Piezoelectric Ceramics: Length-Scale
Dependent Average Structure &
Depolarization Mechanism
by
Dr. Rishikesh Pandey
Lecturer (Physics)
Government Polytechnic Buxar
Department of Science & Technology, Govt. of Bihar
Outlines
Introduction
Synthesis
Crystal Structure
Piezoelectric & Ferroelectric Properties
Summary
7 – types of crystal systems
Crystallographic Classifications
Total 32- point groups
21- point groups non centrosymmetric,
11- point groups centrosymmetric
20 -Piezoelectrics, 10 –Pyroelectrics (few are ferroelectrics)
What are Piezoelectrics?
Discovered in 1880 by Pierre-Curie and
Jacques Curie.
The word Piezoelectric is derived from
the Greek “Piezein” means “Press”.
Piezoelectric Effect (piezoelectricity) is
the ability of certain materials to
generate an electric field in response to
applied mechanical stress,
& vice-versa. Electro-mechanical
response
An electric field can change the shape &
size
Direct and Converse Piezoelectric effects
Ferroelectrics
Spontaneous polarization P
which direction can be reverse
E
by applying electric field
All ferroelectrics are
piezoelectrics
Piezo- Pyro- Ferro-
but all piezoelectrics electrics electrics electrics
are not ferroelectrics
100 years of ferroelectricity - Rochelle salt (1920)
Why Piezoelectrics?
Sensors
Actuators
Capacitors
Storage Devices
Energy Harvesting
Classification of Piezoelectrics
Naturally occurring crystals:
Quartz, Rochelle salt, Tourmaline, etc.
Man-made ceramics:
PbTiO3, BaTiO3, Pb(ZrxTi1-x)O3, etc.
Polymers:
Polyvinylidene fluoride (PVDF)
Perovskite Structure (ABO3) Piezoceramics
Perovskite structure (ABO3)
A: Pb2+, Ba2+, Sr2+, Bi3+ ……….
B: Ti4+, Ni2+, Zn2+, Zr4+ …………
Example: BaTiO3; PbTiO3
Bi(Zn1/2Ti1/2)O3 ; Bi(Ni1/2Zr1/2)O3
(1-x)PbTiO3–xPb(Mg1/3Nb2/3)O3
(1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3
Phase transition in BaTiO3
- 90 oC 5 oC 120 oC
Structure and properties are correlated to each other.
B. Jaffe, W.R. Cook, and H. Jaffe, Piezoelectric Ceramics
(Academic Press, London, 1971).
Morphotropic phase boundary (MPB) in PZT phase diagram
Pb(ZrxTi1-x) O3
D. Pandey, A. K. Singh and S. Baik, Acta K. Uchino, Ferroelectric devices
Cryst. A64, 192–203 (2008).
MPB is the a transition region in the compositional phase diagrams, where the crystal
structure changes abruptly and the electromechanical properties are maximal.
M. Ahart et al. , Nature 451, 545 (2008).
Ultrahigh Electromechanical Response in
Single-Crystal Piezoelectrics
Large strain- better for Pb(Zn1/3Nb2/3)O3-PbTiO3
application in devices
Single-Crystal has no grain
boundary
Strain more than 1% is
reported in the single crystal
piezoelectric
Polycrystalline ceramics have
multi-grains made up of multiple
S. E. Park and T. R. Shrout, J. Appl. Phys.
tiny crystals 82, 1804 (1997)
H. Fu and R. E. Cohen, Nature 403, 281
(2000).
Poling in Polycrystalline Piezoelectrics
(by DC-Electric field)
Polycrystalline ferroelectric with random orientation
of grains before and after poling.
Many domain walls are present in the poled material,
however, the net remanent polarization is nonzero.
D. Damjanovic, Rep. Prog. Phys. 61 1267–1324 (1998) .
Synthesis
Aiming to get high electrostrain
comparable to single crystals
Methods of Synthesis
1. Solid state route Bulk
2. Sol-gel route
3. Hydrothermal route Nano
4. Hot-press route
Synthesis: Solid State
Solid State RouteRoute
(1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3, x=0.38 to 0.44
Chemicals:
Bi2O3 , TiO2, NiO, Mixing
ZrO2 & PbO
Calcination (850 0C); 6h
Furnace
Mixed with PVA
Pellet formation Sintering
(~ 1100 - 1150 0C, 3h)
Steel die Pellets
Calcination & Sintering
PVA- Used as the binder (polyvinyl alcohol)
Calcination- To remove the volatile impurity
like CO2, H2O etc.
Sintering- To obtain dense piezoceramics
Phase identifications by X-Ray diffraction (XRD)
Phase Formation of (1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3
* Shows the
impurity
phases
Room Temperature Crystal Structure (XRD pattern)
Sintered
at
T – Tetragonal (P4mm)
1125 oC
C – Cubic-like (Pm-3m)
( C+T ) phase
MPB coexistence in MPB
region
On global scale
Powder XRD pattern of sintered (1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3, x = 0.38 - 0.44.
Electric-field (E) dependent unipolar strain (%)
(1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3
Electrostrain of 0.25% was
found in the cubic composition
x=0.44.
Contradict the theory.
Piezoelectric response is not
expected in the
centrosymmetric cubic phase.
Electrostrain ~ 0.5% was
obtained for x=0.41.
R. Pandey et al. Phys. Rev. B 97, 224109 (2018).
Local structure by Raman Study of (1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3
Raman patterns for
all the compositions are
similar to tetragonal
phase
Local structure of all
the compositions are
same
What is looking as
cubic-like on global
scale,
has tetragonal
R. Pandey et al. Phys. Rev. B 97, 224109 (2018). structure on local scale
Structure of poled (1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3
Unpoled Poled
E=30kV/cm, cubic
compositions transform
in tetragonal structure
Electric field increases
the size of domains
Proves that local
structure is tetragonal
R. Pandey et al. Phys. Rev. B 97, 224109 (2018).
Depolarization Temperature in (1-x)PbTiO3–xBi(Ni1/2Zr1/2)O3
Depolarization temperature
was ~ 120 oC.
Above this temperature,
piezoelectric coefficient d33
drastically decreases
R. Pandey et al. Phys. Rev. B 97, 224109 (2018).
Impact factor: 3.57
0.55Bi1–yLayFeO3–0.45PbTiO3: A Comparison
Cubic-like+tetragonal phase
coexistence was also
observed in 0.55Bi1–
yLayFeO3–0.45PbTiO3 .
Ultrahigh strain (%) was
obtained for x=0.30.
Such high strain (%) was
only reported in single
crystals.
Strain (%) for
Powder XRD profile for 0.55Bi1–yLayFeO3–0.45PbTiO3
0.55Bi1–yLayFeO3–0.45PbTiO3 with y = 0.20 - 0.37.
with y = 0.10 - 0.37.
B. Narayan, J. S. Malhotra, R. Pandey et al. Nature- Materials, 17, 427–431 (2018).
In-situ XRD study for 0.55Bi1–yLayFeO3–0.45PbTiO3 and PbTiO3–Bi(Ni1/2Zr1/2)O3
• At certain
concentration
of ‘La’,
domains were
mobile in
0.55Bi1–
yLayFeO3–
0.45PbTiO3.
• And were
able to switch
back to
original state
when E=0
kV/cm.
• Reversibility
(a) 0.55Bi1–yLayFeO3–0.45PbTiO3 (b) PbTiO3–Bi(Ni1/2Zr1/2)O3 was absent in
PbTiO3–
Bi(Ni1/2Zr1/2)O3
B. Narayan, J. S. Malhotra, R. Pandey et al. Nature- Materials, 17, 427–431 (2018).
Impact factor ~ 39
Summary
1. We have proved that large piezoelectricity does not necessarily require
interferroelectric instability (and hence morphotropic/polymorphic phase
boundary) as a criterion.
2. In the unpoled state the compositions of PT-BNZ showing large d33 exhibit a
coexistence of tetragonal and cubiclike (CL) phases on the global length
scale.
3. PT-BNZ is therefore qualitatively different from the conventional MPB
piezoelectrics.
4. The CL phase is rather a manifestation of tetragonal regions of short
coherence length. Poling increases the coherence length irreversibly which
manifests as poling induced CL →P4mm transformation on the global scale.
5. The piezoelectric enhancement in the present case is associated with the
inducement of structural heterogeneity via miniaturization of the
ferroelectric-ferroelastic P4mm domains, and does not involve a change of
symmetry (even on the local scale).
Acknowledgement
1. Prof. Satya Prakash, Principal, GP Buxar, DST-Bihar.
2. Science & Engineering Research Board, DST, Govt. of India for financial
support as NPDF.
3. Prof. Rajeev Ranjan (mentor), Department of Materials Engineering, IISc-
Bangalore.
4. Mr. Shekhar Tyagi & Dr. Vasant Sathe, UGC-DAE Consortium for Scientific
Research, University Campus, Khandwa Road, Indore 452001, India.
5. Prof. Ian M. Reaney, Department of Materials Science and Engineering,
University of Sheffield, Sheffield S13JD, United Kingdom.
6. Dr. Anatoliy Senyshyn, Forschungsneutronenquelle Heinz Maier-Leibnitz
(FRM II), Technische Universität München, Garching b. München, Germany.
7. Dr. Pavan Nukala & Prof. Brahim Dkhil, Laboratoire Structures, Propriétés
et Modélisation des Solides (SPMS), CentraleSupélec, CNRS-UMR8580,
Université Paris-Saclay, Gif-sur-Yvette, France.
THANK
YOU
