High Temperature and Pressure Dependent
High Temperature and Pressure Dependent
1088/2053-1591/abcfde
PAPER
1. Introduction
Heusler alloys have been comprehensively and systematically studied in the fields of solid state physics and
chemistry due to their remarkable and multidimensional chemical and physical properties [1–3]. These
materials have grabbed lot of attention due to their peculiar properties like high spin polarization, interesting
electronic structure (half-metallic/semiconducting/spin gapless nature), shape-memory effect, large curie
temperatures, ferromagnetism and thermoelectric properties, which are used in various applications like
magnetoresistive materials, spin valve generators, spin filters, transducers, shape memory devices and
spintronics [4–10]. Among them half metallic ferromagnetic (HMF) are a class of materials that have been
acknowledged by the world class researchers due to their application in spintronics/magneto electronics/
thermoelectrics [11–15]. Thus, spin-based electronics are expected to bring revolution in the field of
information technology, memory devices and telecommunication. The addition of the spin degrees of freedom
to the conventional electronic devices has several advantages like non-volatility, increased data processing speed
and decreased electrical power consumption. In these materials spin resolved bands have special behavior, the
majority spin band shows metallic character while the minority spin band shows semiconducting/insulating
behavior with a gap at Fermi level. The ferromagnetic material delivering half-metallic character is one of the
typical behaviors of Heuslers to demonstrate 100% spin polarization at Fermi level [16–18]. One more
important feature of these Heuslers is the likelihood by exhibiting Slater-Pauling (SP) rule which deliberates the
degree of atomic disorder and exchange interactions strength, atomic ordering in the lattice, valence electron
count [19, 20]. Slater-Pauling rule is a simple way to study ferromagnetic alloys and the interrelation between the
valence electron concentration and the magnetic moments. It is well known that the C1b Heusler alloys with
three atoms per unit cell follow a simple rule that scales linearly with the number of valence electrons:
Mt=Zt−18, where Mt represents the total spin magnetic moment and Zt stands for the total number of valence
electrons per unit cell, which was first noted by Kubler et al and the importance of which was also emphasized by
Jung et al and Galanakis et al [19]. Since with 9 electron states occupied in the minority band for C1b Heusler
alloys. Zt−18 is just the number of uncompensated electron spins. Namely, that is magnetic moment per unit
cell. For ordered alloys with different kinds of atoms, it might be more convenient to work with all atoms of the
unit cell. In the case of four atoms per unit cell, as in Heusler alloys like Co2MnGe with L21 structure, one has to
subtract 24 from the accumulated number of valence electrons to find the magnetic moment per unit cell (Mt):
Mt=Zt−24 with Zt denoting the accumulated number of valence electrons in the unit cell containing four
atoms [19]. In the case of Heusler alloys, the number 24 arises from the number of completely occupied minority
bands that has to be 12 in the half-metallic state.
Thermoelectric (TE) materials are in the center of worldwide research activities due to their ability to convert
waste heat into electricity [21–23]. Thermoelectricity is based upon two principles, due to Seebeck and Peltier,
which in general, convert residual heat into electricity and vice versa. The maximum efficiency (ηmax) of a TE
device is calculated by the cold and hot side temperatures (Th and Tc) and the intrinsic figure of merit (zT)
through the following equation,
1 + ZT - 1 ⎡ T ⎤
hmax = 1 + zT - 1 Tc ⎢
1- c⎥ (1)
1 + ZT + ⎣ Th ⎦
Th
For a given temperature difference, the conversion efficiency depends upon the value of zT. The higher the value
of zT the higher is the conversion efficiency. From the theoretical and experimental studies, the Heuslers alloys
have been predicted by the researchers demonstrating half-metallicity in Fe2YSi (Y = Ni, Fe, Mn, Co, Cr and Ni)
[24], Full Heuslers Co-based nanowires: deposition parameter variation of static and energetic properties [25],
experimental and theoretical Ti-based Heuslers Ti2YAl (Y=Co, Fe) [26], Co2YZ (Y=Cr, Sc and Z=Ga, Al)
[27] respectively. The recent experimental study in the field of thin films of Heuslers including Cr2CoGa [28],
Co2MnGe [29], Co2FeAl [30], Fe2CoSi [31], Fe2CrGa [32], Co2MnSi [33], Co2FeSn [34] and Cu2MnAl,
Co2MnSi, Co2MnGe and Co2MnSn [35] also possesses some novel properties which includes spin transfer
torque for RAM and perpendicular magnetic anisotropy (PMA) [36]. Motivated by above-mentioned properties
and keeping in view the multi-dimensional applications of these materials we have investigated the structural,
magneto-electronic, mechanical, transport and thermal properties of Co2VN (N=Sn, Sb) Heuslers at high
temperature and pressure. Therefore, our results would act as a guide for experimentalists for synthesis of such
ferromagnetic Heusler compounds.
2. Computational details
Highly accurate and precise ground state properties are computed from high-throughput density functional
theory (DFT) calculations using full-potential linearly augmented plane wave method (FPLAPW) method
implemented in the WEIN2k code [37]. The unknown exchange-correlation function in the Khon–Sham
equations is generally approximated by well-known methods such as generalized gradient approximation
(GGA). The GGA additionally includes the information gathered from gradient in the electron density. So,
(GGA) [38] along with (GGA+U) [39] with onsite coulomb interaction (U) have to be selected by substituting
U by Ueff. Here, Ueff=U-J where, J is the onsite exchange interaction and U is the onset coulomb term after
being optimized to deliver more precise band profiles for present set of alloys. In the present study, Co possesses
seven valence electrons in the d-orbital and Coulomb potential (Ueff) was varied by adjusting J=0–0.4. The
optimized Ueff for Co was initiated to be 0.44 Ry (5.98 eV). Since GGA and GGA+U formulism are somehow
in adequate to explain the magneto-electronic structure of correlated systems accurately. Therefore, modified
Becke Johnson (mBJ) [40] has been employed to figure out the exchange correlation which mainly assembled of
d and f-states. In FP-LAPW method, the crystal is divided into the non-overlapping muffin-tin spheres centered
at each nuclei and the interstitial regions among them. The basis functions are expanded into the spherical
harmonic functions within the muffin-tin sphere and the Fourier series within the interstitial region. The
convergence of the basis set was controlled by a cutoff parameter RMT Kmax=8, here RMT shows the smallest
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
radii of the muffin tin sphere and Kmax represents the largest reciprocal lattice vector in the plane wave
expansion. The cutoff energy was limited by −6 Ry value. In the self-consistent iteration cycle, the charge
convergence value was set to 0.0001e. In order to construct the charge density in each self-consistency step, the
tetrahedron method with a k points in the irreducible wedge (3000 k-points in the full BZ) was used at the
Brillouin zone (BZ) integration. Elastic constants are taken from cubic-elastic code for the present set of alloys
[41]. By using the calculation for band occupation, the Boltzmann transport theory is used to figure out the
transport coefficients [42]. Gibbs2 simulation package is used to calculate the thermodynamic properties [43].
The typical code needs the energy band structure altogether lattice’s group symmetry. Hence, tensor of the
electrical conductivity usually is achieved by doing the Fourier expansion expressed as:
sab (i , k) = e 2ti, kva (i , k) vb (i , k) (2)
Where the term and ti, k and e illustrates the relaxation of time and charge of en electron respectively and va (i , k )
represents α component with i band index of the group velocity and is demonstrated as,
1 ¶ei, k
va (i , k) = (3)
¶ka
Seebeck tensors, electrical conductivity and the group velocity can be determined as following relations
expressed as:
S i , j (T , m ) = å (s-1)ai vaj (4)
a
1 ⎛ -¶f (T , m) ⎞
sab (T , m) =
8p i
3 å ò
sab (i , k) ⎜
⎝ ¶e
⎟ dk
⎠
(5)
1 ⎛ -¶f (T , m) ⎞
vab (T , m) = å
8p T i
3 ò
sab (i , k)[e (k) - m] ⎜
⎝ ¶e
⎟ dk
⎠
(6)
The various properties of the materials under consideration have been discussed in the following sections.
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
Figure 2. Graphical representation of crystal structure of Co2VN (N=Sn, Sb) Heuslers in u2MnAl prototype.
Table 1. The calculated values of lattice parameter (a0 in Å), Cohesive energy (eV atom−1), and Formation
energy (eV unit−1 cell) for Co2VN (N=Sn, Sb) Heuslers.
Table 2. The calculated values of elastic constants and its associated parameters for Co2VN
(N=Sn, Sb) Heuslers.
ferromagnetic (spin-polarized) and is demonstrated in figure 1 to define the exact ground state. The associated
lattice parameters as well as atomic positions were completely relaxed within the present calculation process. It is
notified from the stability curves and other theoretical calculated results that the minimum energy of these
Heuslers supports the ferromagnetic phase rather than non-magnetic phase. Howsoever, the stability
components of Co2VN (N=Sn, Sb) Heuslers are illustrated form table 1 and the structure is demonstrated in
figure 2 where Co2VN (N=Sn, Sb) Heuslers prefers Cu2MnAl type.
An elastic property expresses the potential of a material to get back to its original shape upon removal of
deforming force. The elastic constants of a material determine the response to an applied stress. These constants
are important because of due to the fact that these parameters are related to behaviors of materials, including
hardness, durability, strength, reliability, and performance required to designate the type of application and
fabrication [51, 52]. The number of independent elastic constants required for a system is directly related to
symmetry of structure. More symmetric the structure less is the number elastic constant required. For cubic
structures, the number of elastic constants reduces to three C11, C12 and C44. In order to determine them, we
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
Figure 3. Variation of volume with pressure for Co2VN (N=Sn, Sb) Heusler alloys.
have used the rhombohedral and tetrahedral distortions on the cubic structure under volume conserving
constrain. The requirement on these elastic constants leads to the following restrictions C11>0, C12 >0, C44
>0, (C11 − C12)>0, and C12<B<C11 defined by Born-Haung [53–56]. The detailed discussion of different
parameters has been precisely written here shown in table 2. The shear modulus is concerned with the
deformation of a solid when it experiences a force parallel to one of its surfaces while its opposite face
experiences an opposing force. The determination of hardness or strength of a material is related to the Bulk
modulus (B). It also determines the strength against the brittleness. The materials with large bulk modulus are
more strong compared to those with small value of bulk modulus. The calculated values of bulk modulus for the
present alloys suggest these alloys have high facture strength. Young’s modulus is a mechanical property that
measures the stiffness of a solid material. It defines the relationship between stress (force per unit area) and strain
(proportional deformation) in a material in the linear elasticity regime of a uniaxial deformation. The calculated
values of Young’s modulus of these alloys indicating they are stiff in nature. Ductile and brittle nature of an alloy
can also be determined through the elastic constants (Cij). The nature of the atomic binding is related to the
ductile or brittle nature and can be revealed by the Cauchy pressure [57]. For metallic bonding with ductile
nature, the Cp is positive. Moreover, for brittle materials with directional and angular bonding character, it has
negative value. From the observed in table 2, it is clear that Co2VSn is ductile and Co2VSb is brittle in nature.
Brittle and ductile nature can also be interpreted by Pugh’s ductility index (B/G). According to the Pugh’s
criterion, the low (high) B/G ratio is coupled with the brittle (ductile) nature of the materials. The key values
separating brittleness and ductility is 1.75, below this value material possess brittle nature and if B/G>1.75
material has ductile nature. The calculated value for Co2VSn lie above the critical value indicates its ductile
nature while for Co2VSb it lies below the critical value indicating its brittle nature. The ratio of transverse
contraction strain to longitudinal extension strain in the direction of applied force is known as Poison’s ratio. It
is another criterion that has been verified experimentally to determine ductile or brittle nature of an alloy and is
defined by relation. The critical value of n to differentiate brittle and ductile materials is 0.26. Materials with
0.26 < ν < 0.5 are regarded as ductile materials, for 0.12<ν<0.26 materials are supposed to be brittle. The
calculated value of ν in table 2, indicates similar results for Co2VN (N=Sn, Sb) Heuslers as shown by Cp and B/
G values. We have also calculated Lamé Constants that recommends the elastic stress components of a material
to the isotropic deformable of strain at a definite point. Bond twisting along with the bond lengthening can be
designated through the Kleinman parameter. These alloys deliver a significant value of Kleinman parameter,
hence demonstrates their strengthened against various external forces and lends its strong support in
engineering purposes. Melting temperature is also an indicator of atomic bonding strength and there is
relationship with Young’s modulus. The general trend is that a higher melting temperature indicates a higher
modulus and vice versa. Ordering of the crystalline lattice is energetically favorable which means that crystalline
structures are generally more stable thermally as well as chemically. We have calculated the melting temperature
of Co2VN (N=Sn, Sb) alloys from Fine’s relation [58].
The melting temperatures for these alloys are 1931.62 K and 2236.33 K with a standard error of ±300 K suggests
that these alloys preserve their lattice structures over wide range of temperatures. The cohesive energy is an
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
Figure 4. Spin polarised band profile of Co2VN (N=Sn, Sb) Heuslers along high-symmetry Brillion zone.
Table 3. Band profiles including nature and type of band-gaps for Co2VN (N=Sn, Sb) Heuslers in respective GGA and GGA+U and
mBJ formalisms.
Symmetry points
Material VBM CBM Bandgap Nature of band-gap Majority carriers Type of band structure
GGA
Co2VSn Γ = −0.25 X=0.20 0.45 Indirect Electrons n-type
Co2VSb Γ=−0.25 Γ = 0.00 No gap Metallic in nature
GGA+U
Co2VSn Γ=−0.35 X=0.53 0.88 Indirect Holes p-type
Co2VSb X=−0.38 X=0.60 0.98 Direct Electrons n-type
mBJ
Co2VSn Γ=−0.40 X=0.72 1.12 Indirect Electrons n-type
Co2VSb Δ = 0.58 X=0.76 1.34 Indirect Electrons n-type
important thermo-dynamical feature defines its strength capability of the material and can be measured
experimentally by the process of heat of sublimation. It conveys us about the bond strength of a material, which is
equal to the energy needed to break the intermolecular physical links. It is regarded a dynamic quantity by which all
thermodynamic parameters as well as chemical bonding can be elucidated. The prediction of cohesive energy
within the first principles has been calculated for Co2VN (N=Sn, Sb) Heuslers. The calculated values of cohesive
energy for these alloys are 4.11 eV atom−1 and 4.45 eV atom−1 for Co2VSn and Co2VSb respectively. The calculated
values illustrated that the atoms are robustly withheld each other in a crystal lattice and will preserve their respective
structures over extensive range of external forces. Heusler alloys can be synthesized and form stable phases. In order
to demonstrate that Co2VN (N=Sn, Sb) Heuslers could be synthesized with stable phases, we calculated the
formation energy (Ef) by subtracting the sum of equilibrium total energies for the constituent elements from the
equilibrium total energies of corresponding alloys by using the formula. The calculated formation energies turn out
to be negative, which indicates that these alloys can easily be synthesized experimentally. The calculated formation
energies for Co2VSn and Co2VSb are −1.63 (eV unit−1 cell), −1.74 (eV unit−1 cell) respectively comes out to be
negative signifying that theses alloys can be experimentally synthesized.
To analyze the pressure effect on the structural properties, Gibbs 2 code is incorporated to generate pressure-
volume (P–V) data by calculating unit cell volumes under a series of applied hydrostatic pressures and is
represented in figure 3. The continuity in P–V plot indicates the absence of any structural phase transition from
highly symmetric cubic structure to other structural phase.
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Figure 5. Graphical representation of total density of states of Co2VN (N=Sn, Sb) Heuslers from GGA and GGA+U and mBJ
formalisms.
Table 4. The calculated total, atomic magnetic moments ,band gap and total valence electrons (Zt) of Co2VN (N=Sn,
Sb) Heuslers using GGA, GGA+U and mBJ approximations.
profile, are used to describe the electronic structure of Co2VN (N=Sn, Sb) Heuslers is illustrated in figure 4
along with high-symmetry Brillion zone (BZ), nature and type of band profile is represented in table 3. The
materials possessing smart magneto-electronic profile are immensely required in numerous scientific fields. By
using GGA formalism, the energy levels are crossing at Fermi level in up-down spin channel, hence exhibiting
metallic character for Co2VSb alloy. However at Fermi level Co2VSn shows a semiconducting gap of 0.46 eV in
spin down channel and metallic nature in spin up channel delivering half-metallicity. As we know that the
transition metal systems are usually highly correlated, so to further elucidate this discrepancy has to be needed.
Since the GGA method underestimates the band gap, so some sophisticated methods have been adopted in order
to obtain the precise band structure. To eliminate the vagueness, the GGA+U method has been adopted. The
current value of U was precisely chosen for Co-d orbital electrons is 5.98 eV. However, the Hubbard correction is
insufficient for these Heuslers to define the band occupation. So, we have used mBJ potential to define effective
and accurate band profile. The important benefit of the mBJ is the inbuilt potential due to which the accurate
examination of the band gap energies have been investigated for Co2VN (N=Sn, Sb) Heuslers. Mostly the
origin of half-metallic nature of Co2VN (N=Sn, Sb) Heuslers can be examined by presenting the possible
hybridization among the constituent atoms schematically and usually there are three interactions which are
responsible for the origin of gap in materials; these are classified as (i) charge transfer band gap (ii) covalent band
gap and (iii) d-d orbital hybridization band gap. The energy gap in Heusler alloys arises mainly due to d-d
hybridization, so the origin of this gap can be predicted by d-d hybridization between the energy levels in both
majority and minority spin channels schematically. The degeneracy of d-states is lifted when it is acted by
external fields (octahedral or tetrahedral), thus creating a triply degenerated 3t2g and doubly degenerated 2eg
states (bonding) along with formation of anti-bonding states due to crystal field splitting. The transition metal
atom d-states in presence of crystal field are decomposed into double degenerate e.g. (dx 2-y 2, dz 2 ) and triple
degenerate t2g (dxy, dyz, dzx) states. The existence of metallic nature in one spin channel and semiconducting
exhibits100% spin polarization in region of Fermi level.
Next, we tried to figure out the magnetic properties which decide the capability of these materials in spin
based technological fields and covers its attention towards the most remarkable applications such as spintronics,
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
Figure 6. Representation of partial density of states of Co2VN (N=Sn, Sb) Heuslers by mBJ formulism.
Figure 7. Calculated Seebeck coefficients (S) and total Seebeck coefficient (S) with temperature for Co2VN(N=Sn, Sb) Heuslers.
random memory shape devices, spin injectors, spin filters, etc. The magnetic calculation is carried out through
GGA and GGA+U and mBJ formalisms are illustrated in table 4. For full Heusler alloys with an L21 structure
(the present study follows the same rule), the origin of the band-gap and the Mt=Zt − 24 rule are well
understood from the discussions of Galanakis et al based on first-principles calculations and the group theory
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
Figure 8. Graphical variation of electrical conductivity as a function temperature for Co2VN (N=Sn, Sb) Heuslers.
Figure 9. The variation of lattice thermal conductivity with temperature for Co2VN (N=Sn, Sb) Heuslers.
Figure 10. Variation of power factor (a) and figure of merit (b) with temperature for Co2VN (N=Sn, Sb) Heuslers.
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Mater. Res. Express 7 (2020) 125701 S A Sofi and D C Gupta
Figure 11. Graphical variation of specific heat (Cv) of Co2VN (N=Sn, Sb) Heuslers at different temperature and pressures.
[19]. They have demonstrated that in full-Heusler alloys with an L21 structure Cu2MnGe-prototype, the d–d
hybridizations between the Co atoms are very important despite of their being next-nearest-neighbors to each
other. This situation leads to the bonding t2g and eg states and anti-bonding t1u and eu states. The t2g and eg states
are hybridized with the d states of the Mn atom, but the t1u and eu states cannot couple with any of the d states of
Mn due to the lack of symmetry. The t1u states are below the Fermi level and they are occupied, whereas the eu
states are just above the Fermi level. Therefore, the minority occupied bands accommodate a total of 12 electrons
(1 s, 3p, and 8d electrons), and the total magnetic moment Mt=Zt−24 follows. Recent experimental and
theoretical research reveals that the full-Heusler alloys with an Hg2CuTi-type structure can also belong to the
family of half-metallic materials. These types of alloys mostly follow the Mt=Zt−18 rule instead of the
Mt=Zt−24 rule. Thus the present study (following Mt=Zt−24 rule) delivers the magnetism from the
alloys with the maximum contribution of Co-supplies to the lattice structure. The total DOS is illustrated in the
figure 5 elucidates the consequence of mBJ potential mainly on the electronic profiles. The different energy states
are shifted predominantly from the Fermi level offers the band gap there. Further the clarification of the energy
states which are primarily linked with the bands (i.e., to analyses the visibility of the states), we have plotted
partial density of states displayed in figure 6. Whereas, properties of N=(Sn/Sb) states are typically far from the
valance band, thus don’t perform any significant character in defining the electronic band profile i.e. their
contribution of magnetic character is least around the Fermi level in comparison to Cobalt which supplies most
contribution. On comparing the pDOS of the two alloys we examine the d-states of transition atoms through
Fermi level delivers half metallic character of alloys. In Co-based alloy, both dt2g as well deg-states are below Fermi
signifies in p-d hybridization in up-spin channel. However in down-spin dt2g-states are at Fermi level while deg
states are empty lie above Fermi level. The overall combination of ferromagnetic spins alignments constitutes
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Figure 12. The variation of thermal expansion coefficient (α) of Co2VN (N=Sn, Sb) Heuslers at different temperature and pressures.
the net magnetism in their corresponding structures. Hence, the sufficient magnetism comprising these
Heuslers may lend their extending stand in high performance spin electronic devices.
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Figure 13. The variation of Grunsein parameter (γ) of Co2VN (N=Sn, Sb) Heuslers at different temperature and pressures.
8P2kB2 ⁎ ⎛ P ⎞2 / 3
S= m T⎜ ⎟ (8)
3e 2 ⎝ 3n ⎠
AQD V1 / 3m
KL = (9)
g 2n2 / 3T
Where A is a collection of physical constants (A∼3.1×10−8) and γ is Grüneisen parameter. The calculated
value of total thermal conductivity for Co2VN (N=Sn, Sb) Heuslers in up-down channel as a function
temperature is illustrated in figure 9. In up-spin alignment κe/τ with temperature increases linearly, however in
down alignment a small changes up-to 400 K beyond which a swift change can be observed. With the increase in
temperature the total electronic thermal conductivity delivers an increasing trend. The thermal conductivity
rises form 5.34×1015 at 300 K to 17.43×1015 at 1200 K for Co2VSn, and 5.17×1015 W (Kms)−1 at 300 K to
15.9×1015 W(Kms)−1 for Co2VSb Heuslers. The total thermal conductivity shows the decreasing trend up to
the some temperature and then increases slowly as the electronic thermal conductivity becomes dominant at
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Figure 14. Variation of entropy (S) with temperature and pressure of Co2VN (N=Sn, Sb).
higher temperatures. Recently, Co2MnAs alloy predicted with a PF 0.40×10–5 W mK−2 at 0 K and 0 GPa.
Enamullah et al evaluates PF of Co-based Heuslers nearly equal to 0.80×10–5 W mK−2 at room temperature.
However, Sofi et al explored the Power factor of approximately 1.20 W mK−2 for Co2ScSb and 1.80 W mK−2 for
Co2TiSb at 0 K and 0 GPa. On comparing the Power factor of above said materials, the current study delivers a
significant PF and illustrates in figure 10(a). At 0 GPa and 0 K the predicted PF for Co2VN (N=Sn, Sb) Heuslers
is 2.95×10–5 W mK−2, 3.72×10–5 W mK−2 respectively. The present set of Heusler materials demonstrates
the value of PF high in comparison with the Co-based Heuslers at 0 K and 0 GPa. Thus, we conclude that Co2VN
(N=Sn, Sb) Heuslers creates its possibility in thermoelectric applicability. To define the significance of a
material for a TE generation purposes, ZT calculation is the best parameter. The deviation of ZT with
temperature is described in figure 10(b). The calculated value of ZT for Co2VSn is 0.14 and that of Co2VSb is 0.13
at 1200 K respectively. This efficient capability conveys that the present set of alloys find a possible stand for
thermoelectric purposes.
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to store heat as the temperature changes. From this, we can get the information about different properties like
lattice vibration etc. Since in solids volume does not change appreciably with application of temperature, so we
here reported the specific heat at constant volume (CV) shown in figure 11. From this graph, we can see that CV
increases with temperature due to increase in atomic vibrations. At high temperatures, CVtends towards a
constant value showing the Dulong and Petit limit [64]. However, at lower temperature CV changes abruptly
with temperature obeying Debye T3 law.
Thermal expansion (α) is the tendency of matter to change its shape, area, volume, and density in response to
a change in temperature. The graphical representation with respect to temperature and pressure variation for the
present Heusler alloys is displayed in figure 12. The sharp rising trend of (α) followed at lower temperatures
while it attains a constant value at higher temperature. The Grüneisen parameter (γ) is used to designate the
thermo-mechanical properties and clarifies the association between change in volume in case of crystals and
frequency associated with phonon. It is also considered a significant dynamical property used to quantify the
relationship between elastic and thermal description of solids and is directly connected with them. Here in the
present case the Grüneisen parameter (γ) shows an increasing inclining trend with increase in temperature, but
on the other hand shows radical decrease with increase in pressure. The calculated value of Grüneisen parameter
at pressure 0 GPa and temperature 300 K for Co2VSn and Co2VSb is 2.07 and 2.41 respectively shown in
figure 13. Entropy of the material delivers information a crucial understanding related to the vibrational
properties which exhibits the vital significance the presentation of several dispositive’s like heat pumps, heat
engines and refrigerators etc. At fixed pressures the entropy at ambient conditions is exhibited in figure 14. From
the plots we observed that entropy increases from 0 K to 650 K. Additionally, the obtained values of entropy
suggests the value of 45.33 Jmol−1 K−1 for Co2VSn and 47.04 Jmol−1 K−1 for Co2VSb Heuslers, designate that
Co2VSb is less ordered than Co2VSn at ambient conditions. Beyond the temperature 650 K the extensive
property becomes very high. This is mainly due to the vibrational entropy increases of the material with the
rising temperature and shows a declining trend with the rise in cohesive energy.
4. Conclusions
By using the Full potential linearized augmented plane wave method based on the density function theory we
have carried out ab-initio calculations of Co-based full Heusler alloy. The observed band structures was found to
be indirect having n-type semiconducting nature at Fermi level. The strongly dependent elastic constants and
cohesive/formation energies illustrates the stability of these alloys. Transport parameters, viz. electrical and
thermal conductivity, Seebeck coefficient, power factor and zT have been calculated by using the BoltzTraP
code. Meanwhile, thermodynamic properties of Co2VN viz thermal expansion coefficient, unit cell volume and
Grüneisen parameter as a function of the temperature and pressure are evaluated by means of quasi-harmonic
Debye model. The outcomes display that entropy increases with increase in the temperature. Grüneisen
parameter is more sensitive to pressure than temperature, while as specific heat significantly depends on
temperature and follows T3 law. These materials show the possible TE performance with the significant zT value.
Hence, our conclusions will play a starting place to guide experimentalists for developing the high temperature
TE materials.
Acknowledgments
The authors are greatly thankful to Jiwaji University Gwalior for providing facilities to carry out the
research work.
The data that support the findings of this study are available from the corresponding author upon reasonable
request.
Conflict of interest
The authors declare that they don’t have any conflict of interest.
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Author’s statement
All the calculations and manuscript writing have been done by Shakeel Ahmad Sofi under the supervision of
Dinesh C Gupta.
Supplementary material
ORCID iDs
References
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