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Synthesis & characterization of ferroelectric Ba1-xSrxTiO3 nanocrystalline material by conventional heating method J KOWSALYA BASTIEN (M.

PHIL PHYSICS)

INTRODUCTION TO CRYSTAL CLASSES Depending on their geometry crystals are classified into 7 systems.  Triclinic, monoclinic, orthorhombic, tetragonal, trigonal, hexagonal, cubic.  7systems –32 point groups  11-posses centre of symmetry, 21(20-non centric crystal-piezoelectric crystal)  Among 20 non-centric crystals,10 posses unique polar axis belongs to pyroelectric classes.

FERROELECTRICS

Ferroelectric is a class of materials which exhibit a wide variety of physical properties such as relative permittivity, piezoelectricity, pyroelectricity, electrostriction and electro-optical activity. It also acts as a dielectric materials characterized by a reversible spontaneous polarization, which exhibits an electric dipole moment even in the absence of an external electric field. A necessary condition for a crystal to exhibit ferroelectricity is that the crystal structure must be non-centro symmetric crystal

HISTORY OF FERROELECTRICS

In 1920, Valsek discovered NaKC4H4O6.4H2O also known as Rochelle salt Scherrer 1935 and Busch 1938 discovered potassium dihydrogen phosphate KH2PO4 (KDP). In 1950’s Barium titanate (BaTiO3 ) was discovered. In 1960 ferroelectric ceramics including lead titanate (PbTiO3), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), and relaxor ferroelectrics like lead magnesium niobate (PMN) have been developed and utilized for a variety of applications.

CLASSIFICATION OF FERROELECTRICS
Mostly known ferroelectric material are classified into three main groups typically characterized by  Rochelle salt NaKC4H4O6.4H2O (112atoms)  Potassium dihydrogen phosphate KH2PO4 (KDP) (16 atoms)  Barium titanate BaTiO3 (5 atoms)

FERROELECTRIC HYSTERESIS

IMPORTANCE OF PEROVSKITE STRUCTURE
Ferroelectric Perovskite structure is much simpler in structure when compared to Rochelle salt and KDP and hence easier for theoretical understanding.  It is chemically and mechanically very stable at room temperature and could be easily prepared for its practical utility

This structure has a wide capacity characterized by tolerance factor which are responsible for wide spread applications in electro-optical devices, transducers, actuators, capacitors etc.,  It also has high dielectric permittivity which stimulate their applications in ferroelectric non volatile memories such as DRAM, FERAM etc.,

STRUCTURE OF PEROVSKITE

(a) Cubic ABO3 (BaTiO3) perovskite-type unit cell (b) three dimensional network of corner sharing octahedra of O2- ion

IMPORTANCE OF ADDITIVES
BaTiO3 is a perovskite type ferroelectric material used in electronics and its related compounds have been extensively used in the preparation of high dielectric capacitors, PTC transducers and ferroelectric memories.  Nevertheless, this material is not used in its true chemical form, rather combined with special additives to modify and to improve its electrical properties.

Sr+2 are one of the common additives to BaTiO3 for varying its curie temperature. It is noted that the addition of strontium lowers the Curie temperature below normal ambient operating temperature.  The curie temperature of pure barium titanate is 130oc with strontium doping the Curie temperature to room temperature. As a result barium strontium titanate ceramics are now being investigated with regard to various electronic applications

BST AN IMPORTANT CLASS OF MATERIALS.
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BST ceramics exhibit a number of attributes that makes them useful for the fabrication of microwave phase shifters. It is applied in piezo electric sensors, dynamic random access memories, under cooled infrared detectors and also in pyro electric properties. BST is a potential candidate for DRAM because of its high dielectric constant, low leakage current and high breakdown strength at Curie temperature. More over, the temperature range in which ferroelectric behavior exist can be easily controlled by adjusting barium- to- strontium ratio. BST material fit into all variety of applications because of their composition dependent properties simply by changing barium- tostrontium ratio and also by adding alio valent dopant.

INTRODUCTION TO NANO MATERIALS
Nanomaterials are materials where the sizes of the individual building blocks are less than 100nm  The unit of nano meter derives its prefixes from a Greek word meaning dwarf or extremely small.  Nanoscale is usually defined as smaller than a one tenth of a micrometer in at least one dimension.  It has the properties which depend inherently on the small grain size

Nanomaterials can be metals, ceramics, polymeric materials or composite materials.

A technology that operates at the atomic, molecular or macromolecular levels, in a length scale of 1-100 nanometers is known as nano technology.

NANOTECH GENERATION

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First generation: Passive nanostructures in coatings, nanoparticles, bulk materials (nano structured metals, polymers, ceramics): ~2001 Second generation: Active nanostructures such as transistors, amplifiers, actuators, adaptive structures: ~2005 Third generation: 3D nanosystems with heterogeneous nano components and various assembling techniques: ~2010 Fourth generation: molecular nanosystems with heterogeneous molecules based on biomimetics and new design~2020(expecting)

ADVANTAGE OF NANOTECHNOLOGY
Structural properties  Electrical properties  Optical properties  Magnetic properties  Thermal properties  Catalytic properties  Biocompatibility

PROCESS OF PRODUCING NANO POWDERS

SIGNIFICANCE OF NANO LENGTH SCALE
it is possible to vary fundamental properties of materials without changing the chemical composition.  The properties of materials can be different at the nanoscale for two main reasons:  larger surface area  quantum effects

PROPERTIES OF NANOMATERIALS
Nano particles or nanocrystals made of metals, semiconductors, or oxides are of particular interest for their mechanical, electrical, magnetic, optical, chemical and other properties  The often very high surface area to volume ratio of nanoparticles provides a tremendous driving force for diffusion, especially at elevated temperatures  Materials become stronger, more dent resistant, exert higher ductility, are lighter, and obtain a host of other material enhancement characteristics

DIFFERENT TYPES OF NANO MATERIALS

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Carbon Based Materials Metal Based Materials Dendrimers

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Composites

ADVANTAGES OF CONVENTIONAL HEATING METHOD No multiple – step processing, no costly inorganic or organo metallic raw materials are required  No special care is needed for handling and disposing the chemicals.  It always associated with low manufacturing cost, high production yield, and environmental friendly.  Simple and straight forward and hence suitable for large scale productions

Limitations: The temperature required for the synthesis of conventional solid state method is almost above 1200oc which causes agglomeration and grain growth. It is often contributed to compositional inhomogeneous and particle coarsening effect. Overcoming limitations: Indeed for the mentioned limitations of the conventional solid state reaction, the raw materials have to be effectively processed to produce highly homogeneous mixture in terms of composition and particle size. Hence intimate mixing of the raw material is of vital importance.

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Calcinations temperature and time is one of the key parameters that would determine the characteristic of BST. Hence, the optimum calcinations temperature and time must be obtained to ensure the mixture completely formed BST through solid state reaction. If the calcinations temperature is set too low, the mixture will only be partially
reacted.

SAMPLE PREPARATION

Weighing source compound BaCO3,SrCO3,TiO2 Grinding for homogeneous mixture(1 –hr) Calcinations(900oc -6 hrs)

Grinding for particle size reduction

The preparation of desired compound Ba1xSrxTiO3 with varying composition of x=0.1, 0.2, 0.3, 0.4. The reaction involved is

(1-x) BaCO3 + x SrCO3 + TiO2 Srx TiO3 + CO2 ↑

Ba1-x

CHARACTERIZATION
XRD- x-ray diffraction(physical properties)  FTIR- Fourier Transform Infrared Spectroscopy(chemical properties)  Differential thermal analysis, differential scanning calorimeter, thermal gravimetric(thermal properties)

GOLD SCHMIDT STRUCTURE FACTOR
t = (rA+rO) / (√2 (rB +rO)  Where rA - radius of A ion  rB - radius of B ion  rO - radius of O-2 ion and  t - Goldschmidt structure factor  Usually for perovskite t should in between 0.8 to 1.1 t Ba=0.9698 t Sr= 0.8887

3000

2000

intensity

1000
Sr0.4 Sr0.3 Sr0.2 Sr0.1

0

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

2 theta(degree)

D-spacing 3.9267 2.82328

Rel [%] 12.86 100.00

hkl 100 110

2.30608
1.99543 1.63125

24.76
20.73 23.26

111
200 2 11

sr 0.1 volume= 63.8 a=3.98920 b=3.98920

c=4.00710

c/a=1.0044

D-spacing 3.98699

Rel[%] 16.00

hkl 100

2.82321
2.30517 1.99517 1.63101

100.00
21.63 20.87 22.52

101
111 200 1 12

sr=0.2 volume=63.6 a=3.9878 b=3.98780 c=3.99873 c/a= 1.0027

D- spacing 3.98459 2.82491 2.30471 1.99468

Rel[%} 22.02 100.00 26.69 24.37

hkl 100 101 111 200

1.63034

28.97

211

sr 0.3 volume =63.6 a=3.98591 b=3.98591 c=4.00490 c/a =1.00

D- spacing 3.71293 2.78948 2.27813 1.97366

Rel[%] 17.49 100.00 16.18 21.50

hkl 100 101 111 200

1.61202

20.40

111

sr 0.4 volume=56.7 a= b= c= 3.84249

concentration 0.1 0.2 0.3 0.4

Volume 63.8 63.6 63.6 58.4

c/a 1.0044 1.0027 1.00 1.00

RESULT
The result showed that the structure was tetragonal perovskite and their lattice parameter decreased with dwell time  A smaller lattice parameter for longer calcinations should be due to better ionic rearrangement in the structure after decomposition.

Further higher strontium concentration incorporated in barium sites have reduced their lattice parameters.  Taking c/a ratio the degree tetragonality of the structure decreases and approaches unity with increasing x concentration.  The presence of strontium in the barium induced a new equilibrium inducing a shrinkage of both axis a and c in which c –axis shrinkage is more than a- axis.

It can be observed that the increasing of Sr content causes systematic shift of peaks towards higher 2θ angles due to the substitution of Ba+2[r(Ba+2)=1.0325268 by [r(Sr+2)]=0.7640699 Ao ]thus decreasing the d spacing of the structure.

The cell volume decreases with the increasing of Sr concentration

The cubic structure was contributed by Sr+2 . incorporation into BaTiO3 structure where smaller ionic radius replaces larger ionic radius causing shrinkage to the unit cell. As the concentration increases the particle size also decreases ranging from 40nm10.6nm using Debye-Scheer formula.

FTIR SPECTRA FOR Sr 0.1

FTIR SPECTRA FOR Sr 0.2

FTIR SPECTRA FOR Sr 0.3

FTIR SPECTRA FOR Sr 0.4

FTIR  The appearance of bands at high temperature for the prepared SBT samples are 1450.9cm-1, 680.3cm-1, and 450.1cm indicates the presence of C-O stretching mode

It also includes the c=o around 1638.8 ,c=c at 1450.9 and c-o at 1176.4 cm-1

Interpretation of peaks in the fingerprint region of 1500-400 cm-1 is complicated by the large number of different vibrations that occur here. These include single bond stretches and a wide variety of bending vibrations. This region gets its name since nearly all molecules(even very similar ones) have a unique pattern of absorptions in this region.

GRAPH FOR TG
100 100 100 99 99

weight%

99 99 99 98 98 98 0 200 400 600
0

800

temperature c

The weight loss was observed in all samples and the weight loss process started around 600oc.  The weight loss increases as the concentration increases.  The weight loss was due to the decomposition process which happened at an elevated temperature to produce oxides and CO2 gas.

Intimate mixing of through grinding created a large surface area which increased the reactivity of the system. This enables decomposition process happened at much lower temperature at 730 oc  The T- G curve helps to establish the decomposition temperature of the system

Thank you

DTA showed the endothermic phenomena  The endothermic process increases as the temperature increases.  This process is caused by the breaking of bonds and release of CO2 gas.

GRAPH FOR DTA
2000 1500 1000

Heat Flow mW/g

500 0

sr0.2
-500 -1000 -1500 -2000 0 200 400
0

sr0.1

600

800

temperature c

-1708.22

-411.20

1172.26

sr0.3

2136.55

sr0.4

122 120 118 116 114 112 110
112.672 119.683

sr0.4

sr0.3
106.023

weight%

108 106 104 102 100 98 96 94 92 0 200 400 600
0

sr0.2
98.192

sr0.1

800

temperature c

GRAPH FOR TG

100 100 100 99 99

weight%

99 99 99 98 98 98 0 200 400 600
0

800

temperature c