Author’s Accepted Manuscript

In situ TEM observations of microstructural

characteristics of lead zirconate titanate
piezoelectric ceramic during heating to 1000°C

Mitsuhiro Okayasu, Tsukasa Ogawa, Yoshikazu

Sasaki
www.elsevier.com/locate/ceri

PII: S0272-8842(17)31920-X
DOI: http://dx.doi.org/10.1016/j.ceramint.2017.09.001
Reference: CERI16172
To appear in: Ceramics International
Received date: 7 July 2017
Revised date: 22 July 2017
Accepted date: 1 September 2017
Cite this article as: Mitsuhiro Okayasu, Tsukasa Ogawa and Yoshikazu Sasaki,
In situ TEM observations of microstructural characteristics of lead zirconate
titanate piezoelectric ceramic during heating to 1000°C, Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2017.09.001
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 1

In situ TEM observations of microstructural characteristics of lead zirconate titanate

piezoelectric ceramic during heating to 1000C

Mitsuhiro Okayasu1*, Tsukasa Ogawa1, Yoshikazu Sasaki2

1
Graduate School of Natural Science and Technology, Okayama University, 3-1-1
Tsushimanaka, Kita-ku, Okayama, 700-8530, Japan
2
TSD R & D Business Support Department, JEOL Ltd. 1156 Nakagami, Akishima, Tokyo,
196-0022, Japan
*
Corresponding author. Tel/fax: +81 86 251 8025. E-mail address: mitsuhiro.okayasu@utoronto.ca (M. Okayasu)

Abstract
The microstructural characteristics of lead zirconate titanate (PZT) ceramic at high

temperature were examined by in situ transmission electron microscopy (TEM) observations

of lattice and microstructural formations. The PZT ceramic was heated from room

temperature to 1000C using a compact heating device within the TEM. It was found that the

microstructural characteristics of the ceramic changed significantly in various ways as the

temperature was raised to 1000C. Domain-switching-like behavior was detected around

100C. Disordered lattice features such a dislocations disappeared owing to reduction in

internal stress at temperatures above 300C. Heating to more than 800C for a certain period

of time led to the formation of a nanocrystalline microstructure and to sublimation of Pb.

Keywords: In situ observation; TEM, PZT ceramic; Microstructure; Lattice structure; High
temperature

1. Introduction

The piezoelectric properties of lead zirconate titanate (PZT: Pb(Zr,Ti)O3) ceramics have led to

their widespread use in a number of engineering applications, for example as sensors and

actuators. The production process of bulk PZT ceramics can be briefly summarized as follows

[1]. Three different powders are employed to make PZT ceramic, including PbO, ZrO2 and

TiO2. PZT ceramic, made from the three powders, is crushed roughly to small particles. After
 2

the crushed ceramic has been dried, it is pre-heated at a temperature between 700C and

900C. Further crushing is conducted to produce fine grains, which are then mixed with a

binder based on an organic material, such as polyvinyl alcohol (PVA). After the mixture has

been pressed into a suitable shape to allow further machining, the binder is removed by

heating to 300–500C. The PZT ceramic is then calcined by heating to a high temperature

(1100–1300C) in an oxygen-containing atmosphere (such as air), with precautions being

taken to avoid loss of lead as the volatile oxide PbO. After precise machining to the desired

shape, silver-based electrodes are coated onto the ceramic surfaces; these allow application of

an electric field of 2–3 kV/mm to the PZT ceramic at about 100C to obtain piezoelectric

properties.

It can be seen from the above description that the PZT ceramic is subjected to high

temperatures at several stages during its production. In addition, owing to their low cost, light

weight, and capability of miniaturization, PZT ceramics are used in the automotive and power

plant industries for sensing devices that need to be employed at high temperatures [2]. In

previous work, the piezoelectric properties of PZT ceramics have been assessed at different

temperatures within a specified range [3]. The results of these studies have demonstrated that

if the annealing temperature exceeds 700C, diffusion of titanium element within the PZT

ceramics occurs [4]. In situ X-ray diffraction studies of the crystallization of piezoelectric

ceramics of different chemical compositions, namely, lead titanate (PT) and lead zirconate

(PZ) as well as PZT, at temperatures in the range 380–500C have shown that the

crystallization temperatures increase in the sequence PT < PZ < PZT [5]. The crystallization

kinetics of textured (100)-PZT thin films on highly textured (111)-Pt have been investigated

in the temperature range 550–700C. It has been shown that crystallization proceeds by the

formation of globular, Zr-depleted, and Pb-rich particles that exhibit necklace patterns [6].
 3

Furthermore, in a study in which the performance of a piezoelectric sensor in an

accelerometer prototype was examined as a function of elevated temperature in the range up

to 1000C and in a frequency range of 100–600Hz [7], a sensitivity of 2.4  0.4 pC/g across

these ranges was found, indicating a low temperature coefficient. It has also been found that,

unlike ferroelectric polycrystalline materials, piezoelectric single crystals are not subject to

domain-related aging behavior despite their high electrical resistivity, and that they also

exhibit low losses with excellent thermal stability of their properties [8]. It can be seen from

the above results that the material properties of PZT ceramics are sensitive to temperature.

Therefore, the aim of the present work is to investigate the lattice and microstructural

characteristics of PZT ceramics via in situ TEM observation during heating of a sample.

2. Material and experimental procedures

The material used in this work was a commercial bulk PZT ceramic with piezoelectric

polycrystalline structure of nominal composition Pb(ZrTi)O3, produced by Fuji Ceramics Co.

in Japan. The PZT ceramics were made with an average grain size of 5 μm, a density of 7.65

g/cm3 and Curie point of 295C. The PZT ceramic adopts a perovskite tetragonal structure

with aspect ratio c/a = 1.014 (a = 0.4046 nm and c = 0.4103 nm). An initial sample was

machined with dimensions 3 mm  3 mm  40 mm. Changes in microstructural characteristics

were investigated by transmission electron microscopy (TEM, using a JEM-2100F instrument

with an acceleration voltage of 200 kV), with in situ microstructural observations being

conducted at temperatures from 25C to 1000C, increasing at 1C/s. The sample used for

TEM observations was cut from the initial sample using a focused ion beam (FIB) technique:

thickness of the TEM samples are about 150 nm. To allow clear TEM observations at high

temperature, a compact heating system of Aduro500 (Protochips) was employed within the
 4

microscope. The TEM image was continuously monitored using a video camera.

The microstructural characteristics were also examined by energy-dispersive X-ray

spectroscopy (EDS) and electron backscatter diffraction (EBSD). For both of these

investigations, a sample of dimensions 3 mm  3 mm  5 mm was employed. The sample

surfaces were polished to a mirror state using colloidal silica. EDS was carried out using a

JEOL-JIB-4500 scanning electron microscope (SEM) with an acceleration voltage of 15 kV,

and EBSD was carried out using a JEOL-JSM-7001F SEM with an acceleration voltage of 15

kV, a beam current of 10 nA and a step size of 0.1 m.

3. Results and discussion

Fig. 1(a) shows TEM images of a PZT ceramic sample at different temperatures ranging from

room temperature to 1000C. About six grains can be seen, with varying brightness owing to

differences in the lattice orientation of the tetragonal structure. Increasing sample temperature

leads to changes in microstructural characteristics. As can be seen in Fig. 1(b), the dark region

in the sample at room temperature (enclosed by the dashed circle), which has a different

lattice orientation, disappears as the sample is heated to more than 100C. This may be

attributable to domain switching. In our previous work, the effect of thermal stress on domain

switching was investigated by EBSD analysis [9], and it was found that 90° domain switching

occurred significantly around 100C. However, in this case, the lattice orientation has not

been clarified directly, so further analysis will be required in the future. As the sample

temperature is increased to about 300C, disordered lattice formations are replaced by

uniform formations, as can be seen in Fig. 1(c). Note that, in this case, dislocations may be

affected, as the dislocation density could be reduced with increasing the sample temperature.

With increasing temperature, there is also a change in deformation twinning, as can be seen in
 5

Fig. 1(d): the width of twinning band increases when the sample temperature exceeds 400C,

and, in this case, the deformation twin disappears completely at about 529C. These results

suggest that internal stress in PZT ceramics could be removed by heating to more than 300C,

i.e., through an aging effect, and domain switching could occur at relatively low temperatures

of around 100C.

As the sample is heated to more than 500C, thermal expansion of the PZT ceramic

occurs, leading to distortion, as indicated in Fig. 1(e). In this case, several grains are strained

severely at 500C, and convexity along the grain boundaries is observed at 550C, resulting

from the high compressive stress. At a sample temperature of 500C, the internal stress 

might be estimated as  = E    T = 105 MPa, where the thermal expansion coefficient 

= 4  10-6 /C [10] and the elastic constant E = 50 GPa. However, further analysis to assess

the stress value would be needed to understand clearly the deformation characteristics.

It is of particular interest that there is an especially dramatic alteration in

microstructural characteristics around the grains, i.e., at the grain boundaries, when the

sample is heated to more than 800C, as indicated by the arrows in Fig. 1(a). In this case, the

grain boundaries become bright, and this bright zone expands as the sample temperature is

increased further to 1000C. It can be seen from the high-magnification image in Fig. 1(f) that

there is a nanocrystalline microstructure in the bright zone, with a colander-like morphology

with low density being observed as the heating time is increased.

To further understand the microstructural characteristics of the PZT ceramic, SEM

observations and EDS analyses were carried out before and after heating at 1000C for 0, 3,

10, and 30 min, and the results are shown in Fig. 2. Note that each of these investigations was

performed on almost the same area. The EDS analysis examined four chemical elements: Ti,

Zr, Pb, and O. As can be seen from the SEM images, the grain size decreases with increasing
 6

sample temperature, the grains start to collapse after heating to 1000C for 10 min, and a

nanocrystalline microstructure (or flake morphology [11]) is formed after heating for 30 min.

Because bulk PZT ceramic was used in this study, a longer heating time (30 min) was needed

to obtain the nanocrystalline microstructure than was the case for the thin TEM sample. The

results of the EDS mapping showed that the distribution of the chemical elements changed on

heating. The element of Pb was sublimated with increasing the heating time, and rest of Pb

element was randomly distributed. Similar distribution was seen for Ti element. Interestingly,

in the sublimated zones (Pb), Zr element was detected, e.g., segregation of ZrO2. From Fig.

2(b), it can be seen that the amount of Pb clearly decreases with increasing heating time,

where PbO vaporization may have occurred leading to the segregation of ZrO2 [12]. On the

other hand, amount of O increases slightly due to the oxidation with Zr. It has been reported

that segregation of PbO is obtained at the grain boundaries [11,13], but it could not be

detected in our PZT ceramic. It has been also reported in the previous work that at annealing

temperatures exceeding 700C, there is diffusion of titanium element in PZT ceramics [4], but

this was not detected in our study.

To further understand the material characteristics of the PZT ceramic at 1000C,

EBSD analyses were carried out on the sample before and after heating at 1000C for 10 min.

The results are shown in Fig. 3. Note that the heated PZT ceramic was observed both near the

surface and inside the sample, namely, at several micrometers depth. Flake morphology of the

sample was observed on the surface of the PZT ceramic. As can be seen, before the heating

process, the lattice orientation is random, which is the normal lattice structure reported in

previous work [14]. However, it is clear that after heating to 1000°C, the lattice orientation

becomes {100} both near the surface and inside the sample; i.e., there is aggregation of

crystalline structure. Because of the distortion of the surface of PZT ceramic, thermal
 7

expansion occurred in each grain. To elucidate the material properties of the PZT ceramic

after heating, an attempt was made to conduct an EDS analysis inside the sample. The results

appear to indicate that the PZT ceramic consists of 8%Ti–18%Zr–62%Pb–14%O, which

implies no or weak sublimation of the ceramic. These results suggest that lattice orientation of

PZT ceramic can be imposed by the application of thermal energy. To verify this, TEM

observation was further carried out to understand the crystal orientation characteristics. Fig. 4

depicts the TEM image of PZT ceramic at 1000C for about 5 min. As seen, clear lattice

formation was detected, and the lattice orientation is different depending on the grain, which

is different trend compared to the result of EBSD. The reason behind this may be attributed to

the constraint condition, i.e., free surface for the TEM sample may make lattice formation

randomly. In contrast, bulk PZT ceramic for EBSD analysis can lead to the strong constraint

condition, which can be verified by the distorted sample surface, resulting in the organized

lattice formation. However, further analysis is required to interpret the different lattice

formation in the future.

4. Conclusions

The material properties of a PZT ceramic at temperatures up to 1000C have been

investigated directly by TEM, with in situ observation of lattice and microstructural

characteristics during sample heating. The microstructural characteristics change significantly

in various ways as the temperature is increased to 1000C. Domain-switching-like behavior is

detected around 100C. The initially disordered lattice changes to a uniform structure owing

to a reduction in internal stress when the temperature exceeds 300C. A further increase in

temperature to 600C causes significant thermal expansion, leading to distortion of the

sample. Finally, heating to more than 800C leads to the formation of an ordered
 8

nanocrystalline microstructure.

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ultrahigh temperature application, App. Phy. Lett. 96(2010)013506-1–3.

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94(2011)3153–3170.

9 K. Bamba, M. Okayasu, Effect of thermal energy on the domain switching characteristic of

PZT piezoelectric ceramic, J. Jpn. Soc. Mech. Eng. (2017) to be submitted.

10 Murata Manufacturing Co., Ltd. Piezoelectric Ceramic Sensor, p.8 (in Japanese).

11 S.M. Gupta, A.R. Kulkarni, Role of excess PbO on the microstructure and dielectric
properties of lead magnesium niobate, J. Mater. Res. 10(1995)953–961.

12 E.R. Nielsen, E. Ringgaard, M. Kosec, Liquid-phase sintering of Pb(Zr,Ti)O3 using PbO-

WO3 additive, J. Eur. Ceram. Soc. 22(2002)1847–1855.

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titanate-lead zirconate ceramics using microwave sintering, J. Eur. Ceram. Soc.
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piezoelectric ceramics on a nanoscopic scale, J. Eur. Ceram. Soc. 37(2017)145–159.
 9

Fig. 1. TEM micrographs of PZT ceramic at different temperatures. (a) Several grains at
temperatures ranging from 25C to 1000C. (b) Change in lattice orientation. (c) Disordered
lattice. (d) Deformation twinning; (e) Thermal expansion; (f) Nanocrystalline microstructure
and sublimation of Pb.

Fig. 2. (a) SEM micrographs and EDS analyses at different temperatures. (b) Changes in
chemical composition with increasing temperature.

Fig. 3. EBSD analysis of PZT ceramic before and after heating to 1000C, observed both near
the surface and inside the sample.

Fig. 4. TEM micrographs of PZT ceramic at 1000C, showing the lattice formation.
 (a) Several grains at temperatures ranging from 25C to 1000C.

25C 200C

Twin: Fig. 1(d)

Grain boundary (GB)

Different lattice orientation

1µm Fig. 1(b) High dislocation density: Fig. 1(c)

300C 600C

Distortion: Fig. 1(e)

900C 1000C

GB (bright zone) Fig. 1(f)

zone)
Fig. 1(a)
 (b) Change in lattice orientation
25C 50C 75C 100C

Different lattice orientation

0.2µm

(c) Disordered lattice (dislocation)

25C 200C 300C

High dislocation density

Low dislocation density

0.5µm

Fig. 1(b)(c)
 (d) Deformation twinning
25C 400C

Twin

528C 529C

700C

0.5µm

Fig. 1(d)
 (e) Thermal expansion and internal strain
500C 550C

GB
0.5µm High internal strain

(f) Nanocrystalline microstructure and sublimation of Pb

1000C (0 sec) 1000C for 180 sec

Sublimation

Nanocrystalline

Fig. 1. TEM micrographs of PZT ceramic at different temperatures: (a) Several grains at temperatures ranging from 25C to 1000C;
(b) Change in lattice orientation; (c) Disordered lattice; (d) Deformation twinning; (e) Thermal expansion and internal strain; (f)
Nanocrystalline microstructure and sublimation of Pb.
 (a) SEM micrographs and EDS analysis

Before heating 1000C for 3min 1000C for 10 min 1000C for 30 min
SEM

2µm Nanocrystalline
Pb

Sublimation of Pb
O
Zr

Segregation of Zr
Ti

Segregation of Ti

Fig. 2(a)
 (b) Amount of the chemical elements
Pb O
70 70
Amount of Pb element, %

60 60

Amount of O element, %
50 50

40 40

30 30

20 20

10 10

0 0
0 10 20 30 0 10 20 30
Heating time at 1000C, min Heating time at 1000C, min
Zr Ti
70 70
Amount of Zr element, %

Amount of Ti element, %

60 60

50 50

40 40

30 30

20 20
10 10
0 0
0 10 20 30 0 10 20 30
Heating time at 1000C, min Heating time at 1000C, min

Fig. 2. (a) SEM micrographs and EDS analyses at different temperatures. (b) Changes in chemical composition with increasing temperature.
 Before heating After heating at 1000C for 10 min
Surface Inside sample (several µm) Surface
IQ IPF+IQ IQ IPF+IQ IQ IPF+IQ

Distorted Flake
surface shape

110

001 100

Pole figure

5µm

Fig. 3. EBSD analysis of PZT ceramic before and after heating to 1000C, observed both near the surface and inside the sample.
 Grain boundary

Fig. 4. TEM micrographs of PZT ceramic at 1000C, showing the lattice formation.