Synthesis, structure, and properties of EuScCuS3 and SrScCuS3

Русейкина, А. В.; Мolokeev, Maxim S.; Chernyshev, V. A.; Aleksandrovsky, A.S.; Крылов, А. С.; Krylova, S. N.; Великанов, Д. А.; Grigoriev, Maxim V.; Maximov, Nikolai G.; Shestakov, N. P.; Garmonov, Alexander A.; Matigorov, Alexey V.; Tarasov, A. S.; Рауцкий, М. В.; Khritokhin, N. A.; Melnikova, Ludmila V.; Tret’yakov, N. Yu.

doi:10.1016/j.jssc.2020.121926

Cited by 18 publications

(23 citation statements)

References 54 publications

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“…The magnetic properties of EuYCuSe 3 and EuLnCuSe 3 (Ln = La, Tb, Dy, Ho, Tm, Yb, Lu) correlate well with the properties of isostructural sulfides (Table 5) [9,10,68].…”

Section: Magnetic Propertiesmentioning

confidence: 74%

“…Quaternary selenides reported in this work were obtained from the corresponding starting materials, which were carefully prepared before the synthesis by thermolysis of the corresponding co-crystallized metal nitrates. Both Eu 2 O 3 and copper were pretreated as described in the literature [9]. Oxides of rare earth elements were annealed 1070 K to remove sorption water, hydroxides, hydrocarbonates and oxycarbonates [62,63], while Tb 4 O 7 was annealed at 470 K to keep its chemical composition and avoid a stepwise transformation: Tb 4 O 7 → Tb 11 O 20 → Tb 7 O 12 → Tb 2 O 3 [64].…”

Section: Synthesis Of Selenidesmentioning

confidence: 99%

“…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%

“…Quaternary selenides have a high energy conversion efficiency with a figure of merit higher than unity at 600 K [32]. Due to a 4f-5d transition in the Eu 2+ ion, incorporation of this ion into the compound yields in a narrower band gap [9], than, e.g., 1.96 eV obtained for BaGdCuSe 3 [3]. For a series of thermodynamically stable quaternary chalcogenides ALnCuSe 3 (A = Sr, Ba, Pb, Eu), quantum mechanical calculations revealed a very low thermal conductivity of the lattice due to its strong anharmonicity, which enhances phonon scattering [32].…”

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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“…The magnetic properties of EuYCuSe 3 and EuLnCuSe 3 (Ln = La, Tb, Dy, Ho, Tm, Yb, Lu) correlate well with the properties of isostructural sulfides (Table 5) [9,10,68].…”

Section: Magnetic Propertiesmentioning

confidence: 74%