Investigation of Perovskite Type Compounds for

Energy Applications

RESEARCH PROPOSAL FOR THE DEGREE OF

DOCTORATE OF PHILOSOPHY
IN PHYSICS

SUBMITTED BY

Pathak Bhargav Y.

SUPERVISOR

Prof. (Dr.) Utpal S. Joshi

Department of Physics Electronics and Space Science

Gujarat University,

Ahmedabad - 380009, India.

1. Introduction:

In this era of rapid-developing industries and technology, Energy crisis is giant obstacle
since the energy sources are limited. The production and the consumption on both the local
and the global scale, have some major issues like pollution, greenhouse effect, transportation
heat loss etc. The major source of Energy in any country’s total power consumption is
originates from either thermal sources or Nuclear reactor sources. In both ways, they come
with baggage of their respective issues like limited quantity of materials on earth and
radiation and their waste management is major concern. However, as in alternative energy
sources such as thermoelectric and solar energy are one of the vital solutions.

Thermoelectric technology is a promising approach to recover waste heat from different

resources and convert into electrical energy. Thermoelectric (TE) phenomenon is a
generation of small voltage between two dissimilar metals in the form of thermocouples. The
invention of high-efficient semiconductors materials resulted in a rapid development of TE
technologies over the last 60 years and the development of new materials is still rapidly
progressing [1]. The two primary thermoelectric effects are the Seebeck effect and the Peltier
effect. The Seebeck effect defines as temperature difference creates voltage, while the Peltier
effect describes as electrical voltage difference creates a heat flow. There are several
applications that Thermo-electric systems are contributing such as robotics in space [2],
Micro-power generators [3], and Heat sensors [4], wearable devices in medical applications
[5]. However, the conversion efficiency of TE materials is comparatively low. Therefore,
development of material to utilise waste heat is a potential energy source for the TE power
generation systems. For large scale implement of the TE systems, it is imperative to reduce
the cost-per-watt. This can be achieved by modification and optimization of the TE material
geometry, improving the manufacturing quality and achieving high seebeck coefficient (α),
defined as

Which means fraction change in temperature gradient produces voltage, hence

increasing figure of merit [6]. The conversion efficiency of a TE material depends on the
dimensionless figure of merit ZT, which is formulated by:
 Where, α is Seebeck coefficient, T is absolute temperature, ρ is electrical resistivity and κ
is the total thermal conductivity.
On other hand, solar energy is wildly functional in different regimes such as
agricultural, water desalination and in domestic applications to operate lights, pumps,
engines, fans, refrigerators and water heater. In short, solar energy conversion is widely used
to generate heat and produce electricity. However, Efficiency of solar cells depends on
temperature, insolation, and spectral characteristics of sunlight and so on. Presently,
efficiency of photovoltaic cells is about 12–19% at the most promising conditions [7].
In the last couple of decades, many research groups have shown promising results
aimed at perovskite type materials for TEP applications as wells as in the field of solar cells.
In some cases, hybrid approach of organic-inorganic results has shown quite good results. [8].
However, in both the cases improved efficiency and stability is still an issue which needed to
be addressed.

2. Literature review:

Many research groups have supported the perovskite based materials for potential
thermoelectric applications [9] and for the solar cells [10].
For the thermoelectric materials, the aim is to design materials with high Figure of merit
(ZT), low resistivity and high thermal conductivity. The research attention has been focused
on alloys based semiconductor materials for a long time until Terasaki et al. found the
noticeable Seebeck coefficient and typical thermoelectric properties in cobaltite oxides [11].
Cobaltites based TE materials have several advantages comparing with alloys-based TE
materials, for example, resistance to decomposition, easy fabrication, cost-effective,
sustainability at high temperature and so on.
One of the potential candidates for the TE materials is Ca3Co4O9. The thermoelectric
properties of Ca3Co4O9 are fairly consistent with a conductivity of around 104 S m−1, a Seebeck
coefficient of around 150 V K−1 and a thermal conductivity of around 2 W K−1 m−1. Using appropriate
dopants we can achieve significant increase in electrical conductivity and seebeck coefficient. Mostly
Bismuth is used for enhancement of electrical properties. In general, the increase in conductivity is
accredited to an increase in carrier mobility rather than carrier concentration, which is usually
anticipated in thermoelectric materials, since an increase in carrier concentration tends to lead to a
decrease in the Seebeck coefficient [12].
Another potential candidate for the TE applications is NaxCoO2. The variation in concentration of
sodium (Na) has reportedly better results as compared to the variation in Co3Co4O9. It shows the
transport properties are affected by the concentration of sodium ion vacancies. In another report
addition of Ag with light doping also affects the electrical conductivity [13].
However, recent developments have been perceived in n-type and p-type perovskite metal
oxides. In comparison, the p- type perovskite metal oxide such as LaCoO3 with dopant of alkaline
earth metals on La-site or Transition metals on Co-site have shown low figure of merits [14]. On other
hand n-type perovskite structure metals oxides materials have shown promising results in TE
properties such as strontium titanate (SrTiO3), calcium manganite (CaMnO3) have shown
good electrical conductivity and significantly high figure of merit. Other results have been
reported having lanthanides doped strontium titanate. A comparison of some lanthanide
dopants has revealed that dysprosium marks in the highest figure of merit among them [15].
Another promising work on Perovskite would focus on recently discovered organic-
inorganic solar cells, namely, the perovskite solar cells. The photoelectric power conversion
efficiency of the perovskite solar cells has increased from 3.8% to 22.1% in last decade.
Perovskite solar cells are understands to be the best potential candidate for the new
generation of solar cells to replace traditional silicon solar cells in the future. And it is
reportedly one of the top 10 breakthroughs in 2013. Perovskite materials have attracted
extensive attention due to its cubic lattice and octahedral layered structures opening wide
scopes for unique optical, thermal, and electromagnetic properties.

Figure 1 Typical perovskite structure

On recent advancement of couple of years, new generation hybrid perovskite are

widely proposed which have shown promising results in laser devices [16].
The vital requirements for solar cells are: It must possess excellent photoelectric
properties, lower binding energy, High optical absorption coefficient (~104 cm-1) is desirable.
Material should be highly dielectric and charge carriers have to be collected and transmitted
instantaneously. In addition, the transmission distance is up to 100 nm or more and even
more than 1 𝜇m is expected. These features are quite essential which leads to a high open-
circuit voltage ( oc) and a short-circuit current density (𝐽sc).
Throughout the exposure to sunlight, the perovskite layer firstly absorbs photons to
produce excitons (electron-hole pairs). Owing to the difference in the binding energy of
excitons produced in the perovskite materials, it can form free carriers to produce a current or
can recombine into excitons. The low carrier recombination and the higher carrier mobility,
leads to longer lifetime of the carriers reported in CH3NH3PbI3 (MAPbI3) and meso structured
hetero junction of CH3NH3PbI3/TiO2 films.
The challenges which needed to be addressed are improving efficiency while keeping
in mind the basic criteria’s. One way to is by replacing of toxic metal Pb by another metal
like Ba which is more abundant, less toxic for eco-friendly system another way is studying
Morphology of the cell structure and simplification of the cell structure may increase the efficiency of
the perovskite solar cells. [17].

3. Objectives and Methodology:

Our aim will be designing and synthesizing of the materials will be done by using
various thin film growth techniques, such as, chemical solution deposition, Pulse Laser
Deposition (PLD) and chemical bath deposition technique. Different substrate will be used
due to the respective applications. For hybrid perovskite solar cells, mainly chemical solution
deposition using Spin Coating will be employed. It gives an option for good homogeneity and
better stoichiometry of deposition. It also provides good control over crystallite size as well
as over thickness of film. In our case, we will be using oxides, nitrates and halides for the
material synthesis for both Thermo-Electric materials and Solar cells. We will be focusing on
respective characterizations. Mainly we’ll be focusing on structural, Electrical transport and
optical properties. The tentative characterizations which we will be studying are listed below.
X-Ray Diffraction (XRD) for structure analysis

 X-ray Diffraction (XRD) and Grazing incidence XRD

 Atomic Force Microscopy (AFM) for surface morphology and grain size
 Optical techniques like UV-vis, FTIR etc
 I-V measurements (under dark and illumination) for electrical transport behavior
 Dielectric and impedance spectroscopy
 Hall Effect and Magneto Resistance for some magnetic materials
 Raman spectroscopy

4. Expected Outcome:

Our vital goal is to synthesize good quality materials with some advancement based on

perovskite materials for energy applications. A comprehensive study on thermoelectric

materials and solar cells would help us to understand and develop the novel materials for the

progress in alternative energy sources for humanity and future generation.

5. Work Plan:

The plan of action and its execution with tentative time frame is as bellow

1. Literature survey and problem definition: 03 Months

2. Fabrication of material and devices: 10 Months
3. Characterization: 07 Months
4. Data analysis and plan of more work if needed: 10 Months
5. Writing Thesis and Publications etc.: 06 Months

Total time of completion of study and work is proposed to be 36 Months

6. References:
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pages105–114 (2008).
2. Bechtel R, Multi-mission radioisotope thermoelectric generator (MMRTG), National Aeronautics and
Space Administration; (2013).
3. Chou S, Yang W, Chua K, Li J, Zhang K. Development of micro power generators–a review. Appl Energy
88 1–16 (2011).
4. Zadshakouyan, Temperature Control and Energy harvesting by a thermoelectric system, International
Materials Physics Journal 1 2 14-19 (2013).
5. Siddique, A. R. M., Mahmud, S., and Heyst, B. V., A review of the state of the science on wearable
thermoelectric power generators (TEGs) and their existing challenges. Renewable and Sustainable Energy
Reviews, 73, 730–744 (2017).
6. Karthikeyan, B., Kesavaram, D., Ashok Kumar, S. and Srithar K., Exhaust Energy Recovery using
Thermoelectric Power Generation from a Thermally Insulated Diesel Engine, International Journal of
Green Energy, 10(10), 1056–1071 (2013).
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Energy Reviews 15 1777–1790 (2011).
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Perovskites Solar Cell Stability, Advanced Functional Materials, 1808843 (2019).
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Pourfayaz, Lingen Chen, Mohammad Arab Pour Yazdi, Ravinder Kumar, Thermoelectric cooler and
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Energy https://doi.org/10.1016/j.energy.2019.07.179
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Zhi Wang, Weigang Zhu, Junsheng Yu,* Michael R. Wasielewski, Mercouri G. Kanatzidis,* Tobin J.
Marks,* and Antonio Facchetti, Combustion Synthesized Zinc Oxide Electron-Transport Layers for
Efficient and Stable Perovskite Solar Cells, Adv. Funct. Mater. (2019).
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electrical transport properties of Ca3Co4O9 ceramics, Results in Physics, 12 321-326 (2019).
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doped c -axis oriented Ca3Co4O9 thin films by pulsed laser deposition, Journal of Applied Physics 108,
083709 (2010).
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