Intermetallics 35 (2013) 45e52

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Intermetallics
journal homepage: www.elsevier.com/locate/intermet

Peculiarities of structural disorder in Zr- and Hf-containing Heusler and

half-Heusler stannides
V.V. Romaka a, *, P. Rogl b, L. Romaka c, Yu. Stadnyk c, A. Grytsiv b, O. Lakh d, V. Krayovskii a
a
Department of Materials Engineering and Applied Physics, Lviv Polytechnic National University, Ustyyanovycha Str. 5, 79013 Lviv, Ukraine
b
Institut fur Physikalische Chemie der Universitat Wien, Wahringerstrabe 42, A-1090 Wien, Austria
c
Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla and Mefodiya Str. 6, 79005 Lviv, Ukraine
d
SPA “Termoprylad”, Naukova Str. 3, 79060 Lviv, Ukraine

a r t i c l e i n f o a b s t r a c t

Article history: The structural phase transition in half-Heusler e Heusler stannides ZrNiSneZrNi2Sn and HfNiSn
Received 16 August 2012 eHfNi2Sn was studied using XRD and EPM analyses, electrical and magnetic properties measurement.
Received in revised form The influence of the disordering and defects in crystal structure on the physical properties was analyzed.
12 November 2012
The performed electronic structure calculations are in good agreement with electrical and magnetic
Accepted 17 November 2012
Available online
behaviors and allowed to explain limited solubility in these phases.
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
A. Intermetallics
B. Electrical resistance and other electrical
properties
B. Magnetic properties
E. Electronic structure
F. Diffraction

1. Introduction of study [7], as well as the authors of numerous publications

devoted to the experimental study of NNiSn (e.g., [8,9]), were not
A class of half-Heusler stannides with MgAgAs structure type confused by the discrepancy between the data pointing to electron
has been intensively investigated owing to their potential appli- conductivity of the semiconductor within the temperature range
cation in the thermoelectric field. The TiNiSn, ZrNiSn, HfNiSn and T ¼ 1.6e400 K and the calculated position of the Fermi level near
TiCoSb compounds behave as narrow gap semiconductors [1e5]. the valence band indicating hole conductivity of the material.
The semiconducting properties of the MNiSn half-Heusler inter- The authors of study [10] first asked themselves to what extent
metallic phases may be explained by peculiarities of their crystal the wave function obtained by them coincides with that in the real
structure where the M and Sn atoms have tetrahedral bonding and MNiZ crystals, where M ¼ Sc, Ti, Zr, or Hf and Z ¼ Sn or Sb. As is
form the covalent bonds between the Sn and Ni or M atoms [6]. known, if atoms, in virtue of certain circumstances, exchange places
In study [7], the authors calculated for the first time the band insignificantly, then the MgAgAs structural type will transform into
structure of MNiSn (M ¼ Ti, Zr, or Hf) compounds using a pseudo- another, e.g., CaF2 or NaCl [11] and, consequently, the band struc-
potential method and showed that these compounds are semi- ture of a crystal substance will drastically change. Such circum-
conductors, thus confirming the assumptions made in [1]. The stances may be temperature, duration of homogenizing annealing
continuous energy bands of NNiSn were identified, the position of (bringing the substance to the thermodynamic equilibrium), cool-
the Fermi level in the band gap near the top of the valence band was ing methods (hardening or slow cooling), etc. [12].
established, and the values of the band gap (3 g) both in the center of In study [13], the idea stated in [10] was developed and the band
the Brillouin zone and in the X direction were obtained. Note that, structure of MNiSn (M ¼ Ti, Zr, Hf) was calculated by a plane wave
to date, these results have been considered canonical. The authors method for the following three variants of atomic arrangement in
the unit cell of the compound: (i) arrangement of atoms was
considered corresponding to the MgAgAs structural type (ordered
* Corresponding author. Tel.: þ380 322394503.
structure); (ii) Ni and N atoms were interchanged; and (iii) Sn and
E-mail address: romakav@lp.edu.ua (V.V. Romaka). N, N and Ni, and Ni and Sn atoms were simultaneously

0966-9795/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.intermet.2012.11.022
46 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52

interchanged. Comparing the variants of the calculation for package [23]. Rietveld refinement was performed using the Win-
different combinations of atomic arrangement at the sites of the PLOTR program package [24].
NNiSn unit cell with the experimental data, the authors of [13] The chemical compositions of the obtained samples with
came to the conclusion that the crystal structure of the NNiSn accuracy w0.5e0.3 at.% were examined by Scanning Electron
compound is disordered and the composition of the compound is Microscopy (SEM) using Zeiss Supra 55VP scanning electron
similar to that assumed in [12]. Considerable concentrations of microscope. Quantitative electron probe microanalysis (EPMA) of
defects in NNiSn compound cause it’s a priori doping and make this the phases was carried out by using an energy-dispersive X-ray
compound a heavily doped and highly compensated semi- analyzer with the pure elements as standards (an acceleration
conductor (HDHCS) [14,15]. voltage was 20 kV; K- and L-lines were used).
It is known that thermoelectric properties of half-Heusler inter- Measurements of the magnetic susceptibility were carried out at
metallics in many cases are strongly dependent on the microstruc- room temperature and fields up to 10 kOe using a conventional
ture, heat treatments, homogeneity domains, atomic disordering and Faraday method with the tetrathiocyanate Co(II) mercury salt,
partial occupancy of the vacancy sites. It is very important for the Me HgCo(CNS)4, as the susceptibility standard. The copper-constantan
NieSn (M ¼ Ti, Zr, Hf) systems characterized by coexistence of two thermocouple was used. The electrical resistivity and differential
similar phases, i.e. MNiSn with cubic MgAgAs-type (half-Heusler thermopower (pure copper as a reference material) were measured
phases) and MNi2Sn with cubic MCu2Al-type (Heusler phases) [16e in the 80e370 K temperature range using two-probe method.
18]. The lack of mutual solubility of the half-Heusler phases MNiSn Band structure calculations were carried out in the framework
and Heusler phases MNi2Sn with similar crystal structures is quite of DFT using Korringa-Kohn-Rostocker method with coherent
remarkable in all studied systems. The half-Heusler MNiSn structure potential approximation and local density functional (KKR-CPA-
may be obtained from MNi2Sn if one half of the Ni-atoms is removed, LDA) [25]. Parameterization of Moruzzi, Janak, Williams [26] and
which results the presence of the covalent bonds and semi- semi-relativistic treatment of the core shells were used. Number of
conductive properties of the MNiSn compounds. In the TieCoeSn k-points for Brillouin zone integration and energy points for density
system these two phases represent the edge members of the solid of states was equal to 1000 in both cases.
solution TiCo2xSn [19], where the electrical conductivity changes
from semiconducting to metallic type. 3. Results and discussion
Doping of the basic ternary compounds of the MgAgAs structure
type, in particular, TiNiSn, ZrNiSn, HfNiSn, allows to considerably 3.1. Composition and crystal structure of ZrNi1þxSn and HfNi1þxSn
improve the power factor values. In the case of substitution of the solid solutions
crystallographic sites in MNiSn structure by other elements the
studying of disordering phenomena and defect formation in crystal In our work we performed the detailed X-ray and EPM analyses
structure is very important. In Ref. [20] it was showed that TiNiSn of the synthesized samples in both ZrNiSneZrNi2Sn and HfNiSne
stannide has defect structure induced by vacancies in crystallo- HfNi2Sn composition range. The Heusler structure may be
graphic positions which can play a role of acceptor impurities. In conventionally presented as a cubic closest packed Sn atomic cell
[21] the structural disorder in ZrNiSn was found e Zr position where the octahedral voids are occupied by Zr(Hf) atoms and the
appeared to be mixed occupied by 99%Zr and 1%Ni atoms giving the tetrahedral voids are occupied by Ni atoms (Fig. 1).
final composition (Zr0.99Ni0.01)NiSn. According to the EPM analysis (Fig. 2) the ZrNiSn compound is
In work [22] the authors significantly improve the thermoelec- characterized by homogeneity region up to ZrNi1.3Sn composition.
tric properties of bulk nanostructured half-Heusler alloys. The SEM images show that starting from ZrNi1.3Sn sample small
authors showed that in half-Heusler MNiSn alloy that contain both amount of the second phase with composition close to ZrNi2Sn
Zr and Hf the solubility of additional Ni atoms was absent. Instead compound appears (Fig. 3). The boundaries between these phases
of this nanoparticle of full-Heusler phase was obtained. are blurred, however with increasing of Ni content they become
In the present contribution we performed a detailed study of the more contrast. All samples with composition between ZrNi1.3Sn
structural phase transition in half-Heusler e Heusler intermetallics and ZrNi1.65Sn consist of two phases e half-Heusler and Heusler.
MNiSneMNi2Sn (M ¼ Zr, Hf) and the composition influence on the Starting from ZrNi1.65Sn composition and up to ZrNi2Sn the samples
physical properties of the corresponding samples. were single-phase and limited the homogeneity region of ZrNi2Sn
compound. Thus, the final composition of these two phases could
2. Experimental be described as ZrNi1þxSn (0  x  0.3) for half-Heusler phase with
MgAgAs structure and ZrNi1þxSn (0.65  x  1.0) for Heusler phase
In our work samples between ZrNiSneZrNi2Sn and HfNiSne with MnCu2Al structure. The results of EPM analysis of the samples
HfNi2Sn compounds were prepared by a direct arc melting of the with Hf showed similar to Zr results (Fig. 4), however several
constituent elements (zirconium, purity of 99.99 wt.%; hafnium, features were found. The SEM image (Fig. 5) of pure HfNiSn stan-
purity of 99.99 wt.%; nickel, purity of 99.99 wt.%; tin, purity of nide showed several grains with gradient of gray colors (different
99.999 wt.%) under high purity Ti-gettered argon atmosphere on
a water-cooled copper crucible. The alloys were annealed at 1073 K
in the evacuated quartz tubes for 720 h, and subsequently
quenched in ice water.
X-ray phase analysis of the samples was carried out using the
powder patterns obtained on Guinier-Huber image plate system
(CuKa1 radiation) and DRON-4.0 (FeKa radiation) diffractometers.
The data for the crystal structure refinements were collected at
room temperature using STOE STADI P powder diffractometer
(CuKa1 radiation, curved germanium (1 1 1) monochromator) and
Guinier-Huber image plate system (CuKa1 radiation, germanium
monochromator). Lattice parameters were calculated by least- Fig. 1. Structural relationship between half-Heusler ZrNiSn (MgAgAs-type) and
squares fits to indexed 2q-values using the WinCSD program Heusler ZrNi2Sn (MnCu2Al-type).
 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52 47

as HfNi1þxSn (0  x  0.3) for half-Heusler phase and HfNi1þxSn

(0.7  x  1.0) for Heusler phase. Similar investigations for TiNiSn
and TiNi2Sn showed homogeneity region only for TiNi2Sn.
X-ray powder diffraction data for ZrNi1þxSn and HfNi1þxSn
stannides are given in Table 1 and Table 2, respectively. The crystal
structure of pure ZrNiSn was determined earlier by single crystal
and powder X-ray diffraction and appeared to be disordered (1% Ni
occupies 4a site of Zr) [21]. For the site occupancies the EPMA data
were taken as starting values. The small deviation in composition
from EPMA data was observed, but the tendency in Ni content
change remains practically the same. In the final steps the occu-
pancies were fixed and Biso values were refined. The crystal struc-
ture refinement of ZrNi1þxSn intermediate compositions showed
the presence of Ni atoms in 4d site for half-Heusler phase and
vacancies in 8d site for Heusler phase. No significant deviation in
occupancy of Zr site was observed during Rietveld refinement and
it was fixed at 100% of Zr. Cell parameters of each solid solution
Fig. 2. Phase composition of the ZrNiSneZrNi2Sn alloys from EPMA data. were refined using least-squares method and appeared to be
practically the same within physically reasonable values. The
grain orientation), but the microprobe analysis revealed practically structure refinement of pure HfNiSn revealed structural disorder in
identical composition for all of them and as a result single-phase 4a crystallographic site e statistical mixture of Hf and Ni atoms.
sample. The homogeneity regions were found for HfNiSn and Using structural data of disordered ZrNiSn as starting values the
HfNi2Sn. The composition of these two phases could be described composition was refined to w(Hf0.99Ni0.01)NiSn and appeared to be

Fig. 3. SEM pictures of the ZrNi1þxSn alloys: (a) 1. ZrNiSn; (b) 3. ZrNi1.01Sn; (c) 5. ZrNi1.03Sn; (d) 7. ZrNi1.08Sn; (e) 11. ZrNi1.3SneZrNi1.3Sn (gray light phase) and traces of ZrNi1.65Sn
(gray dark phase); (f) 13. ZrNi1.5SneZrNi1.3Sn (gray light phase) and ZrNi1.65Sn (gray dark phase).
48 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52

3.2. Electrical and magnetic properties of ZrNi1þxSn solid solution

Temperature dependencies of resistivity ln r(1/T) (Fig. 6 (left))

and thermopower coefficient a(1/T) (Fig. 6 (right)) for samples
ZrNi1þxSn, x ¼ 0 O 0.10 are typical for heavily doped semi-
conductors with high- and low-temperature activation regions that
prove the existence of several activation mechanisms of conduc-
tion. From high- and low-temperature regions of ln r(1/T) the
activation energy from Fermi level (EF) to percolation level of
r r
conduction band ðE1 Þ and hopping of electrons ðE3 Þ on energy
states close to Fermi level were calculated (Fig. 7). From activation
regions of a(1/T) the activation energies E1a and E3a were
determined.
It should be mentioned, that peculiarity of heavily doped
strongly compensated semiconductors (HDSCs) is significant
difference in values of activation energies determined from
temperature dependencies of resistivity and thermopower coeffi-
Fig. 4. Phase composition of the HfNiSneHfNi2Sn alloys from EPMA data. cient. In HDSCs the fluctuation of significant concentrations of
charged centers results modulation of continuous energy bands,
identical to those, obtained from EPM analysis. Another two and the different nature of activation processes causes difference in
structures from Table 2 were refined from one sample that contains values of activation energies.
half-Heusler and Heusler phases. Some overlap of diffraction peaks Thermopower coefficient of ZrNi1þxSn at x ¼ 0 (n-ZrNiSn) has
doesn’t allow comparing Biso values with pure HfNiSn. The presence negative value and electrons are the main charge carriers. This is
of Ni atoms in 4d site for half-Heusler phase and vacancies in 8d site well known and expected result caused by donor nature of intrinsic
for Heusler phase was observed like in Zr case. No significant structural defects of semiconductor due to partial occupation
deviation in occupancy of Hf site was observed during Rietveld (w1%) of Zr site by Ni atoms. In this case, the Fermi level (EF) is
refinement and it was fixed at 100% of Hf like in ZrNi1þxSn case. located near the bottom of conduction band at a distance

Fig. 5. SEM pictures of the HfNi1þxSn alloys: (a) 1. HfNiSn; (b) 6. HfNi1.60SneHfNi1.3Sn (gray light phase) and HfNi1.70Sn (gray dark phase).

Table 1
X-ray powder diffraction data for ZrNi1þxSn (0  x  1) stannides.

Parameter/compound ZrNi1þxSn (0  x  0.3) ZrNi1þxSn (0.65  x  1)

Space group, prototype F-43m, MgAgAs Fm-3m, MnCu2Al
Composition, EPMA at.% Zr32.5Ni35.5Sn32.5 Zr31.5Ni37.5Sn31.0 Zr27.5Ni46.7Sn27.0
Composition, XPD at.% Zr33.1Ni33.8Sn33.1 Zr33.0Ni34.0Sn33.0 Zr25.6Ni48.9Sn25.6
a [nm] 0.611173(2) 0.611081(3) 0.627252(7)
Reflections measured 15 15 16
P P
RF ¼ jFoFcj/ Fo 0.0067 0.0050 0.0136
P P
RI ¼ jIoIcj/ Io 0.0084 0.0069 0.0172
P P
RwP ¼ [ wijyoiycij2/ wijyoij2]½ 0.0293 0.0263 0.0263
P P
RP ¼ jyoiycij/ jyoij 0.0174 0.0178 0.0178
P
Re ¼ [(NP þ C)/ wiy2oi)]½ 0.0454 0.0427 0.0427
c2 ¼ (RwP/Re)2 1.06 0.550 0.550
Atom parameters
Zr in 4a (0, 0, 0) e e e
Biso (102 nm2) 0.92(4) 0.57(6) 0.41(11)
Sn in 4b (1/2, 1/2, 1/2) e e e
Biso (102 nm2) 0.36(3) 0.38(5) 0.54(9)
Ni in 4d (3/4, 3/4, 3/4) 8c (1/4, 1/4, 1/4)
Occ. Ni/Vac. 0.09/3.91 0.13/3.87 7.65/0.35
Biso (102 nm2) 0.86(4) 0.87(5) 0.75(7)
Ni in 4c (1/4, 1/4, 1/4) e e
Biso (102 nm2) 0.86(4) 0.87(5)
 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52 49

Table 2
X-ray powder diffraction data for HfNi1þxSn (0  x  1) stannides.

Parameter/compound HfNi1þxSn (0  x  0.3) HfNi1þxSn (0.7  x  1)

Space group, prototype F-43m, MgAgAs Fm-3m, MnCu2Al
Composition, EPMA at.% Hf32.9Ni33.8Sn33.3 Hf30.5Ni38.5Sn31.0 Hf27.3Ni45.3Sn27.4
Composition, XPD at.% Hf32.8Ni33.9Sn33.3 Hf33.0Ni34.0Sn33.0 Hf25.7Ni48.6Sn25.7
a [nm] 0.607668(9) 0.607474(13) 0.62425(1)
Reflections measured 16 17 18
P P
RF ¼ jFoFcj/ Fo 0.0322 0.0137 0.0189
P P
RI ¼ jIoIcj/ Io 0.0391 0.0155 0.0247
P P
RwP ¼ [ wijyoiycij2/ wijyoij2]½ 0.0908 0.0705 0.0705
P P
RP ¼ jyoiycij/ jyoij 0.0578 0.0510 0.0510
P
Re ¼ [(NP þ C)/ wiy2oi)]½ 0.0535 0.0538 0.0538
c2 ¼ (RwP/Re)2 11.6 1.72 1.72
Atom parameters
Hf in 4a (0, 0, 0) e e e
Occ. Hf/Ni 3.94/0.06(1)
Biso (102 nm2) 0.11 0.46(4) 0.46(4)
Sn in 4b (1/2, 1/2, 1/2) e e e
Biso (102 nm2) 1.00(6) 0.53(5) 0.61(4)
Ni in 4c (1/4, 1/4, 1/4) e e
Biso (102 nm2) 1.95(11) 1.05(9)
Ni in 4d (3/4, 3/4, 3/4) 8c (1/4, 1/4, 1/4)
Occ. Ni/Vac. 0.11/3.89 7.57/0.43
Biso (102 nm2) 1.05(9) 1.12(5)

Fig. 6. Temperature dependencies of electrical resistivity (left) and differential thermopower (right) of the ZrNi1þxSn alloys.

r
E1 ðx ¼ 0Þ ¼ 97:61 meV from percolation level, and E1a ðx ¼ 0Þ ¼ defects of donor nature are formed, and their concentration
83:8 meV determines amplitude modulation of continuous energy increase with increasing of Ni concentration. In this case, doping of
bands of n-ZrNiSn. n-type semiconductor by donor impurity should drift Fermi level
r
Doping of ZrNiSn by lowest concentration of Ni atoms leads to toward conduction band. The activation energy E1 from Fermi level
sharp decrease of resistivity, for example, at 80 K from r to percolation level in ZrNi1þxSn decrease up to y ¼ 0.08. Moreover,
(x ¼ 0) ¼ 4751.1 mU m to r (x ¼ 0.01) ¼ 231.0 mU m and r such doping should lead to decreasing of semiconductor compen-
(x ¼ 0.10) ¼ 62.8 mU m. Such behavior of r(x) shows that structural sation degree and as a result decreasing of amplitude modulation

r r
Fig. 7. Experimental and calculated values of activation energy ðE1 Þ from Fermi level to percolation level of conduction band (left) and hopping of electrons ðE3 Þ on energy states
close to Fermi level (right) of ZrNi1þxSn solid solition.
50 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52

Fig. 8. Comparison of measured magnetic susceptibility and calculated density of

electronic states (DOS) of ZrNi1þxSn solid solition.

Fig. 10. Distribution of DOS on Fermi level of ZrNi1þxSn solid solition.

values of continuous energy bands. Indeed, the modulation

amplitude decreases down to E1a ðx ¼ 0:01Þ ¼ 51:38 meV and
r
E1a ðx ¼ 0:10Þ ¼ 31:9 meV. Insignificant rise on dependencies E1 ðxÞ
in concentration range x > 0.08 is not affected by reverse of Fermi
level, and has more complex nature.
Investigation of magnetic susceptibility c of ZrNi1þxSn gave
additional information about electronic structure of semiconductor.
In this work the diamagnetism of n-ZrNiSn was confirmed
(c ¼ 0.06$106 cm3/g). Doping of n-ZrNiSn by Ni atoms changes
magnetic state of ZrNi1þxSn from weak diamagnetic (x ¼ 0 and
x ¼ 0.01) to Pauli paramagnetic (x > 0.01) as it is shown on Fig. 8. In
this case the magnetic susceptibility of ZrNi1þxSn would be deter-
mined by magnetic susceptibility of main charge carriers, in
particular by their concentration N (c w N). Taking into account
that Ni impurity generates structural defects of donor nature, and
as a result increases concentration of free electrons, in similar way
the magnetic susceptibility of ZrNi1þxSn should change (Fig. 8).
However, this result also doesn’t explain the nature of structural Fig. 11. Distribution of the total DOS of ZrNi1þxSn (0  x  0.4).
defects in ZrNi1þxSn. Practically identical results were obtained for
HfNi1þxSn solid solution.

Fig. 9. DOS profile of ZrNi1þxSn solid solution e Ni goes into vacant 4d crystallographic site (left) of ZrNiSn (SG F-43m); vacancies created in Ni-filled 8c site of ZrNi2Sn (SG Fm-3m)
(right).
 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52 51

3.3. Band structure calculations gradually filled with Ni to obtain full-filled Heusler phase; (2) the Ni
(8c) site in Heusler phase was gradually filled with vacancies to
Despite similarity in crystal structure, half-Heusler and Heusler obtain hypothetical half-Heusler phase which could be described
phases differ due to the absence of the center of symmetry in half- by formula M(Ni0.5Ni0.5)Sn (M ¼ Zr, Hf). The calculations showed
Heusler phases. Such feature should significantly affect the elec- that in the first case discontinuous change of DOS profile is
tronic structure and chemical bonding of possible solid solutions observed (Fig. 9a), while in the second case e no significant
between half-Heusler and Heusler phases. To verify this assump- changes in band structure were found (Fig. 9b). It means that in
tion, the electronic structure calculations were performed in two half-Heusler phase the occupancy of Ni (4c) site doesn’t change. The
ways e (1) the empty (4d) sites in half-Heusler phase were energy-gap has nonlinear change and completely disappears near

Fig. 12. Distribution of the total and partial DOS of ZrNi1þxSn solid solution.
52 V.V. Romaka et al. / Intermetallics 35 (2013) 45e52

the MNi1.4Sn composition. The density of states at Fermi level magnetic properties of ZrNi1þxSn solid solution. The Ni doping of
dramatically increases after the energy gap disappears (Fig. 10). ZrNiSn and HfNiSn allows tuning up to 10% the thermoelectric
From the chemical point of view the filling of empty sites with Ni power factor.
generates additional d-states in the valence band right inside the
energy gap between valence s- and p-states of Sn
Acknowledgment
(region 5 O 7 eV) and gradually delocalizes them. In such way
the covalent bonding between Ni in 4c and Sn becomes weaker
The work was supported by the Ministry of Education and
(Fig. 11). Further increasing of Ni atoms concentration up to
Science, Youth and Sport of Ukraine (grant No. 0111U001088) and
MNi1.3Sn splits Sn p-states and after this point the structure no
Lviv Polytechnic National University (grant No. 1720).
longer exists. Moreover, the hybridization between these two
components changes dramatically from tetrahedral (non-centro-
symmetric) p orbitals of Sn overlap with dz2, dx2-y2 orbitals of Ni to References
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