2021 IEEE XIIth International Conference on Electronics and Information Technologies (ELIT)

Phonon Spectra of Cu7GeSe5I and Ag7GeSe5I

Crystals
Ivan Nebola
Department of Applied Physics of
“Uzhhorod National University”
State Institution of Higher Education
State Institution of Higher Education
“Uzhhorod National University”
Uzhhorod, Ukraine
ivan.nebola@uzhnu.edu.ua
2021 IEEE 12th International Conference on Electronics and Information Technologies (ELIT) | 978-1-6654-4296-1/21/$31.00 ©2021 IEEE | DOI: 10.1109/ELIT53502.2021.9501096
Anton Katanytsia Viktor Studenyak
Department of Applied Physics of Department of Applied Physics of
“Uzhhorod National University” “Uzhhorod National University”
State Institution of Higher Education
“Uzhhorod National University”
“Uzhhorod National University”
Uzhhorod, Ukraine
Uzhhorod, Ukraine viktor.studeniak@uzhnu.edu.ua
katanitsyaanton@gmail.com

Yurii Pal Aleksyna Shteyfan Vasyl Sidey

Department of Applied Physics of
“Uzhhorod National University”
State Institution of Higher Education
“Uzhhorod National University”
Uzhhorod, Ukraine
paalgyuri@gmail.com
Department of PhD and Doctorate Department of Inorganic Chemistry of
programmes of “Uzhhorod National “Uzhhorod National University”
University” State Institution of Higher Education
State Institution of Higher Education “Uzhhorod National University”
“Uzhhorod National University” Uzhhorod, Ukraine
Uzhhorod, Ukraine vasyl.sidey@uzhnu.edu.ua
aleksyna.shteifan@uzhnu.edu.ua
Ihor Studenyak
Department of Applied Physics of
“Uzhhorod National University”
State Institution of Higher Education
“Uzhhorod National University”
Uzhhorod, Ukraine
ihor.studenyak@uzhnu.edu.ua

Abstract — Model calculations of the phonon dispersion
dependencies have been carried out for the Cu7GeSe5I and
Ag7GeSe5I superionic crystals. For the first time, within the
framework of the superspace symmetry concept the Cu7GeSe5I
and Ag7GeSe5I crystals have been investigated and their (3+d)-
dimensional model descriptions have been developed. The
description of the models of the considered structures was
reduced to the construction of the modulation vectors arrays,
definition of the mass modulation functions, construction of the
generalized dynamic matrix as a superposition of the dynamic
matrices of monoatomic structures; and the eigenvalues of the
dispersion dependencies of the single particle perturbations
have been obtained for the high symmetry directions of the
Brillouin zone. The dynamic matrices Dαβ(k+qi) of the
protocrystals were calculated taking into account a certain
number of the force constant of the influential coordination
groups.
Keywords — argyrodites, phonon spectra, modulation vectors,
eigenvalues, dispersion.
I. INTRODUCTION
Li-, Ag- and Cu-containing argyrodites are actively
studied as one of the most promising solid electrolyte and
thermoelectric materials [1-6]. Cu7GeSe5I and Ag7GeSe5I
compounds belong to the argyrodite family which possess
high ionic conductivity [7, 8]. Thus, Cu7GeSe5I crystal is
characterized by the highest value of electrical conductivity
among the well-known copper-containing superionic
conductors (0.64 S/cm at the frequency of 106 Hz at 300 K).
For (Cu1-хAgx)7GeSe5I the compositional dependence of the
ionic conductivity is non-monotonous with a maximum near
x=0.5, whereas the electronic conductivity for (Cu1-
xAgx)7GeSe5I mixed crystals nonlinearly decreases with x [8].
Investigations of the crystal structures of the argyrodite
phases demonstrating a significant ionic conductivity are of
great interest to both experimenters and theorists in the field
of solid state physics. The physicochemical properties of the
Cu7GeSe5I and Ag7GeSe5I superionic crystalline conductors,
which are the subject of the present study, are actually
determined by their crystal structures featuring the partial
occupations of certain crystallographic orbits with the Cu
(Ag) atoms [7]. The color symmetry theory [9] and the
superspace symmetry concept [10] allow researchers to
consecutively include some additional "physical" parameters
(color, phase, charge sign, spin, etc.) into the symmetrical
description of the crystal structure under study. Among the
varieties of the generalized symmetry, the latter is convenient
and clear when constructing the (3+d)-dimensional models in
order to describe complex crystalline formations of the same
metrics and the same scale of the function of the protocrystal
carrier [11]. The construction of the (3+d)-dimensional
metrics is based on its higher symmetry and connected with
the additional internal "phase" d-dimensional space, which
allows researchers to describe complex crystals and systems
as the natural (sa×sa×sa) superlattices. Furthermore,
different combinations of the bases of the protocrystal and of
the real crystal formation can be taken into account along
with all possible variants of compositional filling of available
crystallographic positions. The use of a complete set of
modulation vectors allows one to determine the amplitudes
of the mass modulation functions and, based on these
functions, to generate a generalized dynamic matrix of a real
physical object as well as a mass perturbation matrix. The
first matrix is given in the form of a superposition of
dynamic protocrystal matrices defined at different Brillouin
zone (BZ) points associated with the modulation vectors,

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 2021 IEEE XIIth International Conference on Electronics and Information Technologies (ELIT)
whereas the second one is described by the amplitudes of the
mass modulation functions.
Thus, the aim of this work is to use the superspace
symmetry concept in order to calculate the phonon spectra of
the Cu7GeSe5I and Ag7GeSe5I argyrodite crystals.
II. CALCULATIONS
In the approaches of the superspace symmetry concept
[12], the dispersion curves of a phonon spectrum of a
crystalline formation under consideration are defined as
solutions of the matrix equation (under the condition of zero
equality of the determinant) of the form:
Dαβ (k + qi ) − ω 2δ αβ δ ij − ω 2 ρ (i − j )δ αβ = 0,
where Dαβ (k + qi ) are the dynamic matrices of a
monoatomic protocrystal, defined at the
the natural FCC [(8a,8a,0); (8a,0,8a); (0,8a,8a)] superlattice,
by using the equidistant approximation of the force field.
It should be noted that superionic representatives of the
argyrodite family belong to the crystal structures
characterized by the partial occupations of certain
crystallographic orbits by the metal atoms (cations) of one
sort. The crystal structures of the title members of this
family, the Cu7GeSe5I and Ag7GeSe5I superionics [7],
consists of a rigid anionic framework and a disordered
cationic sublattice formed by the Cu(Ag) atoms, which is
typical for the argyrodite crystals. In the Paterson projections
of the above structures, the electron density peaks specify the
following crystallographic positions of the atoms: 24-fold
position (g), 48-fold position (h), 16-fold position (e), and
(1) two of the four 4-fold positions (a), (b), (c), (d). Accordingly,
the following atomic positions were chosen: Cu1(Ag1) in
24(g), Cu2(Ag2) in 48(h), 16 of 20 Se in 16(e) with x = 3/8,
(k + qi ) points of and 4 Se in 4(c), I in 4(a), Ge in 4(b) [5]

(
the BZ, ρ ( i − j ) = ρ i qi , ∆ b * *
)
are the amplitudes of the
i j III. RESULTS AND DISCUSSION
mass modulation function given for the (qi – qj), modulation In order to calculate the phonon spectra of the Cu7GeSe5I
vector, k is the wave vector, qi are the modulation vectors, and Ag7GeSe5I crystals, the model structures featuring the
and α,β are the coordinates x,y,z. The solution of the matrix atomic coordinates and occupancies presented in Table 1
equation with respect to ω2(k) allows one to determine the were chosen.
dispersion dependences of a given phonon spectrum, while
taking into account different variants of compositional filling An attempt to take into account the partial occupancy of
makes possible to trace from their genesis [12]. the Cu2(Ag2) position unavoidably requires a transition to a
model that takes into account the 512-fold multiplication of
The dynamic matrices Dαβ (k + qi ) of the protocrystal the unit cells of the protocrystal with the FCC basis (a, a, 0),
(a, 0, a), (0, a, a) and the superlattice with the FCC basis (8a,
are determined from the relationship (2):
8a, 0), (8a, 0, 8a), (0, 8a, 8a), i.e. 8 × 8 × 8 = 512-fold
multiplication.
Dαβ (k + qi ) = α n
nα nβ
n 2
(
1 − ei (k +qi )n , ) (2)
The array of 512 possible positions of atoms covers 30
( n≠0)
orbits, and the set of 512 modulation vectors is divided into
where αn is the force constant of the interaction between the 30 stars (Table 2, Table 3).
atom in the 0th position and the nth neighboring atom, nα and
nβ are the projections of the vector n on the axes α,β. TABLE I. ATOMIC POSITIONS AND OCCUPANCIES OF THE MODEL
CU7GESE5I AND AG7GESE5I ARGYRODITE STRUCTURES
In the equidistant approximation taken for the model, the
force characteristic depends only on the distance between the Coordi- Model
Coordi- Occupan- Coordi- Occupan- nates occupan-
atoms, and then the interaction of different varieties of atoms Atom
nates [7] cy [7] nates [13] cy [13] [this cy [this
in equidistant positions is the same. This approach allows (0.02362, (0.01747,
paper] paper]
Cu1 (0, 1/4,
one to build a dynamic matrix in the quasi-diagonal form. In (Ag1)
0.25, 0.624 0.25, 1.0
1/4)
5/6
the non-equidistant approximation, αn is determined by the 0.25)
(0.01914,
0.25)
Cu2 (0, 5/16,
distance between the positions and also by the difference in (Ag2)
0.30918, 0.376 0.0
5/16)
2/12
0.30918)
physical characteristics of the objects that occupy these I (0, 0, 0) 0.989 (0, 0, 0) 1.0 (0, 0, 0) 1.0
positions. (0.25, (0.25,
(1/4, 1/4,
Se1 0.25, 0.989 0.25, 1.0 1.0
1/4)
0.25) 0.25)
The values of the amplitudes of the mass characteristics (0.62183, (0.62183,
ρ(qj) are obtained by solving a system of equations (3) with Se2 0.62183, 1.0 0.62183, 1.0
(5/8, 5/8,
5/8)
1.0
0.62183) 0.62183)
respect to the amplitudes of the mass modulation functions (0.5, 0.5, (0.5, 0.5, (1/2, 1/2,
Ge 1.0 1.0 1.0
ρ(qj) = ρj: 0.5) 0.5) 1/2)

s3 Description of the structure and calculations within the

m(rk ) = ρ (q j )e
iq j rk
 j =1
, (3)
where s is the number of possible positions of atoms in the
superlattice, m(rk) are the mass characteristics in these
positions, qj is the array of modulation vectors, the number of
which is equal to the number of positions in the superlattice.
Here we describe some members of the argyrodite family
in the superspace symmetry concept, based on the model of
superspace symmetry concept were performed by solving the
secular equation (1) of the order 1536×1536, involving 512
possible positions, 14 of which are occupied by the atoms of
the Cu7GeSe5I and Ag7GeSe5I structures: I [1] (0, 0, 0), Cu2
(Ag2) [142] (3, 3, 0), Cu2 (Ag2) [153] (0, –3, –3), Cu1
(Ag1) [370] (4,4,0), Cu1 (Ag1) [371] (4,0,4), Cu1 (Ag1)
[373] (–4,4,0), Cu1 (Ag1) [374] (–4,0,4), Cu1 (Ag1) [375]
(0,–4,4), Se2 [490] (6,2,2), Se2[491] (2,6,2), Se2 [492]
(2,2,6), Se2 [493] (–6,2,2), Ge [498] (4,4,4), Si [512] (8,0,0).

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 2021 IEEE XIIth International Conference on Electronics and Information Technologies (ELIT)
TABLE II. ARRAYS OF MODULATION VECTORS GATHERED IN STARS L–Г, Г–Х, X–W, W–K, K–Г directions of the BZ are shown
FOR THE CU7GESE5I AND AG7GESE5I ARGYRODITE STRUCTURES WITH THE
FCC [(8A,8A,0); (8A,0,8A); (0,8A,8A)] SUPERLATTICE USED FOR TAKING INTO in Fig. 1.
ACCOUNT THE PARTIAL OCCUPANCY OF THE CU2 (AG2) POSITION

No. of star Modulation vectors TABLE III. ARRAYS OF POSITIONS GATHERED IN ORBITS FOR THE
Atoms CU7GESE5I AND AG7GESE5I ARGYRODITE STRUCTURES WITH THE FCC
(multiplicity) gathered in stars
I 1(1) [ 0,0,0 ] [(8A,8A,0); (8A,0,8A); (0,8A,8A)] SUPERLATTICE USED FOR TAKING INTO
ACCOUNT THE PARTIAL OCCUPANCY OF THE CU2 (AG2) POSITION
2(12) [ π / 8a, π / 8a, 0 ]
3(6) [ π / 4a, 0, 0 ] No. of orbit Atomic positions
Atoms
(position) gathered in orbits
4(24) [ π / 4 a , π / 8 a , π / 8a ] I 1(1) [0,0,0]
5(12) [ π / 4a, π / 4a, 0 ] 2(2-13) [a, a,0]
6(24) [ 3π / 8a, π / 8a, 0 ] 3(14-19) [2a,0,0]
7(8) [ π / 4a, π / 4a, π / 4a ] 4(20-43) [2a, a, a]
8(48) [ 3π / 8a , π / 4 a , π / 8a ] 5(44-55) [2a,2a,0]
9(6) [ π / 2a, 0, 0 ] 6(56-79) [3a, a,0]
Cu2(Ag2)(1/12) 10(12) [ 3π / 8a, 3π / 8a, 0 ] 7(80-87) [2a,2a,2a]
11(24) [ π / 2a, π / 8a, π / 8a ] 8(88-135) [3a,2a, a]
12(24) [ π / 2a, π / 4a, 0 ] 9(136-141) [4a,0,0]
13(24) [ 3π / 8a, 3π / 8a, π / 4a ] Cu2(Ag2)(1/12) 10(142-153) [3a,3a,0]
14(24) [ π / 2a, π / 4a, π / 4a ] 11(154-177) [4a, a, a]
15(48) [ π / 2a, 3π / 8a, π / 8a ] 12(178-201) [4a,2a,0]
16(24) [ 5π / 8a, π / 8a, 0 ] 13(202-225) [3a,3a,2a]
17(48) [ 5π / 8a, π / 4a, π / 8a ] 14(226-249) [4a,2a,2a]
Cu1(Ag1) (5/6) 18(6) [ π / 2a, π / 2a, 0 ] 15(250-297) [4a,3a, a]
19(24) [ π / 2a, 3π / 8a, 3π / 8a ] 16(298-321) [5a, a,0]
20(12) [ 3π / 8a, 3π / 8a, 0 ] 17(322-369) [5a,2a, a]
21(12) [ π / 2a, π / 2a, π / 4a ] Cu1(Ag1) (5/6) 18(370-375) [4a,4a,0]
22(6) [ 3π / 4a, 0, 0 ] 19(376-399) [4a,3a,3a]
23(24) [ 3π / 8a, 3π / 8a, π / 4a ] 20(400-411) [5a,3a,0]
24(24) [ 3π / 4a, π / 8a, π / 8a ] 21(412-423) [4a,4a,2a]
25(12) [ 3π / 4a, π / 4a, 0 ] 22(424-429) [6a,0,0]
Se2 26(8) [ 3π / 4a, π / 4a, π / 4a ] 23(430-453) [5a,3a,2a]
Se1 27(1) [ π / 2a, π / 2a , π / 2a ] 24(454-477) [6a, a, a]
28(1) 25(478-489) [6a,2a,0]
[ π / 2a, π / 2a , π / 2a ]
Se2 26(490-497) [6a,2a,2a]
29(12) [ π / 8 a , π / 8a , 0 ]
Se1 27(498) [4a,4a,4a]
Ge 30(1) [ π / a, 0, 0 ]
28(499) [−4a,−4a,−4a]
29(500-511) [7a, a,0]
The dynamic matrices of the protocrystal were calculated Ge 30(512) [8a,0,0]
at 512 points of BZ. By modifying the occupancies of
crystallographic positions of the atoms, and by adjusting the IV. CONCLUSIONS
values of the force constants in the equidistant As a result of the model analysis of the structures of
approximation, the phonon spectra were obtained for the Cu7GeSe5I and Ag7GeSe5I taking into account the occupancy
high symmetric directions of the Brillouin zone of the FCC of the orbit of the Cu2(Ag2) atom in the metric of the
lattice by using the method described earlier [14]. protocrystal with the FCC basis (a, a, 0), (a, 0, a), (0, a, a)
The values of the force constants αn are given in the order and the superlattice with the FCC basis (8a, 8a, 0), (8a, 0,
of ascending distances between the position of the orbit 8a), (0, 8a, 8a), the rearrangement of the phonon spectrum of
1(0, 0, 0) and n+1, taking into account all possible variants of the Cu7GeSe5I and Ag7GeSe5I crystals was observed, which
the distances between the pairs of occupying atoms. The is apparently caused by the change of the corresponding
force constants were chosen in the equidistant mass characteristics of the Cu and Ag atoms and by a certain
approximation; the interaction was determined only by the expected correlation between the power constants. The
distance and did not depend on the type of interacting pairs results of the calculations performed in this work are in a
fairly satisfactory agreement with the experimental data
of atoms. For example, for the compound Ag7GeSe5I, α26n is
the force constant describing the interaction at a distance of obtained for the frequency range of ~150-550 cm–1 at the Γ
point [14]. The wide frequency ranges of values obtained
4a√3 and equal to 3 N/m, so the others are, correspondingly,
here can actually reflect the effective possibility of their
powerConstants:= Vector[row] (28, [15.1, 0, 0, 0, 0, 0.10e-1,
changes by changing the occupancy of the Cu2(Ag2) atoms
4, 0.10e-1, .6, 1, 0, 0, 0, 0, .7, 0, 3, 7, 0, 0, 0, 2, 0, 0, 0.8e-1,
(i.e. by a "jump" of the metal atoms between the considered
3, 0, 8.5 (N/m)]. For the Cu7GeSe5I argyrodite, the
orbits), which is accompanied by the high ionic conductivity
calculations are analogous: powerConstants:= [82.1, 0, 0, 0,
in the superionic Cu7GeSe5I and Ag7GeSe5I crystalline
0, 3.1, 2.2, 1.7, 0.6, 1, 0, 0, 0, 0, 0.7, 0, 1, 5, 0, 0, 0, 2, 0, 0,
argyrodite phases.
10.0, 53, 0.6, 19 (N/m)]. The dispersion dependences for the

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 2021 IEEE XIIth International Conference on Electronics and Information Technologies (ELIT)
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