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Dielectric and Curie Temperature
Dielectric and Curie Temperature
Dielectric and Curie Temperature
Di-electric Constant
O
4+
Ti
Ba2+
O2 - O
A Perovskite unit cell and the displacements in its ions on the application of
an electric field.
O O
O O O O O O
O O O O
O O
O O
O O O O
O O O O O O
INTRODUCTION:
Ferroelectric ceramics were born in the early 1940s with the discovery of the
phenomenon of ferroelectricity as the source of the unusually high dielectric constant in
ceramic barium titanate capacitors. Since that time, they have been the heart and soul of
several multibillion dollar industries, ranging from high-dielectric-constant capacitors to
later developments in piezoelectric transducers, positive temperature coefficient devices,
and electro optic light valves. Materials based on two compositional systems, barium
titanate and lead zirconate titanate, have dominated the field throughout their history. The
more recent developments in the field of ferroelectric ceramics, such as medical
ultrasonic composites, high-displacement piezoelectric actuators (Moonies,
RAINBOWS) , photostrictors, and thin and thick films for piezoelectric and integrated-
circuit applications have served to keep the industry young amidst its growing maturity.
Various ceramic formulations, their form (bulk, films), fabrication, function (properties),
and future are described in relation to their ferroelectric nature and specific areas of
application.
A huge leap in the research on ferroelectric materials came in 1950 leading to the
wide spread use of Barium titanate (BaTiO3) by the market potential of next generation
memories and transducers. Thin films of ferroelectrics and dielectrics are rapidly
emerging in the field of MEMS applications. Ultrasonic micro-motors utilizing PZT thin
films and pyroelectric sensors using micro-machined structures have been fabricated.
MEMS are finding growing application in accelerometers for air bag deployment in cars,
micro-motors and pumps, micro heart valves, which have reached the commercial level
of exploitation in compact medical, automotive, and space applications. Extremely
sensitive sensors and actuators based on thin film and bulk will revolutionize every walk
of our life with Hi-Tech gadgets based on ferroelectrics. Wide spread use of such sensors
and actuators have made Hubble telescope a great success story. New bulk ferroelectric
and their composites are the key components for the defence of our air space, the long
coastline and deep oceans.
The quest of human beings for developing better and more efficient materials is
never ending. Material Science has played a vital role in the development of society.
Characterization is an important step in the development of different types of new
materials. This experiment is aimed to expose the young students of Dielectric and Curie
Temperature Measurement technique for Ferroelectric Ceramics.
-+ -+ -+
Charge -+ -+ -+
+Q -Q
-+ -+ -+
-+ -+ -+
-+ -+ -+
-+ -+ -+
-+ -+ -+
Electric
Field E -+ -+ -+
-+ -+ -+
Dielectric
Polarized molecules
Fig. 1
become a conductor. Dielectrics are more resistant to ionization than air, so a capacitor
containing a dielectric can be subjected to a higher voltage. Also, dielectric increases the
capacitance of the capacitor. An electric field polarizes the molecules of the dielectric,
producing concentrations of charge on its surfaces that create an electric field opposed
(antiparallel) to that of the capacitor. Thus, a given amount of charge produces a weaker
field between the plates than it would without the dielectric, which reduces the electric
potential. Considered in reverse, this argument means that, with a dielectric, a given
electric potential causes the capacitor to accumulate a large charge.
The electrons in the molecules shift toward the positively charged left plate. The
molecules then create a leftward electric field that partially annuals the field created by
the plates. (the air gap is shown for clarity; in a real capacitor, the dielectric is in direct
contact with the plates.)
Perovskite Structure:
Perovskite is a family name of a group of materials and the mineral name of calcium titanate
(CaTiO3) having a structure of the type ABO3. Many piezoelectric (including ferroelectric)
ceramics such as Barium Titanate (BaTiO3), Lead Titanate (PbTiO3), Lead Zirconate Titanate
(PZT), Lead Lanthanum Zirconate Titanate (PLZT), Lead Magnesium Niobate (PMN), Potassium
Niobate (KNbO3), Potassium Sodium Niobate (KxNa1-xNbO3), and Potassium Tantalate
Niobate (K(TaxNb1-x)O3) have a perovskite type structure (in the para-electric state) with
chemical formula ABO3 as shown in Fig 2 (a) and 2(b).
Fig 2(a) Perovskite B3 structure with the A and b cations on the corner and
body center positions,respectively.Three oxygen anions per unit cell
occupythe faces and form octahedral surrounding the B-site
A practical advantage of the perovskite structure is that many different cations can
be substituted on both the A and B sites without drastivally changing the overall
structure. Complete solid solutions are easily formed between many cations, often across
the entire range of composition. Even though two cations are compatible in solution, their
behavior can e radically different when apart from each other. Thus, it is possible
to manipulate a material’s properties such as Curie Temperature or dielectric constant
with only a small substitution of a given cation.
All ferroelectric material have a transition temperature called the Curie point (T c).
AT a temperature T > Tc the crystal does not exhibit ferroelectricity, while for T < T c it is
ferroelectric. On decreasing the temperature through the Curie point, a ferroelectric
crystal undergoes a phase transition from a non-ferroelectric (paraelectric) phase to a
ferroelectric phase.
Barium Titanate (BaTiO3) has a ferroelectric tetragonal phase below its curie
point of about 1300C and paraelectric cubic phase above Curie point. The temperature of
the curie pint appreciably depends on the impurities present in the sample and the
synthesis processes.
In the paraelectic cubic phase the center of positive charges (Ba2+, Ti4+) coincide
with the center of negative charges (0-2ion) and on cooling below Tc, a tetragonal phase
develops where the center of Ba2+ and Ti4+ ions are displaced relative to the 02-ions,
leading to the formation of electric dipoles.
The dielectric properties of BaTiO3 are found to be dependent on the grain size .
Figure 7 shows the variation of dielectric constant with temperature for BaTiO3 ceramics
with a fine (~ 1 mm) and coarse (~ 50 mm) grain size. Large grained BaTiO3 (³ 1 m m)
shows an extremely high dielectric constant at the Curie point and for a BaTiO3 ceramic
with fine grains (~ 1 m m), leading to a low dielectric constant at the Curie point as
compared to coarse grained BaTiO3 The room temperature dielectric constant (er) of
coarse grained (³ 10 m m) BT ceramics is found to be in the range of 1500-2000. On the
other hand, fine grained ( ~1 m m) BT ceramics exhibit a room temperature dielectric
constant between 3500-6000.
Fig. 7 : The variation of the mr) with temperature for BaTiO3 ceramics with (a) 1 relative
permittivity ( m grain size. grain size and (b) 50
As the BT ceramics have a very large room temperature dielectric constant, they are mainly used
multilayer capacitor applications. The grain size control is very important for these applications.
Dielectric Constant
The dielectric constant of a dielectric material can be defined as the ratio of the
capacitance using that material as the dielectric in a capacitor to the capacitance using a
vacuum as the dielectric. Typical values of for dielectrics are:
C
,
C0
Where
C = capacitance using the material as the dielectric in the capacitor
Department of Physics, IIT Roorkee 6
Thermal Laboratory
1. Probe Arrangement
It has two spring loaded probes. These probe move in pipes and are insulated by
Teflon bush, which ensure a good electrical insulation. The probe arrangement is
mounted in suitable stand, which also hold the sample plate and RTD sensor. The
RTD is mounted in he sample plates such that it is just below the sample,
separated by a very thin sheet of mica. This ensures the correct measurement of
sample temperature. This stand also serves as a lid of the over. The leads are
provided for the connection to RTD and capacitance meter.
2. Sample
Barium Titanate (Ba Ti O3) plate with top and bottom conducting surface.
3. Oven
This is a high quality temperature controlled oven. The oven has been designed
for fast heating and cooling rates, which enhance the effectiveness of the
controller.
4. Main Units
The Set-Up consists of two units housed in the same cabinet.
Experimental Procedure
1. Put a small piece of aluminum foil on the vase plate. Pull the spring loaded probes
upward, insert the aluminum foil and let then rest on it. Put the sample (Ba Ti O 3)
on the foil. Again pull the top of one of the probe and insert the sample below it
and let it rest on it gently. Now one of the probes would be in contact with the
upper surface of the sample, while the other would be in contact with the lower
surface through aluminum foil.
2. Connect the probe leads to the capacitance meter.
3. Connect the oven to the main unit and put the oven in OFF position.
4. Switch on the main unit and note the value of capacitance. It should be a stable
reading and is obtained directly in pf.
5. (i) Switch ON the temperature Controller and approx adjust the set-temperature.
The green LED would light up indicating the oven is ON and temperature would
start rising. The temperature of the oven in 0C would be indicated by the DPM.
(ii) The controller of the oven would switch ON/OFF power corresponding to set-
temperature. In case it is less then the desired, the set-temperature may be
increased or vice versa.
(iii) Because of thermal inertia of oven, there would be some oven shoot and
under shoot before a steady set-temperature is attained and may take 10 minutes
for each reading.
Area (A) : 8 x 6 mm
C 0 A 8.85 10 3 48
; where, C 0 29.9 10 3 pf
C0 t 1.42
Typical Results
From the grapy, Curie Temperature (Tc) – 1310C.
Precautions
(1). The spring loaded probe should be allowed to rest on the sample very gently,
other wise it may damage the conducting surface of the sample or even beak the
sample.
(2). The reading of capacitance meter should be taken when the oven is OFF. This
would be indicated by the green LED. In ON position there may be some pick
ups.
Department of Physics, IIT Roorkee 9
Thermal Laboratory
(3). The reading near the curie Temperature should be taken at close intervals, say
10C.
Reference
(1). Introduction to Solid State Physics- C.Kittel, Wiley Eastern Limited (5 th Edition).
APPLICATIONS:
Beside the common and well known application of capacitors in electrical and
electronic circuits, the capacitors with an exposed and porous dielectric can be used to
measure humidity in air. A huge leap in the research on dielectric (ferroelectric materials)
came in 1950’s leading to the wide spread use of Barium Titanate (BaTiO 3- Perovskite
Structure) bread ceramics in capacitor applications an piezoelectric transducer devices.
Since then, many other ferroelect5ic ceramics have been developed and utilized for
variety of applications: various type of capacitors, non volatile memories in computers,
etc.
PEROVSKITE STRUCTURE:
Perovskite is family name of group of materials and the mineral name of calcium
titanate (CaTiO3) having a structure of the type ABO3.
A practical advantage of perovskite structure is that many different cations can be
substituted on both A and B sites without changing the over all structure. Even though
two cations are compatible in solution, their behaviour can be radically different when
apart fro each other. Thus it is possible to manipulate material’s properties such as Curie
temperature or dielectric constant with only a small substitution of given cation.
All ferroelectric material have a transition called the Curie point (Tc). At T>Tc,
the crystal does not exhibit feroelect5icity, while for T<Tc it is ferroelectric. If there is
more than one ferroelectric phase, the temperature at which the crystal transforms one
phase to another is called transition temperature. Near the Curie temperature point or
transition temperatures, the thermodynamic properties including dielectric, elastic, optical
and thermal constants show an anomalous behavior. The variation of dielectric constant
( ) with temperature for Lanthanum doped Lead Zirconate Titanate (PLZT) ceramic,
which is cooled from its paraelectric cubic phase to ferroelectric rhombohedral phase.
2. Samples:
Barium Titanate (BaTiO3).
3. Oven:
This is a high quality temperature controlled oven. This oven has been designed
for fast heating and cooling rates, which enhances the effectiveness of the
controller.
4. Main Units:
The Set-up consists of two units housed in the same cabinet.
(i) Oven Controller:
Platinum RTD (A class) has been used for sensing the temperature. A Wheatstone
bridge and an instrumentation amplifier are used for signal conditioning.
Feedback circuit ensures offset and linearity trimming and a fast accurate control
of the oven temperature.
SPECIFICATIONS:
Range : 50-6000 pf.
Resolution : 1 pf.
Display : 3 ½ digit, 7 segment LED.