Intermetallics 98 (2018) 154–160

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

Peculiarities of doping of nanograined thermoelectric TiNiSn by 3d noble T

and transition metals
K. Kirievsky∗, Y. Orr, A. O'Neill, D. Fuks, Y. Gelbstein
Materials Engineering Department, Ben Gurion University of the Negev, Beer Sheva, Israel

A B S T R A C T

The effect of nano-structures and in particular nano-grains on reduction of the lattice thermal conductivity, via
enhanced phonon scattering, and thereby increasing of the thermoelectric figure of merit, is well established.
Nevertheless, the effect of grain boundaries on the electronic transport properties of nano-grained thermoelectric
materials, was rarely considered. Such an electronic contribution of the grain boundaries might significantly
affect the thermoelectric efficiency of such materials. In the current research this effect is theoretically studied by
the density functional theory approach, for the thermoelectrically promising half-Heusler TiNiSn compound,
upon a simultaneous introduction of grain-boundaries and either Fe or Cu doping. It is shown that the combined
donor effect of grain boundaries with the Cu donor nature and Fe acceptor nature exhibits interesting pecu-
liarities that should be considered upon synthesis of related polycrystalline materials. For the case of Cu doping,
an enhanced n-type conductivity was attributed to the interaction between the totally occupied 3d-shell of Cu
and grain-boundary states, while upon Fe doping, grain-boundary states interaction with the partly occupied 3d-
states of electrons in Fe, might vanish the energy gap completely, creating a semi-metal. Based on these case
studies, a general route for enhancing of the thermoelectric potential of chemically doped nano-grained ther-
moelectric materials is proposed.

1. Introduction materials for increasing ZT, via the reduction of κl by phonon scat-
tering. The perspective way to improve the desired properties is by
Development of thermoelectric (TE) materials for conversion of heat using TE materials obtained by sintering of nano-powders. This has
into electrical power involves controlling their thermal and electrical drawn much attention primarily due to the prediction that quantum
transport properties, which are both sensitive to the finest features of confinement of charge carriers in low dimensional structures within a
the material's microstructure. The TE figure of merit, ZT, is a di- given matrix could drastically increase Seebeck coefficient together
mensionless parameter that includes thermal and electronic transport with significant decrease of thermal conductivity of the material,
coefficients of the involved material and denotes the energy conversion leading to enhancement of the TE power factor, S2σ, see for example
efficiency with respect to the material's properties. High ZT values are [2,3]. The perspectives to use nano TE materials were discussed in Refs.
typically achieved in heavily-doped semiconductors having relatively [4,5].
high values of electrical conductivity, σ , and Seebeck coefficients, S, at Numerous experimental techniques are being used for preparing
the same time with relatively low values of lattice thermal conductivity, nano-grained TE materials, involving solvothermal method combined
κl [1]. Optimizing the TE performance of single phase materials is with sparking plasma sintering [6], liquid phase compaction method
usually not straightforward, since these three transport coefficients are [7], cryomilling combined with spark plasma sintering [8], arc-melting
inter-related. Increasing the dopant concentration leads to increase of σ [9], etc.
and decrease of |S|, due to the shift of Fermi energy toward the valence While applying such methods for preparing TE materials, the main
(for p-type) or conduction (for n-type) bands. Concurrently, the elec- attention is usually paid to the analysis of the phonon scattering me-
tronic component of the thermal conductivity, κ e , increases whereas its chanisms leading to significant reduction of lattice thermal conductivity
lattice component, κl , decreases due to phonon scattering. This inter- and consequently to the increase of ZT. The paper [10] was seemingly
play demonstrates the complexity of TE optimization. Many studies the first one where the effect of phonon-grain boundary (GB) scattering
focus on nanometer-size features of inclusions embedded in TE on the lattice thermal conductivity and thermoelectric conversion

∗
Corresponding author.
E-mail addresses: kirievsk@gmail.com (K. Kirievsky), fuks@bgu.ac.il (D. Fuks).

https://doi.org/10.1016/j.intermet.2018.05.003
Received 26 February 2018; Received in revised form 2 May 2018; Accepted 4 May 2018
0966-9795/ © 2018 Elsevier Ltd. All rights reserved.
K. Kirievsky et al. Intermetallics 98 (2018) 154–160

efficiency of heavily doped fine grained, hot-pressed silicon germanium Ca3Co4O9+δ GBs. Segregation of Ba and formation of a Ba-enriched GB
alloy was considered. Furthermore, the role of the nanostructuring for work effectively as a carrier filtering layer to decrease the carrier
potential TE materials was continuously discussed. The influence of GB concentration and subsequently increase of the bulk Seebeck coeffi-
scattering on the TE properties of Mg2Si and Mg2Si0.8Sn0.2 was reported cient. Simultaneously, for optimized Ba addition, Ba GB segregation
in Ref. [11]. Enhanced TE performance of nanostructured Bi2Te3 also promotes the development of a desired crystal texture and thus
through significant phonon scattering was demonstrated in Ref. [12]. increases the carrier mobility. The hypothesis was formulated that Ba-
The effect of boundary scattering on the thermal conductivity of Ti- enriched barrier layer could impact the intergranular carrier motion
NiSn-based half-Heusler alloys was considered in Ref. [13] where ex- and carrier transport. The carrier motion across the Ba-enriched GBs
tensive microstructural analysis in the TiNiSn1−xSbx series revealed a may be limited to those carriers with only sufficiently higher energy. It
correlation between κl and the average grain diameter in these mate- is concluded that filtering effect result in only partial carriers contribute
rials. Results reported in Ref. [14] show that a peak ZT can be achieved to the conduction, leading to reduced carrier concentration as well as
in p-type nanocrystalline bismuth antimony telluride bulk alloy. These increased S. On the other hand, such filtering remains questionable
nanocrystalline bulk materials were made by hot pressing of nano- mainly due to the results reported in Ref. [42] where it was shown that
powders ball-milled from crystalline ingots under inert conditions. for low doping concentrations the Seebeck coefficient is indeed in-
Electrical transport measurements coupled with microstructure studies creased due to energy filtering effects, whereas the electrical con-
and modeling, showed that the ZT improvement is the result of low ductivity is strongly decreased. The resulting power factor is also de-
thermal conductivity caused by the increased phonon scattering by GBs creased. For higher doping concentrations, which are necessary for
and defects. In Ref. [15] a combination of advanced molecular dy- large electrical conductivities and thus reasonable ZT values, the double
namics techniques to engineer grains and to evaluate thermal con- Schottky barriers are very small and have therefore an insignificant
ductivity in PbSe was considered. It was found that the lattice thermal impact on the TE parameters. It was concluded that it would be useful
conductivity is significantly lowered with respect to the perfect crystal, to perform ab initio calculations and simulate the GB on an atomistic
and its temperature dependence is markedly suppressed due to an in- scale in order to get more information about the energy-dependent
creased scattering of low-frequency phonons by GBs over different size scattering effects at GBs. It should be mentioned that in this work the
scales. In Ref. [16] for an n-type nanostructured SiGe the enhancement double Schottky barrier across the GB was considered, while the be-
of ZT was found to come mainly from a significant reduction in the havior of the electronic subsystem in the GB plane may also be im-
thermal conductivity caused by the enhanced phonon scattering by the portant. As follows from recent ab initio calculations [38,39], the charge
increased density of nanograin boundaries. In Ref. [17] grain size was distribution in these two directions is significantly different. The
found to largely influence both the thermal and electrical con- changes in the atoms bonding in the vicinity of the GB lead to strong
ductivities. The observed thermal conductivity agreed with the Call- delocalization of the covalent bonds and stimulate the electron trans-
away model, indicating that enhanced phonon boundary-scattering was port along the interfaces between the grains. In Ref. [40] using density
the govern mechanism. On the contrary, Seebeck coefficient is mostly functional theory (DFT) as implemented in the plane-wave based
governed by the effective mass and carrier concentration, and is con- Vienna Ab initio Simulation Package (VASP), the role of GBs in mod-
sidered as independent of the grain size. The dimensionless ZT sys- ification of the structural, electronic, and transport properties of the
tematically increased with the grain size, challenging the effect of na- polycrystalline HfO2 was investigated. It was shown that tilt defects
nograins in this system. In Ref. [18] the scattering of a broad frequency might be crucial for the enhancement of the electronic transport along
spectrum of phonon mean free path to effectively reduce the lattice their channels in relation to leakage current through GBs. A nice review
thermal conductivity in Se-doped PbTe was discussed. The role of GB of the current trends in TE materials can be found in Refs. [43,44], and
scattering in reducing the thermal conductivity of polycrystalline XNiSn specifically for Half-Heusler compounds, in Ref. [45].
(X = Hf, Zr, Ti) half-Heusler alloys was considered in Refs. [19–21]. TiNiSn Half Heusler alloy being a promising high temperature TE
Recently, complicated skutterudite alloys with grain boundaries deco- material for energy generators is an interesting subject for the in-
rated with nano-phase of InSb were obtained by melt spinning followed vestigation of the role of doping elements in changing the conductivity
by spark plasma sintering and their effectiveness in scattering phonons properties. It has relatively high Seebeck coefficient and good electrical
leading to extremely high ZT values, reaching ∼1.5 at 800 K, were re- conductivity making it a favorable candidate for being applied in TE
ported in Ref. [22]. generators. One of the current challenges for increasing the TE figure of
The doping elements segregating to the GBs may play an important merit is to reduce the comparatively high thermal conductivity that is
role in improving of the TE properties. For example, the effect of Bi evident in this material [46]. Two main methods being investigated
doping on the nanostructure and TE performance of polycrystalline trying to resolve the thermal conductivity issue and achieve higher
calcium cobaltite Ca3−xBixCo4O9 system was reported in Ref. [23], power factor values are by doping of the material (that may be easily
where the samples were prepared using a chemical sol–gel route. In Ref. done) or reduction of the average grain size as a method of increasing
[24] GBs related to 2D nano-structuring were shown to reduce the the phonon scattering and consequently decreasing of κl . It is inter-
thermal conductivity in n-type Bi2(Te0.8Se0.2)3 alloys, while Se doping esting to mention in this context that an extensive investigation of the
increased the absolute Seebeck coefficient, which is beneficial for im- microstructure in TiNiSn1-xSbx series has established a direct correla-
proved TE efficiency. tion between κl and the average grain diameter. In these compounds κl
Much less attention was attracted to the study of the influence of systematically decreases within the reduction of the grain diameter
GBs (both in pure and doped TE materials, where the doping elements below 10 nm even with small variations of the grain size [47].
are segregated to GBs) on the type and concentration of charge carriers. Our previous study [38] demonstrated that interfacial states formed
At the same time, a significant influence of the structural and atomic in nano-grained TiNiSn play an important role in determining the n-
bonding conditions in the vicinity of GB on the properties of the elec- type conductivity of the material. Band gap becomes much smaller than
tronic sub-system in the GB interfaces is well recognized in, for ex- in mono-crystal compound and a sharp peak in DOS appears at the
ample, mechanical properties of materials [25–27], catalysis [28–30], vicinity of Fermi energy. DFT calculations [38] also show an en-
magnetic properties of the interface layers [31–33], electro-migration hancement of n-type conduction along GBs due to changes in the nature
[34,35], in some TE materials [36–40], etc. Recently the dramatic in- of the atomic bonding at GBs, leading to strong delocalization of
crease of the Seebeck coefficient and TE performance of calcium co- covalent bonds that may stimulate the electron transport along the
baltite Ca3Co4O9+δ ceramics through non-stoichiometric addition of interfaces between the grains. As reported in Ref. [38] doping with Cu
minute amount of Ba was demonstrated in Ref. [41]. The reported promotes n-type conductivity that is confirmed by experiments [48]
nanostructure analysis revealed that the added Ba segregates to and doping with Fe initiates p-type behavior of bulk TiNiSn in

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accordance with experimental measurements of Seebeck coefficient coordinate into model coordinate. Matrix RB is expressed by RARΣ
[49]. A similar effect on the conductivity type as that of Fe in TiNiSn, where RΣ is the transformation operation for given Σ value. It is as-
was reported for Co in Zr(Ni,Cox)Sn [50]. sumed that two properties are designated for the model construction: Σ
The different role of 3d noble and transition metals stimulates a value and Miller indices (hkl)A which denote the interface orientation
comparative theoretical analysis of their influence on the conductivity of crystal A at A/B boundary. The most important merit of GBstudio is
in nano-grained TiNiSn. In this paper the influence of doping of nano- the applicability to periodic boundary conditions. It is useful for sys-
grained TiNiSn with Cu or Fe additives segregating to GBs is in- tematic studies on grain boundary properties by ab initio or molecular
vestigated. Small doping concentration (∼5 at% of Cu/Fe) on the Ni dynamics simulation.
sub-lattice, hardly expect to form Cu/Fe clusters because of the rather We consider Σ5 36.9°[100] tilt GB between adjacent nano-grains of
dense distribution of surrounding atoms and high preference to occupy ∼20 Å, each. There are several reasons for choosing the geometry of GB
the considered in the model position (in the center of the polyhedron of used in our calculations. First, based on the consideration of the density
surrounding nearest neighbors). High doping levels may lead to dec- of delocalized d-electrons of Ni in TiNiSn in the bonds destroyed by
oration of GBs by one or several layers of metal, which, because of formation of GBs, it may be concluded that the energy of (001) type GB
percolation conductivity effect, will destroy the desirable semi- in TiNiSn will be lower and thus this GB will be energetically preferable
conducting nature of the material. A comparative study of the density of as compared with, let say, (110) and (111) types of GBs. The situation is
states (DOS) for separated Cu/Fe atoms doping is carried out and pe- similar to [58] where based on crystallochemistry consideration it was
culiarities of charge redistribution stimulated by these elements in the shown that the higher the relative number of not-bonded d-orbitals of
vicinity of GB are discussed. Ni, the less energetically stable will be the surface of Ni containing
phases. This is mainly due to the fact that the un-bonded d-orbitals
2. Methodology increase the surface energy. Second, as follows from Ref. [59] the en-
ergy of considered in our paper Σ5 36.9°[100] GB is relatively high,
DFT using the Full Potential method with the Linearized Augmented only ∼10% smaller than the highest Σ73 in the studied series of (001)
Plane Waves (FP-LAPW) formalism, as implemented in the WIEN2k type grain boundaries for Zinc blende structure of SiC, that belongs to
code (Version 10.1) [51–53] was applied in all calculations. In this the same as TiNiSn space group 216 and has Pearson symbol cF8 close
code, the core states are treated as relativistic and the valence states are to cF12 for TiNiSn. According to [60] this may stimulate the segrega-
considered using a scalar relativistic approach. The exchange–correla- tion of doping elements to such GB. The GB's geometry used in our
tion potential was calculated within the Perdew–Burke–Ernzerhof paper also suggests enough free volume for the segregating dopant.
(PBE) generalized gradient approximation (GGA) [54]. The details of Third, the coincident site density and thus the size of the grain should
our calculations were as follows. The muffin-tin radii (Rmt) were taken be chosen in a way allowing escaping the overlapping of the strain
to be equal to 1.9 Bohr for all of the atoms. For the basis-set size at each fields penetrating from the geometric interface plane between two
point, the cutoff parameter RmtKmax = 7 was used, where Kmax presents grains inside the neighboring grains. As demonstrated in the presented
the magnitude of the largest K vector in the wave function expansion. A results, the relaxations of the atomic positions till the third layer from
maximal l, lmax, equal to 10 was taken in the expansion of the radial the interface are still important, that does not allow application of Σ3
wave functions inside the atomic sphere to represent the valence states. GB model. At the same time, for Σ5 GB model the atomic relaxations
The cut-off energy, separating core and valence states, was chosen to be beyond the third layer may be already neglected. Keeping in mind
−6.0 Ryd for all of the atoms. This condition is necessary in order to reasonable running time of the WIEN 2k Full Potential code, the latter
minimize the leaking of the electron core states into the interstitial GB model is applied in our study considering it of the lowest size limit.
region. All of the integrations over the Brillouin zone (BZ) were per- For non-relaxed structure WIEN 2k code determines the symmetry
formed using the TEMPS scheme implied in WIEN2k with the broad- model of the lattice sites generated by GB Studio 3.0 software as 40
ening parameter in Fermi energy calculations equal to 0.002, which Ama2. The supercell with 116 non-equivalent atoms and supercell
corresponds to ∼40 °C. It was found that k-mesh of 8 x 12 x 8 points, parameters a = 26.397 Å, b = 13.198 Å, c = 5.952 Å was considered in
which corresponds to 216 k-points in the irreducible wedge of BZ, is the following analysis. Further, doping Cu/Fe atoms are considered as
sufficient to achieve an accuracy ∼1·10−3 Ryd in the total energy for segregating to GB and occupy the position in GB in the center of the
all the cases applied in the self-consistent calculations. This set of polyhedron of surrounding nearest neighbors. The atomic positions in
parameters allows calculating the numerous mechanical, thermo- the vicinity of the GB were relaxed using the force minimization tech-
dynamic, and electronic properties of the bulk TiNiSn in a very good nique as implied in the WIEN2k code. The calculations of relaxations
agreement with experimental data and with the results of previous were continued until the Hellman–Feynman forces became less than
calculations as demonstrated by Tables 1,2 from Ref. [38]. ∼0.05 eV/Å.
For further analysis the structure of the GB should be determined. Our model corresponds to small alloying levels (∼5at% of Cu/Fe)
Atomistic models of grain boundaries exhibit wide variations because of on Ni sub-lattice. The relaxation of atoms in the vicinity of the GB, DOS
a large number of geometrical parameters. Geometries of coincident for electrons and the topology of the charge distribution in the GB plane
site lattice (CSL) boundaries (see, for example, [55,56]) are dis- and in the plane across the GB, allow prediction of the changes of the
tinguished by Σ value which is defined as the inverse of coincident site electronic properties that occur in nano-grained Cu or Fe doped TiNiSn.
density. The supercell model for grain boundary in TiNiSn was con- Experimental information on segregation of Cu or Fe into GBs in TiNiSn
structed using GB Studio 3.0 software [57]. GBstudio is the easy-to-use is absent. On the other hand there is an evidence that both Cu and Fe
tool software for generating various grain boundary models especially occupy the empty sites in the Ni sublattice [39,48,50] of mono-crystal
for CSL boundaries. It generates periodic models of CSL, tilt and twist phase, preferring thus the largest free volume for their incorporation.
boundaries in easy and systematic ways. In this software the grain We assume that they occupy the positions with the largest free volume
boundary model in a periodic cell is composed of two same, cubic single also at the interface between the grains. In this sense our results have a
crystals A and B. The simplest geometry to satisfy three-dimensional character of a theoretical prediction and provide a challenge for ex-
periodicity is created by assuming the grain boundary being parallel to perimental study that till now was not carried out.
one face of simulation cell, for example XY plane. Such periodic model
is constructed by finding appropriate rotation matrices RA and RB for 3. Results and discussion
both crystals and translation vectors of simulation cell, X, Y and Z.
Rotation matrix RA expressing the orientation of crystal A in model Schematic view of the part of the supercell in the vicinity of the GB
coordinate is determined so as to translate X and Y vectors in crystal is shown in Fig. 1a. Aimed to investigate the role of the relaxation in the

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out of the relaxation energy (when consecutive relaxation of atoms in

the 1st, 1st and 2nd, etc., layers from the GB plane was performed)
demonstrates that, when atomic positions in three atomic layers from
the GB plane inside the grains are relaxed, the relaxation after the third
layer may be neglected. This correlates with the result obtained in the
phenomenological approach [61] where the elastic theory of solids was
applied. Segregating copper or iron atoms were incorporated into the
relaxed GB in the positions displayed in Fig. 1b, and the additional
relaxation shows negligible change of the relaxation energy.
For understanding the influence of the Cu atoms in the GB on the
electronic properties, the DOS calculations were performed for “pure”
GB and GB with Cu as displayed in Fig. 3a. Comparing with the case of
mono-crystal TiNiSn, additional states appear in the vicinity of EF due
to the broken lattice symmetry and due to the interface formation be-
tween the grains, as can be clearly seen. At the same time the DOS for
“pure” GB and for a Cu alloyed material in this region are different.
Analysis of the local partial DOS for Cu and neighboring Ti and Ni
atoms shows that the Cu atoms segregated at the GB restore the band
gap due to hybridization of 4s-states of Cu with 3d-states of Ti and Ni
atoms. At the same time 3d-states of Cu are significantly shifted to
energies far below (∼−6 eV) the Fermi energy because of the repulsion
of the totally occupied 3d-shell of Cu and partly filled 3d-shells of Ti and
Ni. Both effects lead to restoration of the band gap. It becomes wider
(∼0.32 eV) than for “pure” GB (∼0.15 eV) while the magnitude of the
DOS at EF remains almost the same. Further comparison of the “un-
doped” and “doped” GB reveals that in the latter case the peak in DOS
near EF is wider and shifted to −0.2 eV while in the former case it is at
∼0.05 eV and more sharp. It means that the effective mass of the
electrons that may participate in charge transfer is less for Cu-doped
nano-grained TiNiSn and their mobility is higher.
Fig. 1. Top view of the GB: a) without segregating atoms. The arrows sche- This is confirmed by comparing the charge distribution presented in
matically show the displacements of the involved atoms; b) the same illus- Fig. 4a with that shown in Fig. 6c from Ref. [38]. In these Figures the
trating the positions of Cu atoms segregated to the interface. cross-sections that display differential electron density maps are cal-
culated in the GB plane. This electron density is determined as the
considered structure, the influence of the number of relaxed layers in difference between the sum of the electron densities of the involved
the vicinity of the interface between two grains on the relaxation en- atoms and the electron density in the crystal structure obtained as the
ergy, ΔE was calculated. For this purpose the atomic positions in the result of the density re-distribution, calculated in a self-consistent
first, first and second, first, second and third atomic layers from the procedure. The Cu atoms incorporated in the GB partly restore the
interface inward the grains were considered. bonds between the Sn, Ni and Ti atoms, which were broken due to the
The calculation results indicated very small atomic displacements, GB formation in the undoped material, while increasing the covalent
in a decreasing order from the GB geometrical plane, inward the grain. bonding between these atoms. The regions with increased electron
In Fig. 2 the results illustrating the “penetration” of elastic field inside density in the GB plane form well defined channels that together with
the grain are presented. The calculated energy gain due to relaxation the decrease of the effective mass of electrons may stimulate the hoping
was found to be ∼1.5·10−2 Ry for the chosen supercell. It may be seen conductivity along the GB in the material. As illustrated in Fig. 4b the
also that ΔE saturates to this value with an accuracy of ∼2 mRy when formation of covalent bonds between Cu and neighboring atoms in the
the atomic positions in three layers are relaxed. Damping of the re- vicinity of the GB is even more pronounced in the plane perpendicular
laxation energy inside the TiNiSn nano-grain is clearly seen. The fading to the GB plane but in this plane similar channels are not formed. In this
latter case the additional electron charge is well localized between the
doped Cu and the Ti, Ni atoms in its vicinity. So, in this direction the
charge transfer will be difficult as in the case of formation of double
Schottky barriers across the GB considered in Ref. [42]. This may be
considered as the origin for the conductivity variation in different di-
rections of the material.
Upon Fe atoms segregation to the GBs in TiNiSn the situation is
different. The calculated DOS for this case (Fig. 3b) clearly shows the
vanishing of the band gap in the vicinity of EF. The material becomes
not narrow band gap semiconductor but rather a semi-metal. The peak
in the DOS corresponding to interfacial states, is still preserved al-
though much less pronounced. Local partial DOS for Fe in the back-
ground of surrounding Ti and Ni atoms shows that partly occupied 3d-
states of Fe are situated in the vicinity of EF. Significantly delocalized
3d-electrons of Fe interact with 3d-electrons of Ni and Ti. They also
hybridize with s- and p-electrons of Sn, and form a much more smeared
charge distribution in the vicinity of the GB as compared with Cu. The
Fig. 2. Saturation of the energy of relaxation, ΔE when atomic positions in one, charge distribution in the GB plane with Fe, presented in Fig. 4c, clearly
two, or three layers are relaxed. The line is shown to guide the eye. supports this result. This cross-section illustrates the significant

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Fig. 3. Densities of states for "pure" GB and with segregated Cu (a) and Fe (b) atoms. Fermi energy, EF is set to zero. The insets show a magnification in the vicinity of
EF.

decrease of the density of 3d-electrons in the regions near Fe and near electronic properties was investigated in detail. It is demonstrated that
the surrounding Ti and Ni atoms (marked in red), while the space oc- the segregation of copper or iron to the GBs induces important changes
cupied by the regions having an increased density of electrons (marked in the band structure and in the electronic density in the GB's neigh-
as pink or blue) is relatively large. Based on this consideration it is borhood. A systematic DFT study of the electronic properties provides
possible to conclude that the origin of the different influence of the 3d an understanding of the bonding effects upon the introduction of fine
noble and transition metals segregating to the GB on the electronic features that should be considered when nano-grained material with
properties of nano-grained TiNiSn is in the degree of the delocalization dopants is manufactured. The major findings of this investigation are
of 3d-states, which is different for totally occupied states, like in Cu, and summarized as follows:
partly occupied states, like in Fe.
(1) Engineering of nano-grained materials, aimed to influence their TE
4. Conclusions properties, has to account the peculiarities that originate from the
electronic structure of traditionally used dopants that may control
The influence of 3d noble and transition metals segregating to the n- or p-type conductivity of the finally manufactured material.
grain boundaries in nano-grained half-Heusler TiNiSn compound on the (2) Keeping in mind a relatively small solubility of different doping

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Fig. 4. Cross-sections of the differential electron density distribution in the vicinity of the GBs in TiNiSn: (a) charge distribution in the GB plane with segregated Cu
atoms, (b) charge distribution between Cu and neighboring Ti and Ni atoms in the plane perpendicular to the GB, c) the same as (a) with segregated Fe atoms. The
scale is in electrons per Å3.

elements that change the type of conductivity of half-Heusler form instead a narrow region of non-equal to zero states in the DOS
compounds, the effect of their segregation to GBs for powder me- transferring the material into a semimetal.
tallurgy processed materials should be accounted.
(3) Interfacial states formation in nano-grained TiNiSn plays an im- These findings might be useful in the development of TE devices
portant role in determining the n-type conductivity of the material. that are aimed to operate at different temperature regimes. On one
These states are formed due to changes in the atomic bonding in the hand, nano-grains may significantly decrease the thermal conductivity
vicinity of the grain boundaries. The electronic properties upon of half-Heusler alloys. On the other hand the formation of interfacial
doping with different elements strongly depend on the fine features states in nano-grained narrow band gap TiNiSn influences the elec-
of the charge redistribution in the vicinity of the GB. tronic conductivity of material. Efforts to change the type of con-
(4) It is demonstrated that the totally filled 3d-shell of Cu, segregated to ductivity in such materials strongly depend on their electronic structure
the GB in TiNiSn, does not participate in the bonding. At the same and on tiny interplay between the electronic structure of the back-
time, these Cu atoms increase the band gap in nano-grained mate- ground and of the doping elements. The role of dopants may be dif-
rial (as compared with undoped one) and promote formation of the ferent in bulk and nano-grained materials.
covalent bonds due to hybridization of Cu s-electrons with d-elec- Increasing the grains size will obviously decrease the relative ratio
trons of Ti and Ni. This s-d hybridization stimulates the electron of the interfaces to volume atoms, affecting the role of dopants segre-
transport along the interfaces between the grains while in the plane gating to the GBs. Nevertheless this effect has to be considered by re-
perpendicular to the GB, the localization of the excess electron searchers dealing with the synthesis of doped nano-grained thermo-
density restores to high extent the bonds between Ti, Ni and Cu electric materials. Actually, small size of the grains was considered.
atoms. This effect reduces the charge transfer across the GB. Such nano-grained samples can be experimentally produced by con-
(5) Segregation of 3d transition metal (Fe) has an opposite effect - solidating of nano-sized powder particles using rapid spark plasma
partly occupied 3d-states of electrons in Fe mix significantly with 3d sintering, inhibiting grain growth. It should be mentioned that a similar
states of neighboring Ti and Ni atoms. This forms charge depletion behavior is expected also for larger grains, but taking into account that
zones close to Fe as being clearly seen in the differential electron the phonon scattering on GBs will be smaller, the expected decrease of
density map. The charge is transferred from these zones and forms a the lattice thermal conductivity for this case may become less pro-
spreading cloud occupying a significant space in the GB plane. nounced. This encourages new efforts in experimental research and in
These delocalized electrons spoil the semiconductor band gap and engineering of novel, beyond the state-of-the-art thermoelectric

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