CHAPTER – II

MATERIALS AND METHODS

 CHAPTER – II
MATERIALS AND METHODS

2.1 Introduction
This chapter describes the procedure followed during device fabrication and a brief about the
experimental setup employed for various characterization techniques. All the intermediary
steps involved in the fabrication procedure are supervised suspiciously as these directly affect
the performance of the device in context to their physical and chemical properties. Device
geometry essentially involves thin layer of undertaken semiconducting material on to a
substrate ranging from few angstroms to hundreds of micrometers and then various
techniques for growing thin films can be employed as per the requirement. The thin film
satisfies the criterion for simplicity, cost effectiveness, large uniform area and controlled
deposition, yield well-defined structural and opto-electrical properties. The thin film
preparation procedure is very much sensitive to the ambient situation and hence should be
accurately controlled. This chapter focuses at two main streams:

(i) Device fabrication procedure

(ii) Characterization methods and their set-up

2.2 Device fabrication procedure

2.2.1 Working of dye sensitized solar cells (DSSCs)
The working mechanism of (DSSC) depends on the p-n connection as in the conventional
solar cells but on the photogeneration of an electron by a dye, as in photosynthesis. At the
centre of a DSSC is a wide-band mesoporous semiconductor oxide, such as TiO2 is present
which makes the effective conduction to allow the electron flow. The excitation of dye
sensitizer injects the electron to the conduction band of TiO2 which helps in the oxidation of
the dye. With the injection of electron the ground state of the sensitizer is maintained
through the donation of electrons which are regenerated with the reduction of the electrolyte
oxidant on counter electrode [1-2]. The generated voltage is determined with the Fermi level
of the material and the redox potential of the present electrolyte under the photo excitation

64
[3]. DSSCs can be produced at reasonably low cost while yielding relatively recent
efficiencies. The working of DSSCs is shown in Figure 2.1.

Figure 2.1: Working of dye sensitized solar cell

In a DSSC, the dye can be replaced by a quantum dot, thus one then speaks of a quantum dot
sensitized solar cell (QDSSC). The liquid electrolyte can be replaced with a polymer
electrolyte then it called as quasi-solid-state dye sensitized solar cell. The solid conductor
plays the function of regenerating dye through transferring the hole from the dye to the
cathode (and thus an electron from the cathode to the dye). In ss-QDSSC or extremely thin
absorber (ETA), there is both a solid conductor and an inorganic sensitizer in the form of a
quantum dot or an extremely thin layer. In a p-type DSSCs, the illumination of dyes results in
the insertion of a hole into the valence band of the material (generally NiO).

The anode present in the device is an electrode through which electric current flows into the
device. In a solar cell, the anode is then the electrode that collects photoelectrons. It is then
the negative electrode, against a widespread misconception that anode polarity is always
positive (which is true for passive devices). It is at the n-side of the p-n junction, or more
generally at the side of the electron acceptor. The cathode is then the positive terminal that
collects holes. It is also called the counter-electrode for n-type sensitized solar cells. In the
latter, the active semiconductor in contact to the anode is often called the photoanode for n-
65
type DSSCs. For p-type DSSCs, the photocathode is then the semiconductor that collects
holes injected from a sensitizer (and is thus in contact with the proper cathode).

2.2.2 Components of DSSCs

The DSSCs can be considered to be electrochemical devices consisting of following
components (i) Transparent substrate (ii) Photo-anode (iii) Dye as sensitizer (iv) Redox
electrolyte and (v) Counter electrode.

Consecutive steps involved in device fabrication have been discussed below:

(a) Substrate selection and preparation
(b) Film deposition on substrate
(c) Dye impregnation on electrode
(d) Preparation of counter electrode
(e) Electrolytes

2.2.2.1 Substrate selection and preparation

2.2.2.1.1 Cutting of the substrate

Fluorine doped Tin Oxide (FTO) is an important inorganic material used in fabrication of dye
sensitized solar cells (DSSC). It is highly transparent in the visible range, having effective
conduction and efficient substrate obedience [4-5] which make it useful for technological
applications. Commercially available FTO coated glass exhibiting resistance of~7-8 Ω/cm2 of
2 mm thickness, are useful for fabrication of dye sensitized solar cells. The substrate thus was
cut into pieces of approximately 20 × 20 mm using glass cutter (to prevent short circuits
when contacting the top electrodes, some part of the FTO was removed by etching). Part of
the FTO anode layer was etched away by covering the other portion with adhesive tape. Then
the tape was removed and the etched substrates were cleaned with distilled water.

2.2.2.1.2 Cleaning of the substrate

The cleaning of glass substrate is essential before making an effective solar cell device.
Transparent substrate i.e. FTO coated conducting glass of adequate size were subjected to
clean with cedepol neutral soap solution, then sonicated for 15 minutes, rinsed with distilled
water several times. FTO coated conducting glass cleaned with reagent grade acetone were
then sonicated in acetone for 15 minutes and then boiled in propan-2-ol solvent and finally
dried in an oven at 80 oC. The substrate pieces cut in the size 20x20 mm were stored in
66
cleaned glass containers. Maximum precautions were taken to maintain their surface clean.

2.2.2.1.3 Masking of the substrate

The substrate was masked in order to deposit the thin film of composite material under
consideration over the substrate. A thin transparent plastic adhesive tape was applied as a
spacer on FTO plate to identify the area and thickness of TiO2 layer. Transparent tape was
used to mask the substrate in such a way that a small strip of etched portion was masked. This
also solves the purpose of exposing the bottom counter electrode for contact purpose during
characterization of device.

2.2.2.2 Film deposition on substrate

Doctor blade or tape casting is suitable method (as shown in Figure 2.2) applied for making
fine films on huge surfaces. This technique was invented in 1940’s and first applied for
making capacitor and fine sheet of piezoelectric substances [6]. One patent, issued in 1952,
focuses on the use of aqueous and non-aqueous slurries applied to moving plaster batts by a
doctor blading device [7].

Figure 2.2: Doctor blade technique used for thin film formation.

In the doctor blade technique complete homogenous slurry was prepared with binders and
dispersants which were added on a FTO. Then a stable flow was maintained with blade and
the substrate. The homogenous mixer was spread on the FTO to form a thin sheet. The sheet
was dried. The doctor blade could maintain with a speed of several meters/minute. This
technique is suitable to cover materials of broad variety of wet films ranging from 20 to
several microns. This kind of doctor blade is also used in combination with a reservoir. The
effect of the reservoir geometry on the flow of the sol is described by Gaskell [8]. In this
67
technique either the layer is moved or the substrate is moved continuously. The principle is
shown in Figure 2.2. The quality of TiO2 film can be controlled with the help of the
adjustment of blade on the substrate, which is illustrated in Figure 2.3.

Figure 2.3: Frame used for film thickness control.

Wet layer thickness controls the gap between the frame and the blade [9]. These blades
provide very precise thickness control of the final layers. Doctor blade coating techniques are
also used for coating plastic foils with coating liquids [10]. In this case, the blade is
positioned across a roll and the web is moved underneath the blade, as one can see from
Figure 2.4.

Figure 2.4: Doctor blade coating technique for film formation.

The gap between the blades can be adjusted by precision holders in the range of +/- 10 µm.
The tank for the coating sol reservoir can be filled by continuous pumping, in order to avoid
bubbles in the reservoir. The fine layer of oxide was made on the FTO plate using the doctor
plate process by applying the solvents such as glacial acetic acid. In this technique few mg of
the compound was mixed in an appropriate solvent. The well mixed compound was added at
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the centre of the FTO substrate and doctor blade technique was for thin film formation and
then dried. The configuration of the device is shown in Figure 2.5. The DSSC is made up of
working electrode and counter electrode having effective electrolyte. The schematic view of
the DSSCs structure developed in this study is shown in Figures 2.6 and 2.7 and the details of
device fabrication processes are described below:

Figure 2.5: Stepwise representation of device fabrication.

Figure 2.6: Schematic view of developed Dye sensitized solar cell.

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2.2.2.2.1 Preparation of TiO2 paste
The TiO2 nanoparticles paste was prepared by mixing 500 mg of TiO2 (P25 Degussa) in 1mL
glacial acetic acid with a pestle and motor. Then further 0.25 ml increments of acid solution
were added with the pipette while grinding with a pestle to get a uniform and lump free paste.
The titanium dioxide paste in a small vial was sonicated for 30 minutes.

2.2.2.2.2 Depositing the TiO2 layer on the glass plate

A tape was applied at all four sides of FTO plate to define the area of TiO2 layer. The layer
was applied with the doctor blade technique. The thickness of the film was adjusted to 15
µm. The applied nano TiO2 film was dried at 350°C for 2 hours in air to pick up the better
electronic contact not only between the particles and support but also among the particles
[11]. Sintering was also needed to burn out organic binders and surfactants. This finally gave
a nano-structure TiO2 electrode.
2.2.2.3 Dye impregnation on the electrode
The nano-structured TiO2 electrode was immersed in dye solution for a longer time to adhere
the dye molecule with TiO2. During the diffusion procedure there was possibility of water
vapor inside the pores of the electrode. Hence it was heated under the oven at 70oC for 1 hour
to remove the water contents present in the materials of the electrode.
2.2.2.4 Preparation of Counter electrode
The dye absorbed on the nano-structured TiO2 film may be said as dye-sensitized TiO2 film
working electrode. To make a counter electrode, a thin film of carbon was developed on FTO
plate. Counter electrode is made by developing a thin film of carbon over FTO glass
substrate. Carbon black electrode was fabricated by an easy way with moving the conductive
side of (ITO) glass above the flame of candle Figure 2.8 show the fabrication of carbon
counter electrode. After ITO glass gets black. It was left for 5 mints until it was cooled then a
few drops of ethanol were placed to diffuse across the carbon film and dried by heat gun.

Figure 2.8: Carbon coating with carbon counter candle fumes electrode.
70
 .

Figure 2.7: Stepwise representation of Dye Sensitized Solar Cell (DSSC) device fabrication.

71
2.2.2.5 Liquid electrolyte
Electrolyte solutions were prepared as follows. The electrolytes were prepared by mixing
iodine (I2) (0.01M) with potassium iodide (KI) (0.1M) or tetramethylquaternaryammonium
iodide [(CH3)4NI] (0.1M) or tetraethylquaternaryammonium iodide [(CH3 CH2)4NI] (0.1M)
or tetrapropylquaternaryammonium iodide [(CH3CH2CH2)4NI] (0.1M) in acetonitrile solvent.
Four electrolytes thus were prepared and one of the electrolyte solution was injected into the
inter space between the photo-electrode and the counter electrode.

2.2.3 Dye Sensitized Solar Cell Terminologies

The fill factor, short circuit current, open circuit voltage and solar efficiency are essentially
required for the photovoltaic characterization of fabricated DSSC [12]. Systematic I-V
analysis of DSSC is mentioned in Figure 2.9.
2.2.3.1 Short-circuit current (Jsc)
It is the photogenerated current in absence of the applied field or voltage. It is also defined as
the current produced in the external circuit when no external load or voltage available.

2.2.3.2 Open-circuit voltage (Voc)

Voltage developed between the different terminals of the DSSC device in absence of the
external voltage or load is called as open circuit voltage. It depends on the band gap of the
semiconductor and charge carrier recombination of DSSC.
kT nο
For DSSC the Voc is given by: Voc = ln
q noket[I3- ]

Figure 2.9: J-V analysis of fabricated DSSC. The marked area explains the maximum power
developed from the device.

72
where n is the quantum yield of photo generated electron for the given incident photo flux
(ɸo); no represents the electron density on the conduction band of TiO2 in the dark, while ket
reflects the recombination rate for the given triiodide concentration [I3 - ] [13].
The first two terms define the quasi-fermi level of TiO2 and Eredox is the Nernst potential of
the redox mediator.

Figure 2.10: I-V response (red line) in light and I-V response in dark (Black line).

2.2.3.3 Fill Factor(FF)

Fill factor is the measurement of the maximum power output obtained with the DSSC. It
represents the squareness of J-V curve. It is explained as the ratio to the maximum power of
the product of Voc and Jsc of DSSC.
Jmax.Vmax Pmax
FF = =
Jsc.Voc Jsc.Voc
where, Vm and Im are the voltage and current of DSSC at maximum power point.
2.2.3.4 Solar cell efficiency (ɳ)
Solor cell efficiency is the essential parameter of DSSC that indicates the efficient working of
the cell operation. It is explained as the power output to the incident light applied, and may be
shown as
Jsc.Voc .FF
= X100
Pin
where Jsc is the short circuit current in A/cm2, Voc is the open circuit voltage in V, FF is the
fill factor, and Pin is the incident solar radiation in Wm-2.

73
The most important parameter for the efficiency of solar cell depends on J sc, Voc, and FF. The
Jsc of DSSC also depends on the light intensity, absorption rate, exciton formation and
dissociation rate, the carrier transport in the active layer etc. The absorption of light rate
depends on the thickness of active layer and the band gap of the active materials. The exciton
dissociation rate mainly depends on the interfacial area between dye and TiO 2 and
dissociation rate is quite efficient. The charge carrier transport in the active layer is
maintained with the dye-TiO2 interpenetrating network and the morphology of the active film
which plays an essential role. The Voc of DSSC is imperfect due to the morphology of active
layer, electrodes, and film quality, etc [14-16]. Generally, the difference between the HOMO
of the dye molecule and the LUMO of the TiO2 determines the Voc of the DSSC. The third
parameter which explains the efficiency is the Fill Factor. Compared to Voc and Jsc, the FF is
much more sensitive. In general, it depends on the mobility-lifetime product of charges in the
active material, the thickness of the layer, as well as the morphology of the layer. Moreover, a
large resistance would also lower the FF in DSSC.

Figure 2.11: Structure of DSSC.

2.2.3.5 J-V analysis in absence of light

The J-V analysis of DSSC in absence of light is the current developed with the variation of
the electric field (voltage) in forward as well as in reverse direction. For J-V measurements,
74
Keithley Source meter, Model: 2450 (see Figure 2.9.) with built in power supply is used. For
J-V measurements in dark, the device is mounted at the appropriate slot given in sample
holder.

Figure 2.12: Circuit diagram of dye sensitized solar cell for J-V graph.

Figure 2.13: J-V Characterization setup in dark using Keithley Source meter.

This measurement is carried out by applying sweep voltage across the device, and the
corresponding current is measured. Simultaneously, the device temperature is varied by
means of insulated heater coil. The temperature is measured and controlled by the digital
temperature controller.

75
2.2.3.6 J-V Characteristics under illumination
To study the opto-electronic properties of device, J-V characteristics are also studied under
illumination. The same experimental set-up, as employed in dark characterization is used to
measure the J-V properties under photoexcitation. A 100 W tungsten lamp is used to
illuminate the device. The Short Circuit Current (Jsc), Open Circuit Voltage (Voc), Fill Factor
(FF) Power Conversion Efficiency (η) photovoltaic parameters of the device was evaluated
by these characteristics.

Figure 2.14: J-V Characterization on illumination setup using Keithley Source meter.

2.3 Characterization methods and their set-up

2.3.1 UV-Visible spectroscopy
UV-Vis absorption spectroscopy provides the information regarding the absorption of an
electron between the electronic states that are concerned with molecular orbitals of the
system. In general, absorption involves π-orbitals and lone pair of electrons. Ultraviolet-
visible spectroscopy proves to very useful technique for studying the conjugated systems
which have proper absorption. These radiations are highly energetic which are sufficient to
lift the loosely bound electron from outermost shell to high energy state. This technique is
most commonly applicable to molecules, ions or complex in solution. The amount of
analyzed present in the solution can be quantitatively measured by measuring the absorbance
at specific wavelength. The range of UV-Vis radiation varies from 190-1100 nm, extending
to infrared region. This technique is also very helpful to characterize the absorbance,
transmission and reflection of a number of commonly used materials like as dyes, pigments,
coatings etc. In our assignment we used 2450 model UV-Vis spectrophotometer (Shimazdu)
for absorption measurements (Figure 2.15).
76
 Figure 2.15: UV-Vis spectrophotometer

2.3.1.1 Instrumentation
Generally, UV-Vis spectrophotometer consists of three basic component (i) scanning
spectrophotometer having a monochromator and sample holder (ii) scanning
spectrophotometer with dual light beam source and a sample cell (iii) non-scanning
spectrophotometer with a series of detectors for continuous measurements of more than one
wavelength in single time. In single beam and dual beam spectrophotometers, the light from a
lamp is discrete before getting the sample holder. In an array detector, all wavelengths are
passing via the sample as shown in Figure 2.16.
The wavelength range of 2450-model UV-Vis spectrophotometer is 190 to 1100 nm with a
spectral bandwidth of 1 nm. It is a double beam spectrophotometer. The short wavelength
limit for single beam UV-Vis spectrophotometer is the absorption of wavelength less than
180 nm. Purging of an instrument with N2 gas expand this frontier to 175 nm. There are two
light sources in this instrument: a 50 W halogen lamp for visible and near-infrared
dimensions and a deuterium lamp for UV measurements. The wavelengths from the light
source are dispersed through an aberration corrected concave blazed prism. The spectral band
pass is measured by the slit width of single wavelength light source. One of the major
limiting factors of this technique is that it rejects the stray light. Silicon photodiode is used as
a detector in this spectrometer. The changes can be made in the holographic grating and slit
width of the instrument.

77
 Figure 2.16: Showing dual-beam UV-Vis spectrophotometer.

2.3.1.2 Working Principle

A radiation of specified wavelength is obtained by a prism and then broken in two beams of
the same intensity. One beam is the sample beam which passes through a cuvette having a
compound dissolved in an appropriate solvent. The other beam passes through a similar
cuvette with solvent only.

Figure 2.17: Structure of Cuvette.

The structure of cuvette is shown in Figure 2.17. The measurements and comparison of
intensities of these two beams are done by electrical detectors. The intensities of reference
beam and sample beams are referred to as Io and I respectively.
A sample does not absorbs the photon of a incident wavelength, when I = Iο. However, a
sample absorbs the photon only if Io is greater than I. This difference is plotted against
wavelength known as absorption spectrum. Absorption may be presented as either
78
transmittance or absorbance. When absorbance value is equal to zero or transmittance value
reaches to one, indicates that no absorption occurs. Absorptions are mentioned on the vertical
axis and wavelengths are pointed on the abscissa. The maximum absorbance at a specific
wavelength is characteristics value for any given material. The compounds which are
showing high intense absorption are studied in very dilute solution by choosing the proper
solvent. The most used solvents are H2O, C2H5OH, hexane etc. Solvents having conjugation
or other heavy atoms are usually avoided. During the comparison of absorbance of different
samples, a term molar absorptivity is used instead of absorbance.
Different types of materials absorb ultraviolet and visible radiation of corresponding specific
wavelength. A UV-Vis spectrum shows a number of bands relevant to functional groups
present in the molecule. The absorption spectrum of semiconducting materials generally
relies on the transition of π bonding electrons to the π* high energy level as shown in Figure
2.18. These absorptions emerge due to the double bonds or triple bonds present in the
molecule. The solvent also play a major role during the optical absorption as it has its own
effect on the absorption spectrum of the species. As the polarity of solvent increases the
absorption peak () shifts to longer wavelength due to force of attraction between solvent
molecules which results in lowering of energy difference between ground state and excited
state.

Figure 2.18: Different type of transition in organic molecules.

During this research work, the absorption spectra of dye molecules were recorded using a
UV-VIS spectrophotometer model shimazdu 2450 UV-Vis spectrophotometer. For optical
absorption measurement, sample of a dye was taken in 0.01 M aqueous solution and then
absorption spectrum was recorded against wavelength generally between 200 nm to 1100 nm.
Due to delocalization of π-electron, π- π* transition takes place between valence band and
conduction band. Transition may be singlet-singlet or triplet-triplet.
79
2.3.1.3 Optical Band gap
The band gap is define as the energy difference between the upper most level of valence band
and lowest level of the conduction band as shown in Figure 2.19. It is closely related to the
highest occupied molecular orbital/ lowest unoccupied molecular orbital gap in the molecule.
Band gap plays a deciding role in measuring of the conductivity of the material. The
molecules with large band gap are usually insulators, those with small band gap are
semiconductor and those having very less energy difference are conductors. If the valence
band is completely filled and conduction band is empty then transfer of electrons does not
take place. Each solid has its own specific band gap and varies from material to material.
Electrons in a molecule have capability to jump from valence band to conduction band by
absorbing the energy from either heat or light.
At absolute zero temperature a semiconductor material with negligible band gap that behaves
as an insulator. The energy gap of semiconductor material is decreased with rising in
temperature and results in increasing the spacing between the atoms. This relation can be
understood by Varshni's empirical expression as:

T 2
Eg(T) = Eg(0) -
T +

where Eg(0), α and β are constants [17-18]. A semiconductor material has a constant band
gap due to the presence of continuity in their energy levels. In quantum dot, the band gap
depends on the size of the crystal [19].
A substance does not absorb the light when energy of photons is less than the energy gap. A
photovoltaic cell consisting luminescent materials which are used for down conversion of
high energy photons i.e. energy is usually larger than the band gap of materials and changes
to the energy difference of substance comprising the cell [20-22]. The materials with large
binding energy have a clear distinction between optical band-gap and electronic band-gap.
Usually the energy difference is less in optical band-gap in comparison to electronic band-
gap. In this way to get the exact value of optical band gap we follow an empirical relation
given by Tauc’s relation [23-26] referred to as Tauc’s plot as shown in Figure 2.20.

80
 Figure 2.19: Band gap structure of substance.

1.0 Band gap

0.9

0.8
2
Normalised absorbance

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
Energy (eV)

Figure 2.20: Plot of normalized absorbance2 Vs energy in eV.

81
  A
=
 h  (h  E )m
 
g

A is an energy independent constant and Eg is the optical band gap. The band gap was
measured by extrapolating of the straight line of the plot.
2.3.2 Thermogravimetric analysis
Thermogravimetric methods are applied to analyze the weight loss of any material as a
reference of temperature /or with time. It is normally used to determine molecule degradation
temperatures, absorbed moisture content, residual solvent levels, amount of inorganic
(noncombustible) filler available in polymer or composite material and stability of dye
molecules. Thermogravimetric analysis is presented weight versus temperature (or time)
curve or rate of mass loss versus temperature. The thermogravimetric curves may contain the
following features:
• A constant weight as horizontal portion, or plateau
• Rate of mass loss as curved portion
• An inflection (where dw/dt is a minimum, but not zero)
These features in TGA curve are not easily seen but can be more clearly obtained in the first
derivative of the TGA curve. Any change in the rate of mass loss can be analyzed as a trough
with in the first derivative of TGA curve. While a shoulder or tail to the peak, indicate the
two consecutive or overlapping reactions. Differential TGA curves can show considerable
similarity to differential thermal analysis (DTA) curves, which can authorize easy
comparisons to be made [27].

2.3.2.1 Instrumentation
The thermogravimetric analysis of material has been performed with STA-7300 Thermal
analyzer, Hitachi in air. The equipment used in the present study is shown in Figure 2.21.
2.3.2.2 Working
A few mg (5-10) of sample is placed into the TGA sample pan, which is attached to a
sensitive microbalance assembly. The sample holder portion of the TGA balance assembly is
subsequently placed into a high temperature furnace. The balance assembly measures the
initial sample weight at room temperature and then continuously monitors changes in sample
weight (losses or gains) as heat is applied to the sample. TGA tests may be run in a heating
mode at some controlled heating rate, or isothermally. Weight loss profiles are analyzed for
the amount or percent of weight loss at any given temperature, the amount or percent of non-

82
combusted residue at some final temperature, and the temperatures of various sample
degradation processes.

Figure 2.21: Photograph of thermal gravimetric analysis setup used

TGA is analyzed in presence of air or in inert atmosphere [28-30] with special heating rates.
The result of thermal method of any material depends on different conditions i.e amount,
material size, nature of the chemical, rate of heating and the atmosphere used in analyses etc
[31]. The recorder marks the change in mass with respect to the increase of the temperature.
It is also possible to find the temperature at which material starts decomposing [32-33] or
whether the decomposition occurs in one or more stages. Besides the quantitative information
obtained from the thermogram, other information related to the degradation can be analyzed
from the thermal data furnished in DTA or TGA. The apparatus used for TGA analysis is
referred to as a thermobalance. It has a furnace, continuously recording balance, temperature,
programmer and a recorder [34-38].
In TGA, a cylindrical platinum crucible of sufficient height is used and three different types
of sample holders are recommended, viz. gauze crucible, polyp late sample holder and
labyrinth crucible. TGA measures the change in the mass of a sample when sample is heated,
cooled or withheld at a constant temperature [39-42]. The analysis will depend on the
atmosphere used i.e inert or oxidative. Chemical changes occur in an oxidative atmosphere
providing very useful information regarding characterization of the sample. The thermal
analysis of a specimen involves studying the evolution of several physical properties as a
function of the temperature. When the material is subjected to heating or cooling, its chemical
composition and crystal structure undergo such changes as reaction, oxidation,

83
decomposition, fusion, expansion, contraction, crystallization, or phase transition. These
changes can be detected with the differential thermal analysis.
Differential thermal analysis (DTA) measures the temperature, the direction and the
magnitude of thermal transitions induced by heating or cooling a material in a controlled
way. DTA measures these properties by comparing the temperature of the sample and that of
a reference material, which is inert under similar conditions. This temperature difference is
measured as a function of time or temperature under a controlled atmosphere and it provides
useful information about the transition temperature and also about its thermodynamics and
kinetics. Thermogravimetric analysis (TGA) determines the weight gain or loss of a phase
due to gas absorption or release as a function of temperature under a controlled atmosphere.
This technique provides information about the purity of the sample, as well as its water,
carbonate and organic content. It is also useful for studying decomposition reactions. The loss
in weight due to pyrolysis of the material normally the shape of the TG curve depends upon
the nature of the in situ degradation reaction of the sample.

84
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