High Temperature Piezoelectric Materials
Deepam Maurya and Shashank Priya
Acknowledgements
National Science Foundation (NSF)
Department of Energy (DOE)
2
Outline
• Introduction
• Improving piezoelectric response (with
example of lead-free piezoelectric
materials)
• Integration
3
Growing Market for the piezoelectric devices
The current market was estimated to have reached over U.S. $21 billion and is
expected to reach $38.4 billion by 2017.
4
Source: iRAP, Inc
Some examples of the high temperature
environment
• Jet engines,
• Rocket exhausts
• Nuclear Fast Breeder Reactors (FBRs)
• Geothermal exploration and production and
deep bore-drilling
https://en.wikipedia.org/wiki/File:Jet_engine.svg
5
http://ngpdlab.engin.umich.edu/high-altitudeflows/rocket-exhaust-particles
https://www.sintef.no/en/projects/descramble/
Key features of existing high-temperature sensors
6
Selected piezoelectric materials and their
Curie temperatures
7
Usage temperature range for various
piezoelectric materials
The large time constant
indicates the potential
sensing at low frequency
range.
LN: LiNbO3
BLSF: Aurivillius structure
PLS: Perovskite layer structure
LGN: La3Ga5.5Nb0.5O14
CTGS: Ca3TaGa3Si2O14
NdCOB: NdCa4O(BO3)3
GdCOB: GdCa4O(BO3)3
YCOB: YCa4O(BO3)3
τ: time constant
8
Crystallographic structure of piezoelectric cell
ABO3 perovskite structure
BaTiO3
Cubic lattice above
Curie temperature
Tetragonal lattice
below
Curie
temperature
Groups of unit cells with the same orientation are called Weiss
domains
Polycrystalline structure of ferroelectric ceramics below Curie temperature
Curtsey : http://www.physikinstrumente.com
9
Piezoelectric multilayer beam bending actuators: static and
dynamic behavior
How to improve the piezoelectric response
10

Construct solid solution near morphotropic
phase boundaries (MPB)

Modifying composition by doping of various elements

Grain size control

Synthesis of textured ceramics
Enhanced piezoelectric response at MPB of PZT*
At MPB coexistence of two phases gives rise to enhanced
electromechanical response.
11
*PZT: Pb(ZrTi)O3
Soft and Hard piezoelectric Ceramics
Perovskite
ABO3
Pb2+(Zr,Ti)4+O2-3
A site
B site
Lower valence substitution : Hardening
Higher valence substitution : Softening
Doping effect on piezoelectric properties
kind
dopants
effect
- Formation of Oxygen vacancies (increase
Hardner
Acceptor Ion
Li1+, K1+, Fe3+, Ni2+, Co2+, Al3+
A site
Softner
Donor Ion
La3+, Bi3+, Nb5+, W6+, Ta5+
A site
12
B site
B site
space charge, domain motion is difficult.)
- Elastic compliance, dielectric constant, k
and bulk resistivity are reduced.
- Ec, Qm are enhanced.
- Formation of Pb vacancies
(domain motion is easy)
- Elastic compliance, dielectric constant, kp
and bulk resistivity are enhanced.
- Ec, Qm are reduced.
Manifold improvement in piezoelectric response can
be achieved in oriented single crystals as a result of
anisotropy
Single crystal
Polycrystalline piezo
1. High
piezoelectric 1. Reduced
constant
piezoelectric
constant
due
to
averaging effect.
2. High cost
2. Cost effective
3. Low
mechanical 3. High
mechanical
strength
strength
4. Difficult to have fine 4. Fine domain size
domain size
can be induced
5. Large
scale 5. Large
scale
production
is
production is easy
difficult
6. Require
special 6. Require
normal
furnace
and
sintering
furnace
Platinum crucible
and processing
Textured polycrystalline ceramics will be a great combination
13
Zhang and Li, J. Appl. Phys. 111, 031301 (2012)
Texturing of polycrystalline ceramics
What is texturing
Texturing is referred
to have preferred
crystallographic
orientation
in
a
randomly oriented
ceramic
What it does
Single crystal
Un-textured
polycrystalline
ceramics
Polycrystalline ceramics with Ideal
texture
Texturing allow the polycrystalline ceramics to resemble
their single crystal counterparts crystallographically so that
the favorable properties of single crystals may be achieved.
14
Effect of texture in lead-free
piezoelectric materials
15
Why lead-free?
Lead-based piezoelectric materials contains upto 60% of lead
16
http://koonceconsulting.com/lead-poisoning-everyone-is-in-danger/
Rapidly growing world-wide research interest resulting
enhanced number of publications in lead-free
piezoelectric materials
17
Coondoo et al., J. Adv. Dielectrics, Vol. 3, No. 2 (2013) 1330002
MPB in lead-free piezoelectric
• (1-x)Na0.5Bi0.5TiO3-xBaTiO3 exhibits morphotrpic phase
boundary (MPB) around x=0.06- 0.07
• This system has been considered potential candidate to
replace PZT
18
Optimization of properties across MPB in lead-free
piezoelectric (1-x) Na0.5Bi0.5TiO3-xBaTiO3
200
(1-x)Na0.5Bi0.5TiO3-xBaTiO3
50
150
30
20
100
kp (%)
d33(pC/N)
40
10
50
0.05
1500
x = 0.07
x = 0.06
39.5
40.0

2 
40.5
41.0
(1-x)Na0.5Bi0.5TiO3-xBaTiO3
5
1200
4
900
3
600
2
300
1
46.5

2 
47.0
47.5
0
0.05
0.06
0.07
x
0.93Na0.5Bi0.5TiO3-0.07BaTiO3 was identified MPB composition
19
0
x = 0.06
x = 0.05
46.0
0.09
x = 0.07
x = 0.05
39.0

x = 0.08
0.08
o
Intensity (arb. units)
Intensity (arb. units)
x = 0.08
x = 0.09
0.07
x
0.08
0.09
0
tan (%)
x = 0.09
0.06
Unlike lead-based piezoelectric materials elemental
doping has little effect on the functional response in
lead-free piezoelectric
20
Maurya et al. J. Mater. Chem. C, 2013, 1, 2102-2111
Templated grain growth (TGG) method for single
crystals
Single crystal template
Original Interface
Grown crystal
Sintered Polycrystalline
matrix
21
Messing et al. critical review , 2004
Grain oriented NBT-BT ceramics
Schematic of the process
22
Schematic representation of the growth of textured NBTBT grain on NBT template
23
Microstructural development
24
Coherent interface of seed and textured grain
25
Maurya et al. J. Mater. Chem. C, 2013, 1, 2102-2111
The strong texturing
structural distortions
resulted
in
extra
Randomly oriented NBT-BT
a = 5.5017 Ǻ and α=60.28o
Textured NBT-BT
a = 5.4909 Ǻ and α=60.99o
26
Maurya et al. J. Mater. Chem. C, 2013, 1, 2102-2111
Textured specimen was found to depict smaller
coercive field and higher remnant polarization
27
Piezoelectric properties of textured system
Sample
d33 (pC/N)
PZ27 ceramics (Ferroperm)
NBT-BT single crystal[1]
Mn: NBT-BT single crystal(Pt)[2]
Textured NBT-BT ceramics
28
425
280
287
322
kt (%) k31 (%)
47
56
55.6
57.3
33
----39.7
----
1.J. Phys. D: Appl. Phys., 41, 115403, (2008)
2.Appl. Phys. Lett., 95, 102904, (2009)
Maurya et al. J. Mater. Chem. C, 2013, 1, 2102-2111
Pr (μC/cm2) Ec (kV/mm)
---16
35
35
----2.7
2.9
1.8
Giant strain with high temperature stability
in textured ceramics
29
Texturing of new system away from the
morphotrpic phase boundary
30
*K0.5Bi0.5TiO3-BaTiO3-Na0.5Bi0.5TiO3 (KBT-BT-NBT)
Takenaka et al. J. J. App. Phys., 47, 3787, (2008)
Degree of hysteresis in electric field induced
strain plots
31
Relativ
0
6000 200
f100(%)
d33 (pC/N)
Td
160
0.3
140
0.2
3000
2000
Increasing frequency
1000 120
0 100
100
0
200
20
300
40
o
0.1
400
60
( C)
Temperature
f (%)
200
150
100
5000
0.0
500
80
100
0.3
2000
Increasing frequency
0
50
100
100
200
150
300
400
200 o 250
Temperature
( C)
o
Temperature ( C)
250
Non-textured
High temperature
Textured samplestability in
textured
ceramics
200
150
*K0.5Bi0.5TiO3-BaTiO3-Na0.5Bi0.5TiO3 (KBT-BT-NBT)
0.2
(d) (b)
3000
d33(pC/N)
e permittivity
m
d
Tm
0.0
500
4000
0
Loss tange
3000
400
0.1
Td
50 1000
6000
0.5
Increasing
piezoelectric constant
Textured KBT-BT-NBT
(c)
(d
33) with increasing degree of
5000
0.4
T
texture
T
32
o
Textured sample
100
4000
300
250 6000Non-textured
Non-textured KBT-BT-NBT
Loss tangent
0.4
200
Temperature ( C)
0.5
Tm
100
100
(c)(a)
Textured KBT-BT-NBT
5000 180
4000
80
60
Relative permittivity
40
20
0
d33(pC/N)
d3
High piezoelectric constant and High temperature
Increasing frequency
120
1000
stability in textured KBT-BT-NBT*
ceramics
100
Relative permittivity
0.2
2000
ngent
140
100
Giant strain with low degree of hysteresis in
textured sample
0.1
44
30
60
90
Field (kV/cm)
Poled
Unpoled
45
46
o
2( )
120
47
1 Hz
0.2
0.1
48
150
Poled
Unpoled
44
0.0
0
30
60
90
Textured
(002)
0.3
(200)
(200)
(002)
Non-textued
(b)
Intensity (arb. units)
1 Hz
0.2
0.0
0
Textured KBT-BT-NBT specimen
0.4
Intensity (arb. units)
Strain(%)
(a)
33
0.5
Non-textured KBT-BT-NBT specimen
Strain(%)
0.3
45
120
Field (kV/cm)
46o 47
2( )
48
150
High temperature stability of E-field induced strain
34
Enhanced polarization in textured specimen
Polarization (C/cm )
2
Non-textured
20 KBT-BT-NBT
10
(c)
1 Hz
0
-10
-20
-30
-60 -40 -20
0
20 40 60
Field (kV/cm)
(e)
10
1 Hz
0
-10
-20
-30
-60 -40 -20
5
30
40
50
Field(kV/cm)
60
20 40 60
Textured
Randomly oriented
(f)
p = 0.08
p = 0.06
10
p = 0.06
20
0
Field (kV/cm)
20
0
35
(d)
30
p = 0.13
10
10
Ec (kV/cm)
2
Pr (C/cm )
15
Textured
20 KBT-BT-NBT
40
Textured
Randomly oriented
20
30
2
Polarization (C/cm )
30
70
0
10
20
30
40
50
Field(kV/cm)
60
70
Comparative domain structure of textured and nontextured sample
Non-Textured
Textured
36
High piezoelectric response with high temperature stability
37
Giant strain with ultra-low hysteresis and high temperature
stability in KBT-BT-NBT* system
o
(a)
180
*
This work
200
d33 = 192 pC/N
180
o
Td = 165 C
160
160
140
140
120
100
80
60
120
[5]
100
[7]
[8]
[6]
80
[7]
Cu doped NBT
Nb doped NBT
d33 (pC/N)
Depoling temperature ( C)
200
(1-x)BNT-xBC Ta doped BNT-6BT BNT - BKT - BT5
60
Various NBT based systems
38
(b)
[28]
80
[27]
60
[27]
40
20
0
Textured
0.5
Strain(%)
Degree of hysteresis (%)
100
[23]
[25]
[27]
0.2
This work
High strain
and low hysteresis
0.3
0.4
0.5
0.6
Smax (%)
0.7
0.8
0.4
0.3
0.2
Non-textured
0.1
0.0
0
20 40 60 80 100 120 140 160
Field (kV/cm)
*K0.5Bi0.5TiO3-BaTiO3-Na0.5Bi0.5TiO3 (KBT-BT-NBT)
Maurya et al. (Under review in Advanced Functional Materials)
Ren at al., Nature Materials 3, 91 - 94 (2004)
Integration of the piezoelectric
materials
39
3D printing of meso/micro-scale devices
• Printing structures at micro
and meso-scale is quite
challenging.
• Onboard laser can be used for
sintering those structures to
reduce time and cost of
processing significantly.
• We have printed various
complex structures using
this technique
40
Schematic of aerosol deposition process (Optomec)
Dry aerosol deposition and laser sintering process for
printing smart materials (piezoelectric/ferroelectrics) on
low thermal budget flexible substrates
41
Almost identical elemental distributions across the interface of
the laser annealed and as deposited PZT films
As deposited
42
Laser annealed
Enhanced magnetoelectric response
A strong ME coupling with an extremely high value of αME ~ 3V/cm·Oe was obtained at
a very low magnetic field (53 Oe). The inset of (d) shows the schematic illustration of
how αME was measured.
43