Synthesis, growth and structural properties of (Cu<sub>1-x</sub>Ag<sub>x</sub>)<sub>7</sub>GeSe<sub>5</sub>I solid solutions

Authors

DOI:

https://doi.org/10.24144/2415-8038.2019.45.7-13

Keywords:

Solid solutions, Synthesis, Growth, Diffractogram, Lattice parameter

Abstract

Purpose. The purpose of this work was synthesis and crystal growth, X-ray diffraction studies, investigating the compositional
behavior of the lattice parameter and the density of (Cu1−xAgx)7GeSe5I solid solutions.
Methods. Single crystals of quaternary compounds with argyrodite structure Cu7GeSe5I, Ag7GeSe5I and solid solutions
on their basis (Cu1−xAgx)7GeSe5I with x = 0; 0.25; 0.5; 0.75; 1 were grown by direct crystallization
(Cu7GeSe5I, Ag7GeSe5I) and zone crystallization ((Cu1−xAgx)7GeSe5I) from the melt using a modified method.
Structural studies were carried out by the methods of differential thermal analysis (chromel-alumel thermocouples,
heating and cooling speed 700 K/h) and X-ray phase analysis (DRON 4-07, CuKα radiation, scan angle speed 2Θ –
0.02 deg, exposure – 1 s).
Results. In order to establish near-optimal technological regimes for the growth of single crystals as both individual
compounds of Cu7GeSe5I та Ag7GeSe5I, and solid solutions on their basis (Cu1−xAgx)7GeSe5I they were investigated
by the method of differential thermal analysis. The diffraction patterns of Cu7GeSe5I and Ag7GeSe5I compounds
are indexed in a face-centered cubic lattice. The number and nature of the reflexes on diffractograms of solid solutions
indicate that a continuous series of solid solutions is formed in the system. The compositional dependence of the lattice
parameter was constructed, which is described by Vegard law. As the content of silver increases, a linear increase in
the cubic lattice parameter and a nonlinear increase in density are observed.
Conclusions. Synthesis and growth of single crystals of (Cu1−xAgx)7GeSe5I solid solutions was performed. The
growth was carried out by the methods of direct crystallization (Cu7GeSe5I, Ag7GeSe5I) and zone crystallization
(Cu1−xAgx)7GeSe5I from the melt using a modified method. According to the results of X-ray diffraction studies, it is
established that in Cu7GeSe5I – Ag7GeSe5I system a continuous series of solid solutions is formed. The compositional
dependences of the lattice parameter and density are constructed. It was found out that with increasing silver content, a
linear increase in the cubic lattice parameter and a nonlinear increase in density in (Cu1−xAgx)7GeSe5I solid solutions
are observed.

References

Kuhs W.F. The argyrodites – a new family of the tetrahedrally close-packed srtuctures / W.F. Kuhs, R. Nitsche, K. Scheunemann // Mater. Res. Bull. – 1979. – V. 14. – P. 241–248.

Nilges T. A structural differentiation of quaternary copper argirodites: Structure – property relations of high temperature ion conductors / T. Nilges, A. Pfitzner // Z. Kristallogr. – 2005. – V. 220. – P. 281–294.

Стасюк Ю.М. Одержання і деякі властивості сполук Cu7GeS5I та Cu7GeSe5I / Ю.М. Ста-сюк, О.П. Кохан, В.В. Панько, С.К. Ковач // Вісник Ужгородського університету. Сер. Хімія. – 1999. – №4. – С. 9–12.

Tomm Y. Crystal growth of argyrodite-type phases Cu8−xGeS6−xIx and Cu8–xGeSe6−xIx (0 ≪ x ≪ 0.8) / Y. Tomm, S. Schorr, S. Fiechter // J. Cryst. Growth. – 2008. – V. 310. – P. 2215–2221.

Studenyak I.P. Influence of S→Se substitution on chemical and physical properties of Cu7Ge(S1−xSex)5I superionic solid solutions / I.P. Studenyak, O.P. Kokhan, M. Kranjčec, V.V. Bilanchuk, V.V. Panko // J. Phys. Chem. Solids. – 2007. – V. 68. – P. 1881–1884.

Studenyak I.P. Electrical conductivity, electrochemical and optical properties of Cu7GeS5ICu7GeSe5I superionic solid solutions / I.P. Studenyak, V.V. Bilanchuk, O.P. Kokhan, Yu.M. Stasyuk, A.F. Orliukas, A. Kezionis, E. Kazakevicius, T. Salkus // Lit. J. Phys. – 2009. – V. 49, N 2. – P. 203–208.

Studenyak I.P. Temperature variation of electrical conductivity and absorption edge in Cu7GeSe5I advanced superionic conductor / I.P. Studenyak, M. Kranjčec, V.V. Bilanchuk , O.P. Kokhan, A.F. Orliukas, E. Kazakevicius, A. Kezionis, T. Salkus // J. Phys. Chem. Solids. – 2009. – V. 70. – P. 1478–1481.

Studenyak I.P. Temperature and compositional behaviour of electrical conductivity and optical absorption edge in Cu7Ge(S1−xSex)5I mixed superionic crystals / I.P. Studenyak, M. Kranjčec, V.V. Bilanchuk, O.P. Kokhan, A.F. Orliukas, A. Kezionis, E. Kazakevicius, T. Salkus // Solid State Ionics. – 2010. – V. 181. – P. 1596–1600.

Laqibi M. New silver superionic conductors Ag7XY5Z (X=Si, Ge, Sn; Y=S, Se; Z=Cl, Br, I) – synthesis and electrical properties / M. Laqibi, B. Cros, S. Peytavin, M. Ribes // Solid State Ionics. – 1987. – V. 23. – P. 21–26.

Zerouale A. Electrical properties of Ag7GeSe5I / A. Zerouale, B. Cros, B. Deroide, M. Ribes // Solid State Ionics. – 1988. – V. 28–30. – P. 1317–1318.

Belin R. Ion dynamics in the argyrodite compound Ag7GeSe5I: non-Arrhenius behavior and complete conductivity spectra / R. Belin, A. Zerouale, A. Pradel, M. Ribes // Solid State Ionics. – 2001. – V. 143. – P. 445–455.

Belin R. Crystal structure of the non-stoichiometric argyrodite compound Ag7−xGeSe5I1−x (x = 0.31). A highly disordered silver superionic conducting material / R. Belin, L. Aldon, A. Zerouale, C. Belin , M. Ribes // Solid State Sciences. – 2001. – V. 3. – P. 251–265.

Rietveld H.M. A Profile Refinement Method for Nuclear and Magnetic Structures / H.M. Rietveld // J. Appl. Crystallogr. – 1969. – V. 2. – P. 65–71.

McCusker L.B. Rietveld refinement guidelines / L.B. McCusker, R.B. Von Dreele, D.E. Cox, D. Louër, P. Scardi // J. Appl. Crystallogr. – 1999. – V. 32. – P. 36–50.

Урусов В.С. Теоретическая кристаллохимия / В.С. Урусов . – Москва: Изд-во МГУ, 1987. – 275 с.

Published

2019-12-19

Issue

Section

Статті