588 K, ΔHmelt = 17.9 ± 1.8 kJ/mol and 1664 K, ΔHmelt = 25.6 ± 2.5 kJ/mol, respectively. Incongruent melting of the phases proceeds with the formation of a solid solution of EuSe and a liquid phase.

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