LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES
The structure of LaNi9Si4 compound has been investigated by X-ray powder ans single crystal method. This silicide crystalize in CeNi8.5Si4 structure type: space group I4 mcm, Pearson symbol tI56, а = 7.86415(6), с = 11.5101(1) Å, RB = 0.0653; а = 7.83933(17), с = 11.4472(5)&nbs...
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Ukrainian Chemistry Journal| _version_ | 1871465937026154496 |
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| author | Belan, Bohdana Pukas, Svitala Dzevenko, Mariya Manyako, Mykola Kuzhel, Bohdan Gladyshevskii, Roman |
| author_facet | Belan, Bohdana Pukas, Svitala Dzevenko, Mariya Manyako, Mykola Kuzhel, Bohdan Gladyshevskii, Roman |
| author_institution_txt_mv | [
{
"author": "Bohdana Belan",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv"
},
{
"author": "Svitala Pukas",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv"
},
{
"author": "Mariya Dzevenko",
"institution": "Львівський національний університет імені Івана Франка"
},
{
"author": "Mykola Manyako",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv"
},
{
"author": "Bohdan Kuzhel",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv"
},
{
"author": "Roman Gladyshevskii",
"institution": "Department of Inorganic Chemistry, Ivan Franko National University of Lviv"
}
] |
| author_sort | Belan, Bohdana |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:51Z |
| description | The structure of LaNi9Si4 compound has been investigated by X-ray powder ans single crystal method. This silicide crystalize in CeNi8.5Si4 structure type: space group I4 mcm, Pearson symbol tI56, а = 7.86415(6), с = 11.5101(1) Å, RB = 0.0653; а = 7.83933(17), с = 11.4472(5) Å, R = 0.0220, wR = 0.0734 for X-ray single crystal data. Unlike the prototype CeNi8.5Si4.5, where the Wyckoff position 4d is occupied by mixture of Ni and Si atoms, in the structure of the ternary silicide LaNi9Si4, the atoms are ordered in all Wyckoff positions. Additionally, the electrical properties for the compound were investigated. The temperature dependence of the electrical resistivity exhibits metal behaviour (ρ0 = 121.60 μΩ∙cm, θD = 191 K, A = 2.2·10-9 μΩ∙m∙K-3).
  |
| doi_str_mv | 10.33609/2708-129X.89.05.2023.3-12 |
| first_indexed | 2025-09-24T17:43:51Z |
| format | Article |
| fulltext |
3
UDC 548.736.4+546.669:546.747:546.28 doi: 10.33609/2708-129X.89.05.2023.3-12
LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES
B. Belan1, S. Pukas1, M. Dzevenko2*, M. Manyako1, B. Kuzhel1, R. Gladyshevskii1
1Department of Inorganic Chemistry, Ivan Franko National University of Lviv,
6 Kyryla i Mefodia Str., 79005 L’viv, Ukraine;
2Kruty Heroes Lviv Lyceum with intensive military and physical training,
68 Pasichna Str., 79038 L’viv, Ukraine
e-mail: m_dzevenko.teacher@lgk.ukr.education
The structure of LaNi9Si4 compound has been investigated by X-ray powder ans sing
le crystal method. This silicide crystalize in CeNi8.5Si4 structure type: space group I4 mcm,
Pearson symbol tI56, а = 7.86415(6), с = 11.5101(1) Å, RB = 0.0653; а = 7.83933(17),
с = 11.4472(5) Å, R = 0.0220, wR = 0.0734 for X-ray single crystal data. Unlike the prototype
CeNi8.5Si4.5, where the Wyckoff position 4d is occupied by mixture of Ni and Si atoms, in the
structure of the ternary silicide LaNi9Si4, the atoms are ordered in all Wyckoff positions. Ad-
ditionally, the electrical properties for the compound were investigated. The temperature de-
pendence of the electrical resistivity exhibits metal behaviour (ρ0 = 121.60 μΩ∙cm, θD = 191 K,
A = 2.2·10-9 μΩ∙m∙K-3).
Key words: lanthanum, nickel, silicon, crystal structure, electrical resistivity.
INTRODUCTION
The ternary systems RE-Ni-Si (RE = rare
earth metals) have attracted interest of scien-
tist due to complicated interaction of the com-
ponents. A high number of compounds with
various crystal structures and interesting phy
sical properties exists in these systems [1–5].
Probably the La-Ni-Si system is the most inte
resting among them. The isothermal section of
this system has been constructed in the whole
concentration range at 400 ºC [6] and twen-
ty ternary compounds have been found, but
full crystal structure determination has been
performed not for all of them. Given this, we
conducted research the part of the La-Ni-Si
system, namely the section 7.14 at. % La. Pre-
viously we reported on the study of the com-
pound LaNi11.8-11.4Si1.2-1.6, which adopts the cu-
bic structure type CaCu6.5Al6.5 (space group
Fm-3c, Pearson code cF112) [7]. Another phase
exist on this section is LaNi9Si4 compound,
which is isotypic to CeNi8.5Si4.5-type according
to Refs. [8, 9]. Since we were lucky enough to
synthesize a single-phase sample and obtain
a single crystal, the detailed crystal structure
determination of LaNi9Si4 and investigation of
electrical resistivity was performed. Herein we
present the results of these investigations.
4 ISSN 2708-129X. Укр. хім. журн., 2023
LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIESINORGANIC CHEMISTRY
EXPERIMENT AND DISCUSSION OF
THE RESULTS.
X-ray powder investigations
12 ternary samples along the isoconcentrate
7.14 at.% La were melted under an argon at-
mosphere in an arc furnace, and annealed at
870 K under vacuum for 720 h.
In the beginning, the structure of the in-
vestigated phase was studied by X-ray pow-
der diffraction of sample with composition
La7.14Ni61.43Si31.43. The powder intensity data
was collected on automatic diffractome-
ter STOE STADI P with linear PSD detector
(transmission mode, 2θ/ω-scan; Cu Kα1 radia
tion, curved germanium [1 1 1] monochro-
mator; 2θ-range 6.000 ≤ 2θ ≤ 120.225° with
step 0.015 °2θ; PSD step 0.480 °2θ, scan time
250 s/step). The value of linear absorption co-
efficient was estimated from the logarithmic
ratio between the primary beam intensity and
its intensity after passing through background
and measured samples. A preliminary data
processing, X-ray profile and phase analyses
were performed using the STOE WinXPOW
(version 2.21) program package [10]. The pro-
gram DBWS [11] was used for the refinement
of the crystal structure. The crystallographic
data and the results of crystal structure refine-
ments of the silicide are listed in the Table 1.
Fig. 1 shows the X-ray diffraction patterns of
La7.14Ni61.43Si31.43 sample. The results of investi-
gation confirmed that the investigated silicide
is isotypical to the structure of CeNi8.5Si4.5 type.
However, in the structure of our compound,
all crystallographic positions are occupied by
atoms in an orderly manner, and the compo-
sition of the compound is described by the for-
mula LaNi9Si4, while in the prototype one of
the positions occupied by mixture of Ni and Si
atoms.
Table 1.
Crystal data and structure refinements for LaNi9Si4 compound.
Structure type CeNi8,5Si4,5
Pearson symbol tI56
Space group I4/mcm
Unit cell dimensions, Å a = 7.86415(6), b = 11.5101(1)
Volume, Å3 711.84(1)
No. formula units per unit cell 4
Calculated density DX, g/sm3 7.285
Number of reflects 162
Zero value of 2θ, ° 0.0109(6)
Profile parameters U; V; W 0.034(1); -0.012(2); 0.0116(4)
Reliability factors RB; Rp; Rwp 0,0653; 0,0513; 0,0650
La 4a (0 0 1/4)
Biso, Å
2 0.59(2)
Ni1 16l (x y z) x = 0,6294(1); y = 0,1294(1); z = 0,1824(1)
5https://ucj.org.ua
B. Belan, S. Pukas, M. Dzevenko, M. Manyako, B. Kuzhel, R. Gladyshevskii UCJ № 05 / Vol. 89
Structure type CeNi8,5Si4,5
Biso, Å
2 1,20(2)
Ni2 16k (x y 0) x = 0,0692(2); y = 0,2047(2)
Biso, Å
2 1,20(2)
Ni3 4d (0 ½ 0)
Biso, Å
2 1,20(2)
Si 16l (x y z) x = 0,1715(2); y = 0,6715(2); z = 0,1176(2)
Biso, Å
2 1,06(2)
Fig. 1. Observed (۰), calculated (-) and difference X-ray diffraction patterns of LaNi9Si4.
X-ray single crystal investigations
More detail crystal structure investigation
was performed by X-ray single crystal method.
Single crystals were selected from the sample
by mechanical fragmentation from the sample
with composition La7.14Ni67.86Si25. They exhibit
metallic lustre whereas the ground powders are
dark grey. The reflections intensities were mea
sured with graphite-monochromatized Мо Kα
radiation on an STOE IP diffractometer at
6 ISSN 2708-129X. Укр. хім. журн., 2023
LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIESINORGANIC CHEMISTRY
295(2) K. The structures were solved by direct
methods and refined by the SHELX program
package [12] with anisotropic atomic displace-
ment parameters. After the data collection,
the single crystal was analyzed by EDX spec-
troscopy with a Leica420i scanning electron
microscope. The experimentally determined
composition of the grain of is close to the com-
position calculated from the structure refine-
ments.
The crystallographic data and details on the
data collection for LaNi9Si4 are listed in Ta-
ble 2. The structure was refined in space group
I4/mcm with anisotropic atomic displacement
parameters. A final electron-density difference
map was flat and did not reveal any significant
residual peaks. Concerning the occupations of
crystallographic positions, the results of single
crystal investigations correlate with the results
of the X-ray powder study, namely, the fully
and orderly occupations of all crystallographic
positions. Final atomic positional and displa
cement parameters of LaNi9Si4 compound are
presented in Table 3.
Table 2.
Crystal data and structure refinement details for LaNi9Si4.
Empirical formula LaNi9Si4
Formula weight 779.66
T, K 295(2)
Structure type CeNi8.5Si4.5
Space group I4/mcm
Pearson code tI56,140
Unit cell dimensions, Å a = 7.83933(17), c = 11.4472(5)
Volume, Å3 703.49(4)
No. formula units per unit cell 4
Calculated density, g∙cm–3 7.361
Absorption coefficient, mm-1 30.005
Crystal color metallic
Index ranges –11≤h≤11, –9≤k≤10, –16≤l≤17
Measured reflections 2177
Independent reflections / Reflections with I > 2 σ(I) 352 / 343
Data / restraints / parameters 352 / 0 / 24
Goodness-of-fit on F2 1.053
Final R1 / wR2 [I > 2 σ(I)] 0,0220 / 0,0734
Largest diff. peak / hole, e Å−3 2.525 / –1.408
7https://ucj.org.ua
B. Belan, S. Pukas, M. Dzevenko, M. Manyako, B. Kuzhel, R. Gladyshevskii UCJ № 05 / Vol. 89
Table 3.
Atomic coordinates and thermal displacement parameters for LaNi9Si4.
Atom
Wyckoff
Site
G x y z Ueq, Å
2
La 4a 1 0 0 1/4 0.0039(2)
Ni1 16l 1 0.63048(7) 0.13048(7) 0.18442(6) 0.0070(2)
Ni2 16k 1 0.06884(10) 0.20317(9) 0 0.0065(2)
Ni3 4d 1 0 1/2 0 0.0061(3)
Si 16l 1 0.17072(14) 0.67072(14) 0.11833(14) 0.0066(3)
Atom U11 U22 U33 U12 U13 U23
La 0.0028(2) 0.0028(2) 0.0062(3) 0 0 0
Ni1 0.0073(3) 0.0073(3) 0.0064(3) –0.0004(2) 0.0007(2) -0.0007(2)
Ni2 0.0051(3) 0.0058(3) 0.0085(4) –0.0003(2) 0 0
Ni3 0.0047(4) 0.0047(4) 0.0089(6) –0.0006(5) 0 0
Si 0.0062(4) 0.0062(4) 0.0074(7) 0.0016(5) 0.0001(3) -0.0001(3)
The interatomic distances (δ), the values of
interatomic distances reductions from the sum
of atomic radii and coordination numbers of
atoms for LaNi9Si4 listed in Table 4 (values of
the atomic radii are taken from [13]: r(La) =
1.877 Å, r(Ni) = 1.240 Å, r(Si) = 1.320 Å). The
majority of interatomic distances are in good
agreement with the sum of atomic sizes. Some
Ni-Si interatomic distances are rather short
and a few Ni-Ni distances are rather long in
comparison with the sum of the respective
atomic radii.
Table 4.
Interatomic distances (δ), ∆ values (∆ = 100(δ −∑r)/ ∑r, where ∑r is the sum of
the respective atomic radii) and coordination numbers (CN) of of LaNi9Si4 compound.
Atoms δ, Å ∆, % CN Atoms δ, Å ∆, % CN
La 8 Ni1 3.1625(6) 1.5 24 Ni2 2 Ni2 2.3782(11) –4.1 12
8 Si 3.2751(12) 7.5 1 Ni3 2.3887(7) –3.7
8 Ni2 3.3193(4) 6.5 2 Si 2.4633(14) –3.8
Ni1 1 Si 2.3016(17) –10.1 13 2 Si 2.5177(14) –1.7
1 Si 2.3302(13) -9.0 1 Ni2 2.5276(11) 1.9
2 Si 2.4994(13) –2.4 2 Ni1 2.5280(8) 1.9
2 Ni2 2.5280(8) 1.9 2 La1 3.3193(4) 6.5
2 Ni1 2.5376(9) 2.3 Ni3 4 Si 2.3275(13) –9.1 12
8 ISSN 2708-129X. Укр. хім. журн., 2023
LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIESINORGANIC CHEMISTRY
Atoms δ, Å ∆, % CN Atoms δ, Å ∆, % CN
1 Ni3 2.5591(7) 3.2 4 Ni2 2.3887(8) –3.4
1 Ni1 2.8931(8) 16.7 4 Ni1 2.5591(7) 3.2
1 Ni1 3.0459(8) 22.8 Si 1 Ni1 2.3016(17) –10.1 12
2 La 3.1625(6) 1.5 1 Ni3 2.3275(13) –9.1
1 Ni1 2.3302(13) –9.0
2 Ni2 2.4633(14) –3.8
2 Ni1 2.4994(13) –2.4
2 Ni2 2.5177(14) –1.7
1 Si 2.7091(19) 2.6
2 La1 3.2751(12) 7.5
Fig. 2. A projection of the LaNi9Si4 unit cell on ab plane and a view
of the coordination polyhedra of the atoms.
6
transition-metal rich compounds, which have complex multilayer structures with high values for the
coordination numbers of all atom types. The lanthanium atoms have the largest coordination
number (CN = 24) and its pseudo Frank-Kasper polyhedron [La(Ni16Si8)] can be described as a
combination of three antiprisms, two of which consists from eight nickel atoms each, and the third
of eight silicon atoms. A distorted icosahedron with one additional atom [Ni1(La2Ni7Si4)] is the CP
of the Ni1 atoms (CN = 13). The similar types of polyhedra were observed for Ni2 and Ni3 atoms.
The coordination polyhedrons of the these atoms (CN = 12 for both) can be described as distorted
icosahedrons, [Ni2(La2Ni6Si4)] and [Ni3(Ni8Si4)], respectively. The first difference lies in the
greater deformation of the Ni2 polyhedra. Furthemore, the environment of these atoms is also
somewhat different. The atoms of all sorts form the CP of the Ni2 atoms and only nickel and silicon
atoms surround the Ni3 atoms. The Si atoms have 12 neighbors and the polyhedron
[Si1(La2Ni9Si1)] can be described as a strongly distorted icosahedron.
Fig. 2. A projection of the LaNi9Si4 unit cell on ab plane and a view of the coordination polyhedra of
the atoms.
The structure of LaNi9Si4 compound can be considered as a packing of the tetragonal prism
and antiprism, which are built from the eight silicon atoms each (Fig. 2). These prisms and
antiprisms alternate along the c direction, forming endless columns that form a three-dimensional
framework. The La atoms center the antiprism, and a square from the four Ni atoms situate in one
prism. The columns from such clusters connect to each other by common edges and empty trigonal
Si6 prisms or Si4 tetrahedra, which are formed in layers of tetragonal prisms or tetragonal
antiprisms, respectively.
The projection of the crystal structure of
LaNi9Si4 on the ab plane and the coordination
polyhedral (CP) of the atoms are shown in
Fig. 2. The LaNi9Si4 compounds belong to the
family of transition-metal rich compounds,
which have complex multilayer structures with
high values for the coordination numbers of
all atom types. The lanthanium atoms have the
largest coordination number (CN = 24) and its
pseudo Frank-Kasper polyhedron [La(Ni16Si8)]
can be described as a combination of three
antiprisms, two of which consists from eight
9https://ucj.org.ua
B. Belan, S. Pukas, M. Dzevenko, M. Manyako, B. Kuzhel, R. Gladyshevskii UCJ № 05 / Vol. 89
nickel atoms each, and the third of eight silicon
atoms. A distorted icosahedron with one ad-
ditional atom [Ni1(La2Ni7Si4)] is the CP of the
Ni1 atoms (CN = 13). The similar types of po
lyhedra were observed for Ni2 and Ni3 atoms.
The coordination polyhedrons of the these
atoms (CN = 12 for both) can be described as
distorted icosahedrons, [Ni2(La2Ni6Si4)] and
[Ni3(Ni8Si4)], respectively. The first difference
lies in the greater deformation of the Ni2 poly
hedra. Furthemore, the environment of these
atoms is also somewhat different. The atoms
of all sorts form the CP of the Ni2 atoms and
only nickel and silicon atoms surround the Ni3
atoms. The Si atoms have 12 neighbors and the
polyhedron [Si1(La2Ni9Si1)] can be described
as a strongly distorted icosahedron.
The structure of LaNi9Si4 compound can
be considered as a packing of the tetragonal
prism and antiprism, which are built from the
eight silicon atoms each (Fig. 2). These prisms
and antiprisms alternate along the c direction,
forming endless columns that form a three-di-
mensional framework. The La atoms center the
antiprism, and a square from the four Ni atoms
situate in one prism. The columns from such
clusters connect to each other by common ed
ges and empty trigonal Si6 prisms or Si4 tetra-
hedra, which are formed in layers of tetragonal
prisms or tetragonal antiprisms, respectively.
Fig. 3. The arrangement of the tetragonal prisms
(blue) and antiprisms (yellow) in the LaNi9Si4
structure.
The alternative representation as packing
of CP around lanthanium and nickel atoms
shows even more compact filling (Fig. 3). The
structure of LaNi9Si4 can be described as a 3D
compact packing of two types of polyhedron:
24-vertex pseudo Frank – Kasper polyhedra
around the La atoms in Wyckoff position 4a
and icosahedra around the Ni atoms in Wyck-
off position 4d. These both polydrons consists
of nickel and silicon atonms and have the com-
positions [Ni16Si8] and [Ni8Si4], respectively.
7
Fig. 3. The arrangement of the tetragonal prisms (blue) and antiprisms (yellow) in the LaNi9Si4 structure.
The alternative representation as packing of CP around lanthanium and nickel atoms shows even
more compact filling (Fig. 3). The structure of LaNi9Si4 can be described as a 3D compact packing of
two types of polyhedron: 24-vertex pseudo Frank – Kasper polyhedra around the La atoms in Wyckoff
position 4a and icosahedra around the Ni atoms in Wyckoff position 4d. These both polydrons consists
of nickel and silicon atonms and have the compositions [Ni16Si8] and [Ni8Si4], respectively.
Fig. 4. Packing of [La(Ni16Si8)] (yellow) and [Ni3(Ni8Si4)] (blue) slabs in the LaNi9Si4 structure.
Investigation of electrical properties
The specific electrical resistance of a polycrystalline La7.14Ni61.43Si31.43 sample of regular
geometric shape was measured in the temperature range of 11–290 K on a potentiometric setup by
the standard two-probe method. The temperature dependence of electrical resistance, with slight
nonlinearity, was approximated using the Bloch-Grüneisen-Mott formula [14].
Fig. 5 shows the temperature dependence of the specific electrical resistance for the LaNi9Si4
compound. The temperature dependence of the specific electrical resistance indicates the metallic
nature of the conductivity at relatively low absolute values of the specific electrical resistance of the
investigated alloy (ρ290 K / ρ11 K = 156.26 μΩ•cm / 121.60 μΩ•cm). The slight nonlinearity of the
7
Fig. 3. The arrangement of the tetragonal prisms (blue) and antiprisms (yellow) in the LaNi9Si4 structure.
The alternative representation as packing of CP around lanthanium and nickel atoms shows even
more compact filling (Fig. 3). The structure of LaNi9Si4 can be described as a 3D compact packing of
two types of polyhedron: 24-vertex pseudo Frank – Kasper polyhedra around the La atoms in Wyckoff
position 4a and icosahedra around the Ni atoms in Wyckoff position 4d. These both polydrons consists
of nickel and silicon atonms and have the compositions [Ni16Si8] and [Ni8Si4], respectively.
Fig. 4. Packing of [La(Ni16Si8)] (yellow) and [Ni3(Ni8Si4)] (blue) slabs in the LaNi9Si4 structure.
Investigation of electrical properties
The specific electrical resistance of a polycrystalline La7.14Ni61.43Si31.43 sample of regular
geometric shape was measured in the temperature range of 11–290 K on a potentiometric setup by
the standard two-probe method. The temperature dependence of electrical resistance, with slight
nonlinearity, was approximated using the Bloch-Grüneisen-Mott formula [14].
Fig. 5 shows the temperature dependence of the specific electrical resistance for the LaNi9Si4
compound. The temperature dependence of the specific electrical resistance indicates the metallic
nature of the conductivity at relatively low absolute values of the specific electrical resistance of the
investigated alloy (ρ290 K / ρ11 K = 156.26 μΩ•cm / 121.60 μΩ•cm). The slight nonlinearity of the
Fig. 4. Packing of [La(Ni16Si8)] (yellow) and
[Ni3(Ni8Si4)] (blue) slabs in the LaNi9Si4 structure.
10 ISSN 2708-129X. Укр. хім. журн., 2023
LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIESINORGANIC CHEMISTRY
Investigation of electrical properties
The specific electrical resistance of a poly-
crystalline La7.14Ni61.43Si31.43 sample of regular
geometric shape was measured in the tempe
rature range of 11–290 K on a potentiometric
setup by the standard two-probe method. The
temperature dependence of electrical resis
tance, with slight nonlinearity, was approxi-
mated using the Bloch-Grüneisen-Mott for-
mula [14].
Fig. 5. Temperature dependence of specific
electrical resistance for the LaNi9Si4 compound.
Fig. 5 shows the temperature dependence
of the specific electrical resistance for the
LaNi9Si4 compound. The temperature depen
dence of the specific electrical resistance in-
dicates the metallic nature of the conductivity
at relatively low absolute values of the specific
electrical resistance of the investigated alloy
(ρ290 K / ρ11 K = 156.26 μΩ•cm / 121.60 μΩ•cm).
The slight nonlinearity of the temperature de-
pendence of the resistivity at higher tempera-
tures indicates that, in addition to scattering by
lattice phonons, there is an additional mecha-
nism, which can be explained by the process
of scattering of s-d conduction electrons of a
transition metal. Calculation of the obtained
experimental results using the Bloch – Gru-
neisen – Mott formula gives the following pa-
rameters: ρ0 = 121.60 μΩ•cm, θD = 191 K, A =
2.2•10-9 μΩ•m•K-3.
CONCLUSIONS
The crystal structure of ternary compound
LaNi9Si4 have been reinvestigated in detail us-
ing powder and single crystal X-ray data. This
compound is isotypical to the structure of
CeNi8.5Si4.5-type. Additionaly, the investigation
of electrical resistivity was performed.
ACKNOWLEDGMENTS.
This study was performed under the
research international project at Ivan
Franko National University of Lviv
“Search of new structure types”, regis-
tration number: HX-010123.
LaNi9Si4: КРИСТАЛІЧНА СТРУКТУРА
ТА ЕЛЕКТРИЧНІ ВЛАСТИВОСТІ
Б. Белан1*, С. Пукас1, М. Дзевенко2*,
М. Маняко1, Б. Кужель1, Р. Гладишевський1
1 Львівський національний університет
імені Івана Франка,
вул. Кирила і Мефодія, 6, Львів 79005,
Україна;
2 Львівський ліцей з посиленою військово-фі-
зичною підготовкою імені Героїв Крут,
вулиця Пасічна, 68, Львів 79000, Україна
*е-mail: m_dzevenko.teacher@lgk.ukr.
education
Відомим є факт існування вздовж ізо-
концентрати 7,14 ат.% La сполук складу
LaNi11,6-9,5Si1,4-3,5, LaNi8,8-8,4Si4,2-4,6 і LaNi7,8-4,5Si5,2-8,5.
8
temperature dependence of the resistivity at higher temperatures indicates that, in addition to
scattering by lattice phonons, there is an additional mechanism, which can be explained by the
process of scattering of s-d conduction electrons of a transition metal. Calculation of the obtained
experimental results using the Bloch – Gruneisen – Mott formula gives the following parameters: ρ0
= 121.60 μΩ•cm, θD = 191 K, A = 2.2•10-9 μΩ•m•K-3.
Fig. 5. Temperature dependence of specific electrical resistance for the LaNi9Si4 compound.
CONCLUSIONS
The crystal structure of ternary compound LaNi9Si4 have been reinvestigated in detail using
powder and single crystal X-ray data. This compound is isotypical to the structure of CeNi8.5Si4.5-
type. Additionaly, the investigation of electrical resistivity was performed.
ACKNOWLEDGMENTS.
This study was performed under the research international project at Ivan Franko National
University of Lviv “Search of new structure types”, registration number: HX-010123.
LaNi9Si4: КРИСТАЛІЧНА СТРУКТУРА ТА ЕЛЕКТРИЧНІ ВЛАСТИВОСТІ
Б. Белан1*, С. Пукас1, М. Дзевенко2*, М. Маняко1, Б. Кужель1, Р. Гладишевський1
1 Львівський національний університет імені Івана Франка,
вул. Кирила і Мефодія, 6, Львів 79005, Україна;
2 Львівський ліцей з посиленою військово-фізичною підготовкою імені Героїв Крут,
вулиця Пасічна, 68, Львів 79000, Україна
*е-mail: m_dzevenko.teacher@lgk.ukr.education
11https://ucj.org.ua
B. Belan, S. Pukas, M. Dzevenko, M. Manyako, B. Kuzhel, R. Gladyshevskii UCJ № 05 / Vol. 89
Під час детального вивчення системи
La–Ni–Si за температури 600 °С підтвер-
джено існування сполуки LaNi9Si4 та про-
ведено комплексне дослідження її криста-
лічної структури методом порошку та мо-
нокристалу.
Уточнення кристалічної структури спо-
луки LaNi9Si4 спочатку здійснено методом
порошку на основі масиву рентгенівських
дифракційних даних від полікристаліч-
ного зразка складу La7,14Ni61,43Si31,43 (диф-
рактометр STOE Stadi P, довжина хвилі
λ = 1,5406 Å, діапазон кутів 6 ≤ 2θ ≤ 120,225
із кроком 0,015° і часом сканування 250 с):
структурний тип CeNi8,5Si4,5, a = 7,86415(6),
c = 11,5101(1) Å. Оскільки зі зразку складу
La7,14Ni67,86Si25 вдалося отримати монокрис
тал, то подальше детальне дослідження
проведено рентгеноструктурним методом
монокристалу. Масив експериментальних
інтенсивностей відбить отримано на авто-
матичному монокристальному дифракто-
метрі STOE IP (Mo Kα-випромінювання).
Структуру визначено прямими методами
за допомогою комплексу програм SHELX.
Параметри теплового зміщення всіх ато-
мів уточнено в анізотропному наближенні.
Підтверджено приналежність структури
досліджуваної сполуки до структурно-
го типу CeNi8,5Si4,5 (СП tI56, ПГ I4/mcm):
а = 7,86415(6), с = 11,5101(1) Å, RB = 0,0653;
а = 7,83933(17), с = 11,4472(5) Å, R = 0,0220,
wR = 0,0734. Слід відмітити, що на відмі-
ну від прототипу CeNi8,5Si4,5, де положен-
ня 4d-просторової групи I4/mcm зайняте
статистичною сумішшю атомів Ni та Si у
співвідношенні 1:1, у структурі тернарного
силіциду LaNi9Si4 атоми розміщені впоряд-
ковано в усіх правильних системах точок.
Окрім того, досліджено температурну
залежність питомого електроопору для
сполуки LaNi9Si4, що вказує на металічний
характер провідності (ρ0 = 121,60 мкОм·cм,
θD = 191 K, А = 2,2·10-9 мкОм·м·K-3).
Ключові слова: лантан, нікель. силіцій,
кристалічна структура, електричний опір.
REFERENCES
1. Villars P., Cenzual K., Eds. Pearson’s Crystal
Data: Crystal Structure Database for Inorganic
Compounds. Ohio (USA): ASM Internatio
nal®, Materials Park, 2018.
2. Godart C., Gupta L.C., Tomy C.V., Patil S., Na-
garajan R., Beaurepaire E., Vijayaraghavan R.,
Yakhmi J.V. Magnetism and mixed valence
in some R2M3X5 compounds: R = Ce, Eu, U;
M = d metals, X = Si, Ge. Mater.Res.Bull. 1988.
23 (12): 1781–1785.
https://doi.org/10.1016/0025-5408(88)90189-4
3. Kishimoto Yu., Kawasaki Yu., Ohno T. Mixed
valence state in Ce and Yb compounds studied
by magnetic susceptibility. Phys. Lett. A. 2003.
317 (3–4): 308–314.
https://doi.org/10.1016/j.physleta.2003.08.050
4. Pani M., Manfrinetti P., Provino A., Fang Yuan,
Mozharivskyj Y., Morozkin A.V., Knotko A.V.,
Garshev A.V., Yapaskurt V.O., Isnard O. New
tetragonal derivatives of cubic NaZn13-type
structure: RNi6Si6 compounds, crystal struc-
ture and magnetic ordering (R = Y, La, Ce, Sm,
Gd–Yb). J. Solid State Chem. 2014. 210: 45–52.
https://doi.org/10.1016/j.jssc.2013.10.046
5. Bodak O.I., Gladyshevskii E.I., Ternary sys-
tems containing rare earth metals. Lviv: Vysh-
cha shkola, 1985. (in Russian)
6. Bodak O.I., Gladyshevskii E.I., Ternary com-
pounds of the NaZn13 type and related types in
the systems {La, Ce, Pr, Nd, Sm, Eu, Gd}–Ni–Si
and {La, Ce}–{Fe, Co}–Si. Dopov. Akad. Nauk
Ukr. RSR, Ser. A. 1969. 12: 1125. (in Russian)
7. Belan B., Bednarchuk T. J., Kinzhybalo V.,
Dzevenko M., Pukas S., Gladyshevskii R.
12 ISSN 2708-129X. Укр. хім. журн., 2023
LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIESINORGANIC CHEMISTRY
Crystal structure of the new silicide
LaNi11.8–11.4Si1.2–1.6. Z. Naturforsch. B. 2021. 76
(3–4): 243–247.
https://doi.org/10.1515/znb-2021-0021
8. Bodak O.I., Gladyshevskii E.I. Crystal Struc-
ture of the Compound CeNi8.6Si2.4 and Related
Compounds. Dopov. Akad. Nauk Ukr. RSR,
Ser. A, 1969. 6: 452–455. (in Russian)
9. Michor H., Berger St., El-Hagary M., Paul C.,
Bauer E., Hilscher G., Rogl P., Giester G. Crys-
tal structure and Kondo lattice behavior of
CeNi9Si4. Phys. Rev. B: Condens. Matter Mater.
Phys. 2003. 67: 224428 (1–10).
https://doi.org/10.1103/PhysRevB.67.224428
10. Stoe WinXPOW, version 2.21. Darmstadt: Stoe
& Cie GmbH, 2007.
11. Young R.A., Sakthivel A., Moss T.S., Pai-
va-Santos C.O. DBWS-9411 – an upgrade of
the DBWS, J. Appl. Crystallogr. 28, 366 (1995).
https://doi.org/10.1107/S0021889895002160
12. Sheldrick G. M. SHELX-97 – WinGX Version.
Release 97-2, Germany: University of Göttin-
gen, 1997.
13. Emsley J., The Elements, 2nd ed. Oxford: Cla
rendon Press, 1991.
14. Mott N.F., Jones H. The theory of the proper-
ties of metals and alloys. Oxford: University
Press, 1958.
Стаття надійшла 29.05.2023.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-550 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:09:58Z |
| publishDate | 2023 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/5b/e68799bfd9405e286cf0987f93778d5b.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5502026-07-22T08:23:51Z LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES Belan, Bohdana Pukas, Svitala Dzevenko, Mariya Manyako, Mykola Kuzhel, Bohdan Gladyshevskii, Roman lanthanum, nickel, silicon, crystal structure, electrical resistivity. The structure of LaNi9Si4 compound has been investigated by X-ray powder ans single crystal method. This silicide crystalize in CeNi8.5Si4 structure type: space group I4 mcm, Pearson symbol tI56, а = 7.86415(6), с = 11.5101(1) Å, RB = 0.0653; а = 7.83933(17), с = 11.4472(5) Å, R = 0.0220, wR = 0.0734 for X-ray single crystal data. Unlike the prototype CeNi8.5Si4.5, where the Wyckoff position 4d is occupied by mixture of Ni and Si atoms, in the structure of the ternary silicide LaNi9Si4, the atoms are ordered in all Wyckoff positions. Additionally, the electrical properties for the compound were investigated. The temperature dependence of the electrical resistivity exhibits metal behaviour (ρ0 = 121.60 μΩ∙cm, θD = 191 K, A = 2.2·10-9 μΩ∙m∙K-3).   V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-06-26 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/550 10.33609/2708-129X.89.05.2023.3-12 Ukrainian Chemistry Journal; Vol. 89 No. 5 (2023): Ukrainian Chemistry Journal; 3-12 Украинский химический журнал; ##issue.vol## 89 ##issue.no## 5 (2023): Ukrainian Chemistry Journal; 3-12 Український хімічний журнал; Том 89 № 5 (2023): Ukrainian Chemistry Journal; 3-12 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/550/280 Copyright (c) 2023 Bohdana Belan, Svitala Pukas, Mariya Dzevenko, Mykola Manyako, Bohdan Kuzhel, Roman Gladyshevskii https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Belan, Bohdana Pukas, Svitala Dzevenko, Mariya Manyako, Mykola Kuzhel, Bohdan Gladyshevskii, Roman LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES |
| title | LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES |
| title_full | LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES |
| title_fullStr | LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES |
| title_full_unstemmed | LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES |
| title_short | LaNi9Si4: CRYSTAL STRUCTURE AND ELECTRICAL PROPERTIES |
| title_sort | lani9si4: crystal structure and electrical properties |
| topic_facet | lanthanum nickel silicon crystal structure electrical resistivity. |
| url | https://ucj.org.ua/index.php/journal/article/view/550 |
| work_keys_str_mv | AT belanbohdana lani9si4crystalstructureandelectricalproperties AT pukassvitala lani9si4crystalstructureandelectricalproperties AT dzevenkomariya lani9si4crystalstructureandelectricalproperties AT manyakomykola lani9si4crystalstructureandelectricalproperties AT kuzhelbohdan lani9si4crystalstructureandelectricalproperties AT gladyshevskiiroman lani9si4crystalstructureandelectricalproperties |