Synthesis of high density - FeSi2 : Structural and electrical

characterisation
by Abu Anand ( SB-1312004)
Guide : Prof. Arun M Umarji

Materials Research Centre

Indian Institute of Science (IISc), Bangalore

Contents
1 Introduction

1.1

Thermoelectric effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.2

Thermoelectric materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.2.1

Transition metal silicides as thermoelctric materials . . . . . . . . . . . . . . . .

2 Experimental techniques

2.1

Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.2

Hot pressing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.3

Heat treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3 Characterisation of samples

3.1

X-ray diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.2

Scanning electron microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.3

Electrical resistivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.3.1

Two probe method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.3.2

Four probe methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.4

Seebeck coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4 Conclusions

14

5 Acknowledgment

14

References

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Introduction

There has been a dramatic escalation in worlds demand for energy in the past few decades which
resulted in a lot of political and social unrests. Scavenging of waste heat through thermoelectric
generators is a sustainable way of tackling the situation. Home heating,automotive exhaust, and other
industrial processes all generate an enormous amount of unused waste heat that could be converted
to electricity by using thermoelectrics. Since thermoelectric generators are solid-state devices with
no moving parts and scalable, making them ideal for small, segmented as well as distributed power
generation.[1]

1.1

Thermoelectric effect

Thermoelectric effect generally deals with the inter-conversion of thermal energy and electrical energy.
The thermoelectric effect arises because the charge carriers in metals and semiconductors are free to
move like gas molecules while carrying charge and heat as well. When a material is subjected to a
temperature gradient, these charge carriers which are mobile will diffuse from hot end to cold end.
This migration will create a build-up of a net charge in the cold end in turn leading to the development
of an electrostatic potential (voltage). At some point, the electrostatic repulsion due to the build-up
of charge separation between the hot and cold end will get in equilibrium with the chemical potential
for diffusion. This is called the Seebeck effect. The voltage developed in the material will be directly
proportional to the temperature gradient applied.[2]
V = ST

(1)

Proportionality constant used here is the Seebeck coefficient (S) of the material, named after T J
Seebeck who first reported this phenomenon in 1821.
In the other hand, keeping a potential difference between two ends of a conducting material will
lead to generation of a thermal gradient. This phenomenon is called the Peltier effect
Q = I

(2)

is the Peltier coefficient of the material and Q is the heat flow through the material. Peltier and
Seebeck coefficients can be related as
= ST

(3)

Thermodynamically, these thermoelectric phenomenons are reversible. However, in practice, it is

affected by irreversible phenomenon like electrical resistivity, thermal conduction. The performance of
any thermoelectric device will be dependent on these transport properties. The coefficient of performance of a thermoelectric device is given by
COP =

[1, 3]

TH TC
1 + zT 1

TH
1 + zT TTH
C

(4)

where z is the figure of merit of the material times the operating temperature given as a function of
the transport properties
z=

S2
k

(5)

Figure 1.1: Change of transport properties and zT with carrier concentration

In this expression, S 2 is defined as the power factor of the material.
For the efficient working of a thermoelectric material, its zT value should be maximised.

1.2

Thermoelectric materials

Choosing material for the manufacturing of a thermoelectric device is at-most important thing. The
material chosen should be having maximum zT value as mentioned earlier but along with that for
practical purposes we should also consider the production cost, mechanical strength, chemical and
thermal stability over the operating temperature in which the device manufacture out of the material
is used.
Maximisation of zT is a task of mutually conflicting ideas. Looking into the expression of zT, it
could be found that for its maximisation, the Seebeck coefficient and the electrical conductivity should
be increased whereas the thermal conductivity should be decreased. Since these cannot be achieved
simultaneously, there should be an optimum value for the transport properties at which the zT is
maximum. The transport properties are a function of the charge carrier concentration. When we are
plotting carrier concentration and transport properties (Figure 1.1), the zT could be found maximum
when the concentration is in the range of 1019 1021 . This is the typical carrier concentration of
semiconductors. So semiconductors could be used to get efficient thermoelectric devices.
1.2.1

Transition metal silicides as thermoelctric materials

In the field of high temperature thermoelectric applications, transition metal Silicides are of high
importance due to their thermal and structural stability, high electrical conductivity at elevated temperatures. Also, the elements that are used for the synthesis are naturally abundant and non toxic;
hence the production cost will be low which increases the practical feasibility of the thermoelectric
devices.
Aim of this project is to investigate -FeSi2 , which is the semiconducting phase of Iron Silicide,
as a potential thermoelectric material and to improve its thermoelectric properties by doping. -FeSi2
is a TMS having large Seebeck coefficient, high electrical conductivity, high thermal stability and low
4

Figure 1.2: Fe-Si phase diagram[4]

production cost as well as non toxic in nature. This makes it a potential candidate for a thermoelectric
material for high temperature applications.
From the Fe Si binary phase diagram (Figure 1.2), - FeSi2 will get solidified from the peritectoid
decomposition of -FeSi2 and -FeSi, which are metallic phases. Since it is a peritectoid reaction, the
complete conversion of entire -FeSi into - FeSi2 will take lot of time for completion. This is because
of the low rate of diffusion in the solid state.
-FeSi2 crystallises in orthorhombic structure with 48 atoms per unit cell. It exists in Cmca space
group and have lattice parameters a = 9.863 , b = 7.884 and c = 7.79 .[5] Theoretical calculations
performed suggested that there exists an indirect between Y (valence band) and a non-symmetry point
between and Z (conduction band) with a value of 0.67 eV.[6, 7]
Small polaron model has been used to study the conduction mechanism in - FeSi2 and was found
that there is semiconductor to metal transition at 1259 K.[8] Thermal conductivity as discussed earlier
will have two main contributions, one due to electrons and the other due to the phonon scattering.
In - FeSi2 the phonon contribution is found to be predominant. So in the optimisation of zT, the
main challenge would be the reduction of this lattice contribution of thermal conductivity. Doping in
thermoelectric systems can be used as a tool to optimise the carrier concentration. It can also act as
scattering centres for phonons to reduce lattice thermal conductivity.

Figure 1.3: Crystal structure -FeSi2

Figure 1.4: Band diagram of - FeSi2

Experimental techniques

In this work - FeSi2 sample with high bulk density is prepared. Doping with phosphorous is carried
out in a sealed tube reaction. Phase characterisation X-Ray diffraction and SEM is carried out.
Electrical characterisation by 4 probe electrical resistivity and Seebeck measurement is done.

2.1

Synthesis

Initially, stoichiometric amounts of iron (Sigma Aldrich - 99.98%) and silicon (Alfa Aesar - 99.9999%)
were arc melted in Argon atmosphere. To remove the oxygen content in the chamber, Titanium gutter
was melted before doing the melting Iron and Silicon.

2.2

Hot pressing

Hot pressing is a non equilibrium/ rapid solidification process which is used to make densified samples
out of the arc melted ingot. Since the transport properties are significantly dependent on the density of
the material it is important to obtain dense samples. Ingot synthesised from arc melting was crushed
using a mortar and pestle to get powder. These powdered samples were taken in a graphite die
where the sample was sandwiched between graphite sheets to make the pressure applied uniform. This
graphite die was placed in the middle of the heating coil of the HP apparatus. The heating is happening
in the apparatus due to the induction of eddy currents when the current is passed. Atmosphere inside
the apparatus was maintained inert using Argon in order to avoid oxidation of graphite die. Uni-axially
a pressure of 35 MPa was applied using a hydraulic press at a slow rate to avoid sample breakage for
7 minutes.
Density measurement
Density of the sample pellet synthesised using hot pressing was measured using Archimedes principle.
Here, the weight of sample was measured in air as well as in the liquid. Sample density is calculated
using the Archimedes equation.
Density =

Ws
L
Ws WL

(6)

Density of the sample was found to be 4.60 g/cc whereas the theoretical density is 4.80 g/cc.

2.3

Heat treatment

Hot pressed pellets, since the arc melted FeSi2 will be containing and phase, was heat treated.
Heat treatment was done in a vacuum sealed quartz tube at 800o C for 12 hrs. Phosphorous doping
was also tried to study the effect of dopants in the enhancement of thermoelectric properties. This
was done by heat treating the hot pressed samples in a quartz tube containing 20mg of phosphorous
(Merck - 99%).

Characterisation of samples

To confirm the presence of expected phases in the synthesised samples powder X-ray diffraction and
Scanning electron microscopy was done.

Figure 3.1: XRD patterns (Bottom to top) a) Arc melted b) Hot pressed c) Heat treated 800o C/12
hrs

Figure 3.2: BSE image and EDAX analysis of heat treated sample

3.1

X-ray diffraction

XRD spectrum was taken using Panalytical Xpert Pro (Cu-K source) for the arc melted, hot pressed
and heat treated samples and was compared with the literature spectra for the phase confirmation.
Arc melted and hot pressed samples where showing and phase as expected from the binary
phase diagram of Iron and Silicon since these processes where happening above the peritectoid point.
XRD patterns (Figure 3.1) of heat treated sample was showing phase with slight presence of phase
since the peritectoid reaction is solid state diffusion process which will be happening in very slow rate.

3.2

Scanning electron microscopy

The SEM (JEOL JXA-8530F Electron Probe Micro analyzer) images and EDAX analysis of the heat
treated sample is shown in Figure 3.2. The existance of -FeSi in - FeSi2 matrix is clealy seen. This
is further clarified elemental analysis by EDAX for the grey and dark region.

3.3

Electrical resistivity

Resistivity measurement techniques

According to Ohms law, the current flowing through a substance will be directly proportional to the
potential difference applied across it.
V = IR

(7)

The constant of proportionality used in this statement is the resistance of that material which
depends on the microscopic as well as the geometric properties of it. So even for the same composition
sample the resistance will be different according to the dimensions of the sample. The dependence of
sample geometry in the resistance is as follows
R=

l
A

(8)

where is the resistivity of the material. Inverse of resistivity is termed as the conductivity (). In
calculating the zT of a thermoelectric material it is very important to have accurate measurements of
the electrical conductivity. There are various methods used for the conductivity measurement which
can be broadly classified into two.
3.3.1

Two probe method

In this method a current is passed through the sample and the potential drop across the sample will
be measured using a voltmeter. This method can be adopted only if the sample resistance is high.
It is because the resistance that we are measuring includes the resistance of the contacts made by
the probes also. So, if the sample is having low resistance, then the contact resistance will mask the
resistance of the sample.
3.3.2

Four probe methods

3.3.2.a Linear four probe

This method was first reported by L. B Valdes in 1954. In this method, the probes will be kept collinear
as the name suggests. The outer probes are to pass current and the inner probes are used to measure
the voltage as shown in the figure. The calculation of resistivity from the readings of this method is
done by the following equation

[9]

V
2s
I

(9)

The equation is derived using the method of images in electrostatics assuming the sample is having
semi-infinite volume i.e. of infinite area but the thickness is very small. So in reality there should be
some correction factors introduced to rectify the errors caused by the geometry as well as the thickness
of the sample. This correction factors were calculated by F M Smit in 1958.[10]
A C programme code was written for generating the correction factors in linear four probe when
the sample dimensions are provided (Appendix 1). In the code correction factors given in the Smits
paper was taken as data points to generate Lagrangian interpolating functions[11] and the geometrical
dimensions given by the user will be evaluated using these Lagrangian functions to get the correction
factors.

3.3.2.b Van der Pauw method

Van der Pauw method is a four probe resistivity measurement method which can be used to obtain
the resistance values of arbitrary shaped samples. Experimental setup is as shown in the figure.
Van der Pauw method was used to calculate the sample resistivity with temperature, in the home
built apparatus. A resistive furnace was used to reach higher temperature values. Four electrical
contacts made where of pressure contact type using platinum wires and the resistivity was calculated
using the Van der Pauw equation. -FeSi2 shows the same trend of general p-type semiconductors.
Band gap of the sample was calculated by linearly fitting the intrinsic region of the curve.[12]

3.4

Seebeck coefficient

Seebeck coefficient metrology techniques can be broadly divided into two types
Integral method
Differential method
Steady state method
Quasi steady state method
Transient method
Integral method can be used when the temperature gradient is very high. Here, we plot thermo emf
generated as a function of temperature and the Seebeck coefficient at any particular temperature is
given by the slope of the curve at that particular point.
Differential methods can be used when the temperature gradient is small so that the coefficient
can be determined directly. In this type of measurements, we can wait for the achievement of a steady
state (ie the rate of change of the heat flux through the sample is zero). This is called the steady state
differential method. This method will be more accurate but will take lot of time for the measurement
to get completed. Since the gradient should be holded for a long time span it cannot be implemented
where the sample is not thermally very stable.

[13]

In quasi steady state differential method, we will not wait for the constant heat flux condition. This
method will be less accurate but is more practical in scenarios like sample with less thermal stability.
Transient method is the one in which the direction of thermal gradient is cycled as a function of time
inorder to make Seebeck measurements. This is to get rid of some offset thermal emfs generated in
some materials due to the unidirectional heat flow[14, 15] .
Steady state method was used to measure the Seebeck coefficient in room temperature. Undoped
sample was showing a positive Seebeck coefficient whereas the doped sample was giving negative. This
suggests the undoped sample is p-type (positive charge carriers) and the phosphorous doped ones are
n-type (negative charge carriers).
Sundoped = +180 V /K
SP doped = 198 V /K
Power factor = S 2 was found to be for each samples
undoped = 1.19 W/mK 2
P doped = 1.44 W/mK 2

10

Figure 3.3: Two probe method

Figure 3.4: Linear four probe schematic[9]

Figure 3.5: Resistivity vs Temperature Undoped beta-FeSi2

11

Figure 3.6: log resistivity vs 1000/T Band gap determination

Figure 3.7: Van der Pauw method : Schematic experimental setup[16]

12

Figure 3.8: Van der Pauw method : Sample orientation and connections

13

Conclusions

High density -FeSi2 was prepared by arc melting followed by hot pressing. Inclusion of -FeSi phase
in matric of -FeSi2 is revealed by SEM and XRD results.
A C programme to obtain bulk resistivity from surface resistance obtained from linear four probe
electrical resistance measurement is written and implemented.
The power factor S 2 for -FeSi2 (undoped) and phosphorous doped samples are shown to be
undoped = 1.19 W/mK 2 and P doped = 1.44 W/mK 2 .

Acknowledgment

I would like to express my sincere gratitude to Prof. Arun M Umarji, Materials research centre, IISc
Bangalore for his invaluable guidance in my summer term 2015. I thank Rajasekar P and other lab
mates in AMU lab for their guidance and affection they have shown during my stay. I would also like
to thank Kishore Vaigyanik Protsahan Yojana (KVPY), Department of Science and technology, Govt.
of India for providing me an oppurtunity to do this summer project.

14

References
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[10] FM Smits. Measurement of sheet resistivities with the four-point probe. Bell System Technical
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[11] William H Press. Numerical recipes 3rd edition: The art of scientific computing. Cambridge
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[14] Joshua Martin. Apparatus for the high temperature measurement of the seebeck coefficient in
thermoelectric materials. Review of Scientific Instruments, 83(6):065101, 2012.
[15] V Ponnambalam, S Lindsey, NS Hickman, and Terry M Tritt. Sample probe to measure resistivity and thermopower in the temperature range of 3001000k. Review of scientific instruments,
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[16] T Das Gupta. PhD Thesis. IISc, Bangalore, 2007.

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