Intermetallics 92 (2018) 62–71

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

Oxidation of half-Heusler NiTiSn materials: Implications for thermoelectric MARK

applications
A. Berche∗, P. Jund
ICGM-Université de Montpellier, UMR-CNRS 5253, Pl. E. Bataillon CC1506, Montpellier, 34095, France

A R T I C L E I N F O A B S T R A C T

Keywords: Oxidation of phases such as NiTiSn is critical for understanding the mechanisms involved during the experi-
A. intermetallics (half-Heusler) mental synthesis and may also have an influence on the thermoelectric properties of this half-Heusler phase.
B. phase stability Indeed, oxygen may dope the phase by entering in its structure or generate secondary oxide phases which may
B. oxidation improve or decrease the global figure of merit of the sample. In this study, an ab initio method is used to predict
E. ab–initio calculations
the behavior of the NiTiSn phase in the presence of oxygen. For that, the thermodynamic database containing
G. thermoelectric power generation
enthalpies of formation at 0 K of the intermediate phases of the Ni-O-Sn-Ti system is calculated. This base will
allow us to predict multiphased regions as a function of the composition of an alloy. The enthalpy of formation of
the NiTiSn phases containing oxygen atoms is then compared to the enthalpy of formation of the multiphased
regions with the same composition. Using this methodology, thermodynamics can predict if oxygen will enter
the structure or if a multiphased alloy is thermodynamically more favorable. Results show that oxygen will
decompose the NiTiSn half-Heusler into titanium oxide and nickel stannides. On the basis of the literature
review, it seems that the presence of metallic titanium oxides will decrease the Seebeck coefficient and the
thermal conductivity but will highly improve the electrical conductivity. Finally, for a moderate amount of
oxygen, the figure-of-merit of the sample may be globally unchanged.

1. Introduction and possibly secondary intermetallic phases. These two mechanisms

It is well known that new green energy sources such as thermo-
electricity are needed in order to fight against global warming.
Thermoelectric materials possess the ability to directly convert waste
heat into electricity using the Seebeck effect. To improve the efficiency
of thermoelectric modules, two semiconductors (respectively n and p)
with a high figure-of-merit (ZT) have to be associated. This figure-of-
merit is given by the formula ZT = S2σT/κ where T is the temperature,
S the Seebeck coefficient, σ and κ the electrical and thermal con-
ductivity respectively. One important aspect for the sustainability of an
energy source is to use non toxic, recyclable and abundant elements.
Therefore, materials such as half-Heusler materials (NiTiSn for ex-
ample) are good candidates. However, it is experimentally difficult to
obtain pure NiTiSn samples by melting methods [1–5] due to its peri-
tectic formation [6–8]. Moreover, titanium is known to be easily oxi-
dizable and α-Ti can dissolve up to 33.3 at.% of oxygen in its structure
at 1000 K [9,10]. In these conditions, it is unrealistic to synthesize
NiTiSn without oxygen. Oxygen can react with a phase by two ways: in
the first case, oxygen will enter the structure, as it is the case of pure α-
Ti. In the second case, oxygen will react with the phase to form oxides
will have different incidences on the thermoelectric properties. Indeed,
in the first case, NiTiSn will be doped by oxygen which can change the
Power Factor (PF=S2σ) of the material or even the n/p-type behavior
of the semiconductor. In the second case, secondary phases will be
formed and this may change the ZT. The purpose of this paper is to
predict the oxidation behavior of the NiTiSn phase. For that, DFT cal-
culations have to be performed in the Ni-O-Sn-Ti system to calculate the
enthalpy of formation of the different phases in this quaternary.
Calculating enthalpies of formation of oxides by DFT has been
heavily discussed. The best way to perform such calculations would be
to use specific hybrid functional such as HSE06. However, calculation
times are unreasonable (for example 4 [11] to 75 [12] times longer
than the Generalized Gradient Approximation (GGA) and the Local
Density Approximation (LDA) for relaxing a structure) especially for
point-defect studies that require cells with around 100 atoms. Both GGA
and LDA don't succeed to represent correctly the electronic structure of
metallic oxides (V to Cu) since the d-electrons are not localized enough.
To solve this problem, GGA + U has been developed in the 90's
[13,14]. There are different ways to use this correction; the simplest is
obtained by using a single parameter: the Hubbard effective term Ueff.

∗
Corresponding author.
E-mail address: alexandre.berche@gmail.com (A. Berche).

http://dx.doi.org/10.1016/j.intermet.2017.09.014
Received 29 June 2017; Received in revised form 21 September 2017; Accepted 22 September 2017
0966-9795/ © 2017 Elsevier Ltd. All rights reserved.
A. Berche, P. Jund
This parameter can be calculated or fitted to improve a given property
(gap, magnetic moment, enthalpy of formation …). However, generally,
if the gap is improved, the enthalpies of formation of the oxides are not
well represented. This may be due to an inaccurate calculation of the O2
molecule as suggested by Wang et al. [15]. For this reason, a systematic
correction of the total energy of the O2 molecule has been suggested
[15,16]. This correction is performed by fitting a corrective term
Ecor(O2) to represent the experimental enthalpies of formation of the
oxides. For the present study, we need to use the same protocol for
calculating both oxides and intermetallic phases. But the best way to
represent the electronic structure of intermetallic phases is to use the
classical GGA method. This is why a method which combines GGA and
GGA + U calculations has been suggested by Jain et al. [17]. In their
methodology, intermetallic phases are calculated by GGA whereas
oxides phases are calculated by GGA + U taking into consideration the
correction of the calculation of the O2 molecule [15,16]. An additional
corrective term (ΔEX) is used to correct the systematic error introduced
by calculating the enthalpy of formation of the oxide OXn (calculated in
GGA + U) from O2 (fitted with Ecor(O2)) and the metal X (calculated by
GGA). Using such a protocol allows having a good representation of
some ternary phase diagrams as shown by Jain et al. [17]. But this
methodology needs to adjust 3 corrective terms: Ueff, Ecor(O2) and ΔEX.
In these conditions, the calculations are not really first-principles cal-
culations anymore. This is the reason why we have decided to use an-
other methodology in this work. The principle is to fit Ueff of nickel
from the enthalpy of formation of the main oxide (NiO here). This term
will then be used for all the phases containing Ni atoms.
In the first part of this publication, the methodology of the calcu-
lations is described. In the second part, the enthalpy of formation of the
binary and ternary phases involved in the Ni-O-Sn-Ti system are cal-
culated; the predicted phase diagrams are compared to the experi-
mental ones to validate the global methodology. In the third part, the
point-defect calculations are presented and the oxidation processes of
NiTiSn are then presented and discussed.
2. Methodology
The DFT calculations are performed using the Vienna ab initio si-
mulation package (VASP) [18,19] and the projector augmented waves
(PAW) technique [20,21] within the generalized gradient approxima-
tion (GGA). The Perdew-Burke-Ernzerhof parameterization (PBE) is
applied [22,23].
Standard versions of the PAW potentials for Ni, Sn and Ti are used.
The pseudo-potential names are respectively Ni, Sn_pv, Ti_sv. For
oxygen, the “soft” pseudopotential (O_s) is selected. Four electronic
states are included in the valence shell for Sn (5s25p2) and Ti (3d24s2),
whereas ten are taken for Ni (3d84s2) and 6 for O (2s22p4).
The calculations are performed using the “accurate” precision set-
ting in the VASP input file to avoid wrap-around errors. The first
Brillouin zone is integrated using Monkhorst-Pack k-point meshes. The
reciprocal space mesh is set so as to obtain a number of k-points mul-
tiplied by the number of atoms higher than 500 in the irreducible part
of the Brillouin zone. The cutoff energy is set to 450 eV for the whole
study.
For phases containing nickel atoms, two methods have been in-
volved. The first one consists in the GGA + U method. However, the
“simple” GGA methodology is also used in some cases. For GGA + U
calculations, the method of Dudarev et al. [14] is used. The choice of
the parameter Ueff is detailed in section 3.1.
The total energy of each structure is minimized by relaxing the
volume of the cell and the ionic positions starting from the experi-
mental cell parameters and crystallographic positions [24]. For point-
defects in the half-Heusler NiTiSn (F 43m , cF12, prototype MgAgAs),
calculations have been done with a primitive 3*3*3 supercell (P333)
containing 81 atoms. For interstitials defects, two possible positions are
taken into consideration: (4d) Wyckoff position (¾; ¾;¾) and (24g)
63
Intermetallics 92 (2018) 62–71
Wyckoff position (0.49; ¼;¼). We have arbitrarily chosen this last
position as the most probable interstitial position in the Heusler phase.
For the other binary and ternary phases, conventional cells are used
except otherwise mentioned in the text.
For solid solutions or partial site occupations (with a Site
Occupation Factor (SOF) lower than 1), the distribution of atoms is
generated in a supercell by Special Quasi-random Structures (SQS [25])
using the ATAT software suite [26] to avoid artificial ordering effects in
the distribution of the atoms. In this methodology, 15 cells are initially
generated and the “less ordered” structure is selected for the DFT cal-
culations.
The calculated enthalpy of formation of a binary phase AxBy is given
by equation (1), the one of a phase containing one point defect by
equation (2). In the example given in equation (2) we assume a NiTiSn
P333 supercell with one interstitial nickel defect.
ΔfH0K(AxBy) = [E(AxBy) – xE(A) − yE(B)]/(x+y) (1)
ΔfH (Ni28Sn27Ti27) = [E(Ni28Sn27Ti27) - 28E(Ni) - 27E(Sn) - 27E(Ti)]/82
0K
(2)
In these 2 equations, E(phase) corresponds to the DFT-calculated
energy of the different phases. The DFT-calculated energies are divided
by the total number of atoms of the cell and converted from eV to J to
obtain enthalpies in kJ/mol of atoms. Such quantities can then be di-
rectly compared whatever the number of atoms contained in the
structure is.
To estimate the stability of a point defect, several methods can be
used. In the most basic approach [27,28], the enthalpy of formation of a
defect is calculated according to equation (3).
ΔdefH0K(Xi) = [ΔfH(Ni28Sn27Ti27) – ΔfH (Ni27Sn27Ti27)]/xdef (3)
In this equation, ΔfH (Ni28Sn27Ti27) corresponds to the enthalpy of
formation of the phase containing the defect (in this example, Nii in a
P333 cell), ΔfH (Ni27Sn27Ti27) corresponds to the enthalpy of formation
of the pure phase and xdef is the considered concentration of defects.
The calculated energies are converted from eV to J. The enthalpy of
formation of the defects is then given in kJ/mol of atom. Depending on
the value of this enthalpy, we can judge of the probability of existence
of a given defect: negative, the defect exists even at 0 K; slightly posi-
tive, the defect will not exist at low temperature, but taking into con-
sideration entropic effects, the defect can exist at higher temperature;
highly positive, the defect is improbable to exist even at high tem-
perature. The limit between slightly positive and highly positive will
change depending on the system; a reasonable value of 100 kJ/mol of
atom (≈1 eV/defect) is generally admitted.
However, in this first method, the influence of the other phases in
the system is not taken into consideration. To correct this phenomenon,
two methodologies can be used. In the first one, one assumes that
adding a defect in the structure will not change the global composition
of the sample. In these conditions, at infinite dilution, the influence of
the chemical potentials of the pure elements and the other phases is
taken into consideration and an additional term is used to correct the
size effect. Such a method was used recently [29] on half-Heusler
phases.
The main problem of such an approach consists in the infinite di-
lution assumption. Indeed, in GGA type calculations, we are limited to
cells containing around 100 atoms, sometimes up to 150 (calculations
with more atoms take more time and are not reasonable if a whole
phase diagram has to be explored). In these conditions, adding one
defect in such a cell will generate a concentration of 0.5–1% of defects
which is far from the infinite dilution. In our approach, we assume that
adding a defect in the cell will change the global composition. We then
compare the energy of the phase with the defect to the one of the
multiphased domain predicted by the phase diagram for the same
composition. The new parameter is named ΔH and is given by equation
(4):
A. Berche, P. Jund Intermetallics 92 (2018) 62–71

Table 1
ΔH = ΔfH0K(Ni28Sn27Ti27)−ΔfH0K(multi) (4) Calculated magnetic moment of Ni in Ni and NiO, energy gap and enthalpy of formation
of NiO at 0 K obtained for different values of Ueff.. For comparison, experimental values
In this equation, ΔfH0K(multi) corresponds to the enthalpy of for- are taken from Refs. [38–41].
mation of a mix of several phases (2 or 3 in a ternary system, up to four
in a quaternary) whose composition is calculated using the lever rule. Ueff (eV) Ni NiO
In some cases, especially when defects highly change the energy of a
mNi (μB) mNi (μB) Energy gap (eV) ΔfH (kJ/mol of atoms)
phase by introducing different bonds (such as metal – oxygen bonds),
the enthalpy of formation of a point defect (ΔdefH0K) can become highly 0 0 – – −60.34
negative whereas the enthalpy of formation of the compound with the 1 0 1.641 – −77.88
defect will be less stable than a mixed alloy made of the pure compound 2 0.691 1.692 0.242 −92.77
3 0.717 1.726 0.796 −111.39
and one oxide for example. This method has been used in a previous
3.5 0.730 1.743 1.057 −120.71
paper [30]. It is more rigorous but requires the knowledge of the as- 4 0.738 1.760 1.316 −130.04
sociated phase diagram. This is why prior to calculate the ΔH of the 5 0.757 1.792 1.842 −148.72
point-defects, the constitutive binary and ternary phase diagrams in- 6 0.767 1.823 2.336 −167.47
Expe. 0.600 1.6–1.9 4.0 −120 ± 5
volved in the Ni-O-Sn-Ti system have to be known. For that, the en-
thalpies of formation of the binary and ternary intermediate phases
have been calculated using DFT calculations.
Table 2
Enthalpy of formation of the phases of the binary oxide systems calculated in GGA or
3. Quaternary phase diagram Ni-O-Sn-Ti GGA + U (for Ni atoms) at 0 K compared to experimental values [42–44] at 298 K.

Phase Compo at% O ΔfH (kJ/mol of atom)

This section will be divided as follows: in the first part, the choice of
the value of Ueff is discussed; then the enthalpies of formation of the DFT Expe.
binary oxide phases are compared to the experimental ones in the
Ni-O
second part; in the third part, the effect of the GGA + U method (for the
NiO 50.00 −120.71 −120 ± 5
Ni atoms) on the binary and ternary Ni-Sn-Ti phase diagram is de- NiO2 57.14 −113.87
scribed; finally, ternary systems containing oxygen are discussed in the Ni3O4 66.67 −90.21
fourth part. O-Sn
SnO 50.00 −139.57 −143.0
Sn5O6 54.55 −149.19 −166.3
3.1. Choice of Ueff SnO2 66.67 −177.39 −192.0
O-Ti
Ti6O 14.29 −82.97
In this study, we have decided to limit the use of the GGA + U
Ti3O 25.00 −141.94
method to Ni atoms since for Sn and Ti, the GGA gives a correct esti- Ti2O 33.33 −183.96
mation of the enthalpy of formation of the oxides. Moreover according a-Ti3O2 33.33 −90.95
to Wang et al. [15] for titanium oxides, “as they are metallic in their b-Ti3O2 40.00 −208.99
partially reduced states, GGA + U might not be an appropriate ap- TiO 50.00 −257.88 −271.4
Ti2O3 60.00 −296.86 −304.0
proach”.
TiO2 66.67 −311.07 −313.3
Prior to calculate the enthalpy of formation of the phases, we have α-Ti 0.00 0.00
to set the value of Ueff for the nickel atoms. In the literature, several Ueff 5.89 −33.05
values have been used. With a value of Ueff = 5.2eV, Bengone et al. 11.12 −62.36
[31] obtain a correct representation of the optical properties even if the 20.00 −109.84
27.27 −147.20
value of the gap is underestimated. Values around 6–7 eV have to be set 33.33 −175.48
to have a good representation of the gap [15,17,32,33]. However, these 42.86 −212.39
values seem to be too high if we compare them to the calculated values 50.00 −226.42
of Ueff which are around 4–5 eV [34–37].
Since it is not possible to definitively choose a value for Ueff, we will
use the method of Wang et al. [15] who suggest to fit the value of Ueff to phase diagram [43] at low temperature. However, the calculated me-
obtain the correct enthalpy of formation of NiO. For that, we calculate tastability is rather small since Sn5O6 is only 0.7 kJ/mol of atom above
different physical and chemical properties of metallic Ni and of the a mechanical mix of SnO + SnO2, small entropic effects may thus
oxide NiO. These calculations are performed for different values of the stabilize Sn5O6. Concerning the absolute values of the enthalpies of
Ueff term. The calculated properties are gathered in Table 1. Finally, the formation, a variation of around 8% is obtained for SnO2. The re-
best enthalpy of formation of NiO is obtained with Ueff = 3.5eV. In this maining values are gathered in Table 2.
case, the magnetic moments of Ni and NiO are in reasonable agreement For O-Ti, there are a lot of intermediate oxides reported in the lit-
with the experimental values. However, a large disagreement is ob- erature, especially between 60 and 66 at% O [44]. Among these phases,
tained concerning the gap of the oxide. Such an underestimation of the all the crystal structures are not solved. The aim of this work is not to
gap is nevertheless rather usual in DFT calculations within the GGA. completely describe the binary phase diagram but to calculate the en-
thalpy of formation of each phase supposed to be stable at low tem-
perature. This is why in this work, only a selection of the known
3.2. Binary oxide systems
structures has been used. Especially, the 7 potential phases (Ti3O5,
Ti4O7, Ti5O9, Ti6O11, Ti7O13, Ti8O15 and Ti9O17) reported [24] between
At first, we have calculated the enthalpy of formation of binary
Ti2O3 and TiO2 are not taken into consideration. The calculated en-
phases (Table 2) reported in Ni-O, O-Sn and O-Ti systems. For Ni-O, in
thalpies of formation are in very good agreement (less than 1% dif-
addition to NiO, the two other phases (Ni3O4 and NiO2) reported in the
ference for TiO2 and around 5% for TiO) with the measurements
literature [24,42] are calculated as stable at 0 K even if their structures
(Table 2). For the Ti-rich side, even if a high solubility of oxygen in α-Ti
are uncertain [42].
is reported at high temperature, below 800 K ordered forms are re-
For O-Sn: SnO2 and SnO are calculated as stable at 0 K whereas
ported for stoichiometries around Ti2O, Ti3O, Ti6O and even Ti12O
Sn5O6 is metastable which is in perfect agreement with the accepted

64
A. Berche, P. Jund Intermetallics 92 (2018) 62–71

Table 3
Enthalpy of formation of the phases in intermetallic systems. The references for experi-
mental values are available in our previous work [8]. GGA calculations are from a pre-
vious work [8] except * from Colinet [47].

Phase Compo. ΔfH (kJ/mol of atom)

GGA GGA + U Expe.

Ni-Sn At% Sn
Ni3Sn 25.00 −20.12* −20.14 −22.5 to −26.3
Ni3Sn2 40.00 −28.10* −29.52 −28.1 to −38.5
Ni3Sn4 58.00 −24.61* −25.43 −29.0 to −31.4
Ni-Ti At% Ti
Ni3Ti 25.00 −47.00 −41.90 −42.2 to −46.5
NiTi 50.00 −38.78 −30.91 −33.1
NiTi2 66.67 −27.05 −22.16
Sn-Ti At% Ti
Ti2Sn3 40.00 −31.92 –
Ti6Sn5 54.55 −37.32 – −43.4
Ti5Sn3 62.50 −34.90 –
Ti2Sn 66.67 −32.77 –
Ti3Sn 75.00 −29.25 –
Fig. 1. Enthalpies of formation of O-Ti phases at low temperature (0 K for DFT and 298 K
Ni-Sn-Ti At% Sn/at%Ti
for experimental). Metastable structures are presented by open circles and open dia-
Ni2Ti2Sn 20.00/20.00 −45.60 −42.80
monds. Ni2TiSn 25.00/25.00 −43.21 −44.58 −46.8
NiTiSn 33.33/33.33 −52.79 −50.24 −52.6
NiTi5Sn3 33.33/55.55 −36.96 −37.53
[44]. For this part, both solid solutions and ordered forms (except for
Ti12O whose crystal structure is unknown) have been calculated. For
the solid solutions, a conventional 2*2*2 (C222) supercell (containing
16 to 32 atoms) is used; several compositions are then generated by
using SQS (oxygen is placed in the octahedral interstitial sites). As
shown (Fig. 1), the ordered structures (blue diamonds) are more stable
than the solid solutions of oxygen in α-Ti (black circles). This is in
agreement with experimental measurements and the difference be-
tween both crystal arrangements (around 5 kJ/mol of atom at 75 %at
Ti) could explain why at higher temperature (above 800 K experi-
mentally), the α-Ti phase is stabilized by entropic effects. For the Ti3O2
phase, the experimental composition is not clearly defined. The phase
has the P6/mmm space group and Ti atoms are ordered on the (1a) and
(2d) Wyckoff positions whereas O are on the (3f) positions. However,
the occupation ratio of oxygen atoms is not clearly established. Ac-
cording to Andersson [45], only half of the positions are occupied
leading to a stoichiometry around Ti2O whereas an occupation ratio of
2/3 would be necessary to obtain the experimental stoichiometry of
Ti3O2. For this reason, in this work, the enthalpy of formation of both
structures has been calculated. They are respectively named a-Ti3O2
(SOF = 0.5) and b-Ti3O2 (SOF = 2/3). Calculations show that both
crystal structures are metastable even if the a-Ti3O2 phase is highly
metastable in comparison to Ti2O. For this phase, a more rigorous ex-
perimental determination of the structure appears to be necessary.
For all these systems, DFT calculations show a nice representation of
the low-temperature binary phase diagrams.

3.3. Binary and ternary intermetallic systems Fig. 2. Ni-Sn-Ti phase diagram calculated by GGA or GGA + U (for Ni atoms) at 0 K.

If the enthalpy of formation of NiO is highly modified by GGA + U,

the case with the GGA formalism which overestimated NiTiSn in
globally the enthalpies of formation of the binary phases in the Ni-Sn,
comparison to Ni2TiSn and Ni2Ti2Sn [8]. It is worth noting that a better
and Ni-Ti remain practically unchanged by the use of the GGA + U
agreement between the calculated phase diagram and the experimental
formalism (Table 3). For these 2 binary systems, the discussion about
section at 1073 K was obtained by Douglas et al. [4] who performed
the comparison between experimental and calculated phase diagrams
GGA + U calculations using Ueff = 5eV both for Ni and Ti atoms.
has been undertaken in a previous paper [8].
However, using such values of Ueff for the Ti atoms will clearly degrade
Concerning the ternary phases, the values of the enthalpies of for-
the calculations of the enthalpies of formation of titanium oxides which
mation calculated by GGA + U remain globally similar to those cal-
is not suitable for this study.
culated by GGA (Table 3). The calculated enthalpies of formation are
still in good agreement with the experimental values. However, using
these enthalpies of formation for the ternary phases, the phase diagram 3.4. Ternary oxide systems
at 0 K (Fig. 2) is in better agreement with the experimental one at
1073 K [46] than with the values from GGA. In particular, both phases The ternary system Ni-O-Ti has been investigated experimentally
Ni2TiSn and Ni2Ti2Sn are now calculated as stable at 0 K which was not [48–51]. On the basis of these studies, the ternary system was assessed

65
A. Berche, P. Jund
using the Calphad method [52]. Two ternary phases have been reported
in the literature: NiTiO3 [53] and Ni2TiO4 [54]. Moreover, it is reported
that Ti2Ni can dissolve a high quantity of oxygen up to 14 at% O [55] at
1173 K. Finally, oxygen is soluble in NiTi at around 1200 K, however at
low temperature, the solubility is negligible this is why it has not been
taken into consideration in this study.
Three crystallographic arrangements have been suggested for
NiTiO3:
- Above 1560 K, neutron investigations [53] suggest the structure of
Al2O3 (R3c ) with an equal repartition of Ni (SOF = 0.5) and Ti
(SOF = 0.5) on the Al Wyckoff position (12c);
- At room temperature, the phase has to have the R3h space group
[53]. However, depending on the investigation method used, two
different arrangements between Ni and Ti atoms have been found.
According to powder analyses [53], the Ni (SOF = 1) and Ti
(SOF = 1) are positioned on 2 different (6c) Wyckoff positions.
According to single crystal refinement [53], a repartition of Ni
(SOF = 0.91 and SOF = 0.09 respectively) and Ti (SOF = 0.09 and
SOF = 0.91 respectively) on each (6c) Wyckoff sites is suggested.
These 3 structures (named R3c , R3h for the ordered structures and
R3h for the disordered one) have been used for DFT calculations, their
enthalpies of formation are presented in Table 4. For the disordered R3h
structure, a supercell built by doubling the conventional cell in the a
direction (C211 with 60 atoms) was taken into consideration. This cell
was used to allow a good representation of the Ni and Ti repartition on
each (6c) Wyckoff position with the lowest number of atoms. This re-
partition on each site has been performed using the SQS method. Re-
sults of the calculations confirm that the R3c structure is metastable at
0 K whereas the R3h phases are stable. At 0 K, the ordered structure is
slightly more stable than the disordered one which may be stabilized
due to entropic effects at higher temperature. Moreover, using the G-
GA + U method for Ni atoms gives a perfect prediction of the enthalpy
of formation (−239.6 kJ/mol of atom for the ordered form) of the
NiTiO3 phase whose ΔfH298K was measured at −240 kJ/mol of atom
[56]. Even if the GGA + U method permits to calculate the enthalpy of
formation of NiTiO3 in better agreement with experiments than with
GGA (−216.0 kJ/mol of atom), the phase NiTiO3 is calculated stable
both in GGA and in GGA + U.
The crystal structure of Ni2TiO4 has been reported [54] with the
MgAl2O4 structure (space group Fd3m ). Oxygen is on the (32e) Wyckoff
position, the (8b) positions are filled with Ni whereas Ni (SOF = 0.5)
and Ti (SOF = 0.5) are shared on the (16c) sites. For the DFT calcu-
lations, the conventional cell is used, the repartition of Ni and Ti on the
(16c) site is performed using SQS. Ni2TiO4 is calculated as metastable at
0 K. The difference between the enthalpy of formation of this phase and
Table 4
Enthalpy of formation of the phases of the ternary oxide systems calculated in GGA and
GGA + U (for Ni atoms) at 0 K compared to experimental values [56] at 298 K.
Phase Space group ΔfH (kJ/mol of atom)
DFT Expe.
NiTiO3 R3c −220.8
R3h - ordered −239.6 −240
−236.5
R3h - disordered
Ni2TiO4 Fd3m −201.5
Ti2NiO0.5 Fd3m −102.9
NiSnO3 R3h - in order −153.2
R3h - disordered −149.7
Pm3m - perovskite −65.2
Ni2SnO4 Fd3m +15.4
SnTiO3 R3h - in order −245.13
Pm3m - perovskite −124.13
66
Intermetallics 92 (2018) 62–71
Fig. 3. Mixing enthalpy between Ti2Ni and Ti2NiO0.5 calculated by GGA + U at 0 K.
the enthalpy of a mix of NiTiO3 and NiO is of 4.1 kJ/mol of atom. In
these conditions, this phase can't be stable at low temperature, how-
ever, it is possible that a metastable phase can be synthesized.
For the oxygen solubility in NiTi2, oxygen may enter the structure in
interstitial positions according to X-ray powder analyses [57]. When all
the positions are filled with O, the composition of the phase is Ti2NiO0.5
which is consistent with the maximum solubility of oxygen in the phase
suggested experimentally. The enthalpy of formation of such a com-
pound has been calculated using DFT and this phase is estimated as
stable. To complete the study of the solubility of oxygen in Ti2Ni, the
enthalpies of formation of several compositions between Ti2Ni and
Ti2NiO0.5 have been calculated by DFT. The repartition of oxygen on
the interstitial sites has been performed with the SQS method in the
conventional cell. The mixing enthalpy in this solid solution is pre-
sented in Fig. 3. According to these calculations, at 0 K, a phase se-
paration may occur; however since the maximum of the ΔmixH curve is
around 400 J/mol of atom, at higher temperature, an experimental
solid solution may form due to entropic effects.
Finally, the ternary phase diagram at 0 K (Fig. 4) is predicted on the
basis of DFT calculations. Globally we have an extremely good re-
presentation of the experimental phase diagram [52]. Nevertheless
some discrepancies seem to exist, such as the phase separation between
Ti2Ni and Ti2NiO0.5 or the stability of Ti6O and Ti3O prior to the so-
lubility of O in α-Ti. However, as previously discussed, this is due to the
fact that the phase diagram is calculated at 0 K. At higher temperature,
the experimental phase diagram may be perfectly represented.
For the Ni-O-Sn ternary system, the experimental data are scarcer
since no experimental diagram is available. The oxidation behavior of
the Ni-Sn phases has been studied using Auger analyses [58]. If the
analyses show that all the phases can be oxidized, the formed phases
involved in the oxidation have not been identified neither by XRD nor
by microscopy examinations. Only the Auger profiles are available but
since the number of phases involved is not given it is not possible to
identify the formed phases. In addition, contradictions exist for higher
oxygen contents in the ternary phase diagram. If the NiSnO3 phase has
been identified [59], phase separation between SnO2 and NiO was also
shown experimentally [60]. The reciprocal solubilities have also been
measured. The crystallographic details of such solid solutions are not
given and thus it is not possible to predict where Ni and Sn atoms may
be introduced in SnO2 and NiO respectively. As a consequence, DFT
calculations can't be performed on these solubilities. The crystal
structure of NiSnO3 is not clearly defined. If the cubic-perovskite crystal
structure has been clearly identified [61], other studies suggest the R3c
A. Berche, P. Jund Intermetallics 92 (2018) 62–71

energy of only 1.56 kJ/mol of atom would stabilize the structure. This
means that a NiSnO3 phase certainly exists even if its crystal structure
(which is not the cubic-perovskite structure) has not been clearly
identified yet: more experimental analyses appear to be necessary. Our
calculated phase diagram at 0 K is given in Fig. 5.
In the O-Sn-Ti system, practically no experimental study has been
published. It has been shown that a complete phase separation occurs
between SnO2 and TiO2 [63]. The Ti-rich corner has been experimen-
tally studied [64] but the authors didn't distinguish Ti3Sn from α-Ti and
as a consequence, no indication on the relative equilibrium can be
deduced. However it seems that Sn can be dissolved inside the α-Ti
solid solution. But since this solid solution is not stable at 0 K, it has not
been taken into consideration in this study. The existence of a ternary
phase Ti12Sn3O10 (Fm3m ) has been reported [65]. The crystallographic
structure is complex with 248 atoms in the conventional cell. This is
why we were not able to calculate the enthalpy of formation of this
phase. Finally, in comparison to the previous oxide systems, the en-
thalpy of formation of the R3h ordered-NiTiO3 phase has been calcu-
lated. This phase is calculated as stable and is, as a consequence, added
to the database. In addition, the perovskite structure was taken into
consideration, but its calculated enthalpy of formation clearly shows
that this phase is metastable. Based on the DFT calculations, the pre-
dicted O-Sn-Ti phase diagram at 0 K is presented in Fig. 6.

4. Oxidation behavior of NiTiSn

Fig. 4. Ni-O-Ti phase diagram calculated by GGA or GGA + U (for Ni atoms) at 0 K.

The database of the enthalpies of formation of the quaternary Ni-O-

Sn-Ti system has been calculated in the previous chapter. The second
step of the study consists in determining the oxidation behavior of the
NiTiSn half-Heusler phase. For that, the enthalpy changes induced by
the addition of oxygen in NiTiSn have been calculated. The stability
parameter ΔH described in section 2 will be taken into consideration.
For comparison, the ΔdefH parameter is also calculated.
Prior to calculate the influence of oxygen, we will check the effi-
ciency of the ΔH parameter in comparison to the enthalpy of formation
of the defect, ΔdefH. The intrinsic point defects such as vacancies, and
antisites on each Wyckoff positions (4a), (4b) and (4c) have been

Fig. 5. Ni-O-Sn phase diagram calculated by GGA or GGA + U (for Ni atoms) at 0 K;

NiSnO3 whose crystal structure is not clearly described is not presented here.

hexagonal structure [62], but only the space group and the XRD dif-
fractograms are available. In addition, Ni2SnO4 (Fd3m ) was synthesized
on thin film samples. The enthalpies of formation of these different
crystallographic structures have been calculated by DFT. Since no
complete crystal structure definition is given for the R3c hexagonal
structure, the R3h structure of NiTiO3 has been tested instead. The
enthalpies of formation (Table 4) clearly show that Ni2SnO4 is unstable
while the perovskite NiSnO3 is highly metastable at 0 K. For the R3h
structure, the calculations predict a metastable phase; however, an Fig. 6. Predicted O-Sn-Ti phase diagram calculated by GGA at 0 K.

67
A. Berche, P. Jund Intermetallics 92 (2018) 62–71

Table 5 explanation is generally assumed in the experimental papers.

Calculated enthalpies of point defects in NiTiSn at 0 K. ΔdefH and ΔH are given in kJ/mol The second way of synthesis consists in direct reaction of the Ni, Ti
of atom (see text for definition).
and Sn elements at low temperature without melting. It is generally
Wyckoff Defect ΔdefH ΔH Multiphased domain achieved by ball-milling (BM). In these methods, the amount of oxygen
position is generally higher than by direct melting since the bowls are not al-
ways perfectly airtight and since the ball-milling device is generally not
(4a) – Sn vSn 391.0 4.41 NiTiSn + Ni2Ti2Sn
placed into a glove box. In the literature, only two tentative to obtain
NiSn 303.0 3.29 NiTiSn + Ni2Ti2Sn + Ni3Ti
OSn 184.31 7.20 NiTiSn + Ni3Ti + Ti2O3 pure NiTiSn by BM have been published. In the first paper, the direct
TiSn 235.6 1.92 NiTiSn + Ni2Ti2Sn + Ti3Sn BM leads to the formation of Ni3Sn4 without the presence of NiTiSn
(4b) – Ti vTi 292.3 3.07 NiTiSn + Ni3Sn4+ Ni3Sn2 [67]. In the second paper, a pre-melting by microwave is performed and
NiTi 294.5 2.80 NiTiSn + Ni3Sn2+ Ni2Ti2Sn NiTiSn + Ni3Sn4 phases are obtained but no analyses prior to annealing
OTi 298.46 7.80 NiTiSn + Ni3Sn4 + Ni3Sn2 + Ti2O3
are given [3]. These results may then be consistent with our DFT cal-
SnTi 177.1 1.06 NiTiSn + Ni3Sn4 + Sn
(4c) - Ni vNi 144.9 1.22 NiTiSn + Sn3Ti2 + Sn5Ti6 culations. Especially in the study of Zou et al. [67] in which, after BM,
ONi 107.98 5.91 NiTiSn + Sn3Ti2 + Sn + Ti2O3 only the Ni3Sn4 phase is detected without Ti and Ni, which indicates
SnNi 352.8 3.47 NiTiSn + Sn3Ti2 + Sn that Ti seems to be missing after the synthesis. Indeed, the detection of
TiNi 412.45 4.44 NiTiSn + Sn3Ti5 + SnTi3
small amounts of the Ti2O3 phase may not be possible by XRD analyses.
(4d) – VA Nii 53.5 0.36 NiTiSn + Ni2TiSn
Oi,4d −26.77 4.32 NiTiSn + Ni3Sn4 + Ni3Sn2 + Ti2O3 Even after SPS (at 1073 K and 1223 K respectively), NiTiSn is obtained,
Sni 372.9 3.93 NiTiSn + Sn but secondary amounts of Ni3Sn4 + Ni2TiSn or Ni3Sn4 remain in the
Tii 187.4 1.78 NiTiSn + Ni2Ti2Sn + Ti3Sn first [67] and second [3] sample respectively. In addition, Zou et al.
(24g) - VA Oi,24g −44.71 4.10 NiTiSn + Ni3Sn4 + Ni3Sn2 + Ti2O3 [67] suggested that the presence of the secondary phase could be due to
slight variations of the sample composition and tried to increase the
initial amount of titanium. With a composition of Ni1Ti1.4Sn1, they
calculated. In addition, interstitial Ni, Sn and Ti atoms on the (4d) site
obtained a pure NiTiSn phase after SPS at 1073 K or at 1123 K. How-
have also been considered. The results are presented in Table 5. With
ever, careful analyses of the sample by TEM and EDS confirm the pre-
the ΔH parameter, no point defect in NiTiSn is probable at 0 K. How-
sence of titanium oxide all over the sample. According to their EDS
ever, at higher temperature, Nii on the (4d) Wyckoff position may occur
measurements, the oxide may be TiO2. However, without structural
(bold in Table 5). Such results are consistent with the results obtained
data, it is not possible to be sure of the exact stoichiometry of the ti-
with the ΔdefH criterion and in good agreement with previous results
tanium oxide.
[28].
Except in the study of Zou et al. [67], secondary oxide phases were
For oxygen point defects, it is obvious that oxygen can't substitute
not evidenced experimentally. This may be due to insufficient analyses
Ni, Sn or Ti atoms (Table 5). For both interstitial sites, the ΔdefH is
of the sample prior to the measurement of the properties. However,
negative. Considering only this parameter would lead to the conclusion
since the presence of such secondary phases may change the thermo-
that oxygen can be inserted in the NiTiSn structure. However, as
electric properties, it is necessary to take high precautions to avoid
mentioned in section 2, the addition of oxygen tends to diminish the
oxygen contamination and to characterize it systematically. This is
total energy of the structure by introducing highly (negative) energetic
especially true for the low temperature reaction synthesis way. But, for
metal – oxygen bonds. As a consequence, for such defects, the ΔH cri-
direct-melting synthesis, if annealing or SPS cycles are necessary to
terion should be preferred to the ΔdefH criterion to predict the defect
homogenize the sample, a too long annealing time at a too high tem-
stability. The calculated ΔH for the two interstitial defects Oi,4d and
perature may also increase the quantity of secondary oxide phases.
Oi,24g are very high. This means that even in interstitial positions,
To complete this study, the thermoelectric properties of NiTiSn
oxygen can't be inserted in the structure.
previously published in the literature are gathered and re-analyzed
These calculations clearly show that in presence of oxygen, NiTiSn
taking into consideration such oxidation phenomena. It is rather diffi-
can't dissolve it and as a consequence, the NiTiSn half Heusler com-
cult to choose the most representative samples. However, when XRD
pound will have a tendency to be decomposed by oxygen. Titanium
analyses clearly show a high content of secondary phases [3], the
oxide (presumably Ti2O3) will be formed and residual Ni and Sn will be
thermoelectric measurements are not taken into consideration in this
available. At low temperature, these elements could form additional
review. The aim here is to analyze the influence of titanium oxide on
phases such as Ni3Sn2 and/or Ni3Sn4. At higher temperature, Ni can
the thermoelectric properties; this is why all the studies about the in-
also be inserted in the (4d) interstitial position and only pure liquid Sn
fluence of other secondary phases (Ni2TiSn for example) are not taken
and titanium oxide can be expulsed from the structure.
into consideration. Five studies are finally selected. The samples are
These predictions may have an important influence on the synthesis
generally synthesized by melting [1,68,69]. In one study [68], the effect
of the pure NiTiSn phase. If several methods can be used to obtain the
of the annealing conditions is tested on two different samples (sample 1:
phase, two general synthesis ways can be used: melting or solid state
3 weeks at 1113 K followed by 2 additional weeks at 1223 K; sample 2:
reaction. In the first way, all the elements are fused (by arc melting,
1 and 4 weeks at 1073 K). In another study [70], a “solid state reaction”
resistance furnace, induction furnace, levitation furnace …), cooled and
is performed by annealing in vacuum at 900 K elemental compacted
then annealed (resistance furnace) or pressed by Spark Plasma Sintering
powders. Due to the temperature, this method is no more a solid state
(SPS) to obtain the pure phase. Annealing is necessary since NiTiSn is
reaction since Sn melts at 505 K. However, such a method avoids the
formed by peritectic reaction [6]. Using such methods, after cooling,
formation of secondary phases during the cooling and limits the oxygen
samples are generally composed of 4 phases (NiTiSn, Ni2TiSn, Ti6Sn5
quantities entering the compound in comparison to BM methods. In the
and Sn) [1,4,5]. The mechanism leading to such alloys is explained by
last study [67], as previously explained, a sample with the initial
the Ni-Sn-Ti phase diagram [7,8]. Even after annealing or after SPS at
composition Ni1Ti1.4Sn1 is ball milled. The obtained powder is com-
temperatures between 1073 K and 1273 K, small amounts of free Sn
pacted by SPS at 1073 K and the sample contains NiTiSn and titanium
[1,2], full Heusler Ni2TiSn [4,66], Ni3Sn4 [3] or Ti6Sn5 [1,2] usually
oxide. The thermoelectric properties of these alloys are compared in
remain. The present insights about oxidation may explain the presence
Fig. 7 (Seebeck coefficient), Fig. 8 (electrical conductivity) and Fig. 9
of Sn or Ni3Sn4 if a part of the sample was oxidized during the synthesis.
(thermal conductivity). To be exhaustive, this study could have taken
However, since these 4 phases are in equilibrium with NiTiSn, a small
into consideration the global density of the pellets used for the mea-
variation of the initial composition of the sample could also explain the
surements; however such data is only available for 2 of the 5 selected
presence of all these secondary phases after annealing or SPS. This last
sources. This is why the influence of this parameter is neglected in the

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following discussions.
The most obvious difference comes from the samples of Zou et al.
[67]. As previously explained, the alloy is composed of pure NiTiSn
mixed with titanium oxide. According to our calculations, this oxide
could be Ti2O3 which is metallic according to its band structure. We can
see that the Seebeck coefficient and the electrical conductivity of the
alloys of Zou et al. [67] are the highest of all the samples. This behavior
is consistent with metallic inclusions of Ti2O3 as shown for example in
the measurements of Liu [71] for metallic inclusions (Cu or Sn) in a
semiconductor (PbS). For the other samples, it is not straightforward to
extract a clear tendency. It is possible that during the electrical con-
ductivity measurements, the sample 1 of Cook [68] has been oxidized
which explains why results differ at high temperature for this sample
and tend to the values of the sample of Zou et al. [67]. Except for this
sample, the thermoelectric properties of the other alloys are globally
similar even if those of Downie et al. [70] have a slightly lower Seebeck
coefficient and a significantly lower electrical conductivity than the
others. Such differences may be due to different carrier concentrations
in the samples or to small quantities of secondary phases which are
assumed by Katayama et al. [1]. To clearly solve this point more ana-
Fig. 7. Evolution of the Seebeck coefficient of NiTiSn as a function of temperature.
lyses appear to be necessary, and especially a careful analysis of the
samples is required.
Taking into consideration these elements, the thermal con-
ductivities are reanalyzed as well. Only 3 series of measurements for the
total thermal conductivity are available [1,67,69]. In addition, the
thermal conductivity of pure NiTiSn has been calculated using first-
principles methods [72,73]. Hermet et al. [72] were able to reproduce
the experimental values of Katayama et al. [1] and Kanemitsu et al.
[69] by modeling materials with grain sizes around 175 nm. In these
conditions, inclusions of titanium oxide contained in the sample of Zou
et al. [67] may slightly reduce the lattice thermal conductivity of Ni-
TiSn by metal-semiconductor heterostructures as observed by Liu et al.
[71] for Cu or Sn inclusions in PbS.
Even if oxide inclusions in the sample of Zou et al. [67] decrease the
thermal conductivity, the global figure-of-merit (ZT) shows a maximum
around 770 K with a value of 0.32 which is similar to the ZT obtained
by Kanemitsu et al. [69] (ZT = 0.3) or by Katayama et al. [1]
(ZT = 0.39) who assumed secondary phases. Finally whatever the
secondary phases (titanium oxides or intermetallic phases) present in
the half-Heusler NiTiSn alloy are, the ZT values are similar even if the
effects on the Seebeck coefficient and the electrical conductivity are
completely different. This behavior is rather surprising since the pre-
Fig. 8. Evolution of the electrical conductivity of NiTiSn as a function of temperature.
sence of secondary metallic phases often degrades the global ZT of a
thermoelectric material by modifying the charge carrier concentration.
More experimental and computational investigations on the global in-
fluence of oxidation on the thermoelectric properties are thus necessary
in order to understand the mechanisms involved in NiTiSn. These
findings are finally positive for applications since if a thermoelectric
module was made with n-type NiTiSn legs, a slight oxidation of the legs
wouldn't significantly change the global ZT of the module. However
from that point of view, additional measurements are necessary, since
the formation of secondary phases could degrade the contacts between
the leg and the metal layer in the module which may be detrimental for
the global performance of the module.

5. Conclusions

In this study the oxidation behavior of the NiTiSn half-Heusler

compound was calculated by ab initio methods. For that, GGA + U is
used for the Ni atoms. This methodology permits us to have a good
representation of the ternary sub-systems of the Ni-O-Sn-Ti quaternary.
Enthalpies of formation of defects (intrinsic or extrinsic oxygen) have
been calculated assuming the correct composition due to these defects
in the supercell. Calculations predict that small amounts of oxygen may
partially decompose the NiTiSn phase into titanium oxide (Ti2O3) and
Fig. 9. Evolution of the thermal conductivity of NiTiSn as a function of temperature.
nickel stannides (Ni3Sn2 + Ni3Sn4) which seems to be confirmed in

69
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