REPORT TO THE DOCTORAL COMMITTEE FOR RESEARCH

METHODOLOGY EXAMINATION
by
Tathagata Sarkar
IPHD15025
School of Physics, IISER-TVM

GERMANIUM TELLURIDE (GeTe)

I have been working on a thermoelectric material called GeTe. Thermoelectric

materials have the ability to convert waste heat to useful electrical energy. The
performance of a thermoelectric material is measured by a quantity called the
Thermoelectric Figure of Merit (Z).

The symbols have their usual meaning.

Higher the Z the better. Now, GeTe has been found to be a decent TE material with
high Z at high temperatures. The inspiration behind choosing this material (as i had
pointed out in my last DC meeting) is from a review paper by Perumal, Roychaudhuri
and Biswas [1]. But GeTe has shortcomings as a TE material due to its large hole
density which increases the electrical and thermal conductivities and Z remains low.
The ways to get around the problem has been discussed in [1]. One way is to reduce
the carrier concentration in native GeTe by doping with various elements (like Mn
and Bi) leading to the enhancement of the Seebeck coefficient accompanied by
considerable reduction in the electronic thermal conductivity in compositions of the
form Ge1-xMxTe. The other way is the to alloy GeTe with other compounds (like
AgInTe2, Bi2Te3, Bi2Se0.2Te2.8) yielding compositions of the form (GeTe)1-x(ABC)x. In
this case, apart from reducing carrier concentration, the alloyed compounds modulate
the micro/nano-structure of the materials, like the formation of twin boundaries,
inversion boundaries, herringbone structures, anti-phase domains, etc. These are very
efficient scatterers of phonons and they bring down the lattice thermal conductivity of
the materials, greatly enhancing the Z. [1] has provided an extensive survey of a wide
range of such materials, especially TAGS, Ge-Pb-Te and Ge-Sb-Te as provided
below.
Our aim to synthesize such compositions by allowing Cr with GeTe (not reported
before). We aim to arrive at both Ge1-xCrxTe and (GeTe)1-x(CrTe)x or anything in
between and then go about measuring the TE properties in hope of achieving high Z
values.

There is another part of the GeTe story which has to do with GeTe nanomaterials like
nanowires and thin films. This plan is inspired from the theoretical paper by Xu, Gan
and Zhang [2]. They have shown that in topological insulator materials, Z becomes a
strong function of dimensions of the material. The size parameter can then be tuned
to drastically enhance Z.
These plots from [2], strongly suggest that with TIs we can dramatically enhance Z
by obtaining thin films of the material.

Work so far

i) I have been able to synthesize GeTe in pure phase (confirmed from XRD and XPS
data) as I had mentioned in my last DC report.

ii) I am in the process of synthesizing GeTe in larger amounts for all the things I have
mentioned above like soping with Cr, forming thin films and growing nanowires.

iii) I am also trying to optimize and calibrtate the sputtering instrument to obtain
uniform and controllable thin films.

iv) We are also planning to grow single crystals of GeTe as direction dependent
studies haven’t yet been conducted on this system.

FULL HEUSLER COMPOUNDS Fe2YZ

As mentioned above, it is the enhancement of Z that we are after. One of the

approaches, as said above, is to reduce the thermal conductivity of the material by
using specific crystal structures or by nanostructuring. But this has only led to Z
being enhanced from 1-2.4. So the next frontier is to enhance the power factor (PF).
Mahan and Sofo in [3] have pointed out the ideal shape of the Transport
Distribution Function that can maximize the Z. The criteria, according to them, are
that the distribution of the carrier energies should be as narrow as possible and the
mobility of the carrier should be high along the direction of the applied field. But the
two conditions require diametrically opposite band structures. The narrow
distribution of carrier energies require flat bands while the high velocity of carriers
demand highly dispersive bands. Surprisingly enough, Bile et. al. in [4], have found a
way to have both these characteristics within the same band of some semiconductors,
utilizing the highly directional character of some orbitals. And according to them, this
can be achieved in bulk phases of Fe2YZ full Heusler compounds, without requiring
any nanostructuring [5].

In [4], calculations have been done for some six such Fe2YZ full Heusler compounds.
In the first compound, Fe2VAl, the lowest conduction band is of dominant V eg
character and is highly dispersive. But we notice another conduction band of Fe eg
character which is extremely flat in one direction and dispersive in the others. This
band fulfils the criteria given by Mahan and Sofo [3]. But the band has to be brought
down to the bottom of the conduction band. This can be achieved by substitutions at
the Y and the Z sites. The paper considers five such compositions and make the
observation that moving from 3d to 5d transition metal elements at the Y site pushes
the Y eg level up, as can be clearly seen in the band diagrams above. Also putting
higher mass elements at Y and Z sites reduces the distance between the Fe2 layers,
thus reducing the interlayer Fe-Fe interaction. As expected, the authors demonstrate
conclusively that there is a remarkable change in the PFs of these materials, from
3 mW/mK2 in Fe2VAl to about 16 mW/mK2 in Fe2NbGa and Fe2TaIn. In the second
set of compounds, the Y eg is pushed even higher and are predicted to show even
higher values of PFs.
[4] also provides a plausible explanation for the enhanced transport properties in one
of the compounds, Fe2TiSn, which can be attributed to the tubular shape of the Fermi
surface coming from the flat band along the gamma-X direction, as compared to the
small disconnected pockets of electrons in Fe2VAl. As indicated in the crystal
structure above, the Fe2YZ structures have alternating Fe2 planes in all three
directions. Now the Fe-Fe interactions are confined to the Fe2 planes but do not
interact with the iron atoms of the next plane, like in the {001}-Fe2 planes there is
strong overlap of the Fe d x2-y2 orbitals, but do not interact along z and this gives rise
to the tube along z in the Brillouin zone. This anisotropy in orbital interactions gives
rise to electronic bands that are highly dispersive in two directions (mt ~ 0.3 me for
Fe2TiSn) and flat in the third one (ml ~ 26me in Fe2TiSn). This large effective mass
ratio (ml/mt ~ 87 for Fe2TiSn) is responsible for the tubular shape of the Fermi
surface. This highlights the fact that there is a kind of a two dimensional transport
going on here. So they have achieved all the properties demanded by Mahan and Sofo
in [4] as well as a low dimensional transport like in quantum wells as shown by Hicks
and Dresselhaus in [3], all in a bulk cubic compound, to enhance the thermoelectric
figure of merit. Further study and discussion is required on my part to better
understand some of the portions of this paper which are still a bit cloudy to me.

In [4], they have additionally studied the thermodynamic stability of these

compounds as given below. Green on the diagram suggests a stable composition and
the circles indicate the ones that have already been synthesized. The existence of such
a wide variety of isostructural stable compounds with such attractive PFs has another
advantage. As has been pointed out in [4] and [6], combining these compounds in
solid-solution can additionally reduce the lattice thermal conductivity of the system
thus further improving upon the Z.

So, [4] has inspired me to take up the Fe2YZ full Heusler compounds as a potential
candidate for high zT materials.
Work so far
i) Completed the literature survey of these compounds [4], [6], [7]. Some parts of [4]
are still unclear to me and requires further reflection on my part. Another paper has
the synthesis of some 200 such Heusler alloys.

ii) Have gone through papers on synthesis of Fe2YZ family of Heuslers and have
found a handful of references with ternary phase diagrams of these compounds [6],
[7]. The dominant synthetic method seems to be through the solid-state route
consisting of arc-melting followed by vacuum annealing.

iii) From [4], I have shortlisted a few compounds that are predicted to be stable:
Fe2TiSi, Fe2TiSn, Fe2VGa, Fe2NbAl and Fe2TaAl and I am planning to synthesize
them.

iv) Once these compounds are formed (preferably single crystals of them), we will go
on with characterization and TE measurements.

REFERENCES

[1] Perumal, Roychaudhuri, Biswas, J. Mater. Chem. C, 2016, 4, 7520

[2] Xu, Gan, Zhang, Phys. Rev. Lett. 112, 226801(2014)

[3] Mahan, Sofo, Proc. Nat. Acad. Sci. USA, Vol. 93, pp. 7436-7439, July 1996

[4] Bilc, Hautier, Waroquiers, Rignanese, Ghosez, Phy. Rev. Lett. 114, 136601 (2015)

[5] Hicks, Dresselhaus, Phy. Rev. B, Volume 47, Number 19, 15 May 1993
[6] Kocevski, Wolverton, Chem. Mater. 2017, 29, 9386-9398

[7] Yin, Hasier, Nash, J. Mater. Science 2016, 51:50-70