Materials Letters 60 (2006) 1937 – 1942

www.elsevier.com/locate/matlet

Pyroelectric ceramics for infrared detection applications

Padmaja Guggilla a , Ashok K. Batra a,⁎, James R. Currie b , Mohan D. Aggarwal a ,
Mohammad A. Alim c , Ravindra B. Lal a,1
a
Department of Physics, P.O. Box 1268, Alabama A&M University Normal, AL 35762, USA
b
Avionics Department, NASA-Marshall Space Flight Center Huntsville, AL 35812, USA
c
Department of Electrical Engineering, P.O. Box 297, Alabama A&M University Normal, AL 35762, USA
Received 29 November 2004; accepted 12 May 2005
Available online 20 March 2006

Abstract

Pyroelectric and dielectric behavior of cation(s) modified lead zirconate titanate (PZT) ceramic has been studied for their use in infrared
detectors. Various materials' figures-of-merit for their use in infrared detector are calculated. The results are compared with several existing
candidate materials including PZT type ceramics.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Pyroelectric; Infrared sensor; PZT ceramics

1. Introduction PZT (lead zirconate titanate) based ferroelectric oxide

Pyroelectric Infrared detectors offer an advantage of room
temperature operation and wide spectral response. In the past
few decades, major thrust for infrared detection and the thermal
imaging has been used for military night vision, target
acquisition, and missile guidance. Non-military applications
include infrared detecting head in imaging system for product
inspection in faults isolation assuring quality, automotive vision
enhancement, fire detection and prevention, remote temperature
measurements, medical diagnostics (cancer and rheumatism
detection), and monitoring patients' burns. For these applica-
tions, efforts have been made to develop uncooled infrared and
imaging devices [1-8]. As a result of these efforts, the use of
crystalline ferroelectrics, such as triglycine sulfate (TGS),
polyvinyldifluoride (PVDF), strontium barium niobate (SBN),
lithium tantalate (LT), and ferroelectric pervoskite ceramics
have been developed [1-8].
⁎ Corresponding author.
E-mail address: ashok.batra@email.aamu.edu (A.K. Batra).
1
Present address: NASA Administrator's Fellow, Exploration Science and
Technology Division, XD40, NASA-Marshall Space Flight Center, Alabama
35812, USA.
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.05.086
ceramics, for use in pyroelectric infrared detection, offer
number of advantages over single crystalline materials such as
triglycine sulfate (TGS), lithium tantalate (LT), polyvinyldi-
fluoride (PVDF), etc. Ferroelectric oxide ceramics for use in
pyroelectric infrared detectors are relatively low cost to
manufacture by using standard mixed ceramic oxide proces-
sing steps, and also they are both mechanically and
chemically robust. Their good mechanical strength allows
large area wafers to be made, which can be easily machined
into thin sections. They are not hygroscopic as are high
pyroelectric performance TGS single crystals. Furthermore,
TGS single crystals' are fragile in nature which causes
technical difficulties in the processing. Also, the environmen-
tal temperature is a problem for using and storing the devices.
Ferroelectric materials used in pyroelectric IR detectors
operate only below the Curie temperature (Tc) because
above Tc they get depoled. Ferroelectric oxide ceramics also
have a high Curie temperature so that there is no danger of
depoling during normal usage over a wide range of ambient
temperatures (e.g., − 50 to 70°C). The pyroelectric perfor-
mance of PZT type ceramics can readily be modified by
inclusion of selected dopants (elements) into the lattice, and
thereby controlling important parameters such as pyroelectric
coefficient (p) and dielectric constants (ε′, ε″) which have
1938 P. Guggilla et al. / Materials Letters 60 (2006) 1937–1942

Table 1
Physical properties and figures-of-merit of various pyroelectric materials [4-14]
Parameter Units LiTaO3 TGS Mod. PZT PLZT [8] PLZT [14] PLTM [9] PSTM [9] PETM [9] STPZT1 STPZT2 BM740
(crystal) (crystal) (ceramic) (ceramic) (ceramic) (ceramic) (ceramic) (ceramic) (present (present (present
work) work) work)
P µC m− 2 K− 1 180 280 380 450 350 13.2 at Tc 6.14 at Tc 5.51 at Tc 379.5 408.5 300
ε′ – 47 38 290 700 1129 132,365 at Tc 6140 at Tc 5510 at Tc 1156.67 768.65 631.39
tan δ – 0.005 0.01 0.003 0.01 0.028 – – – 0.01866 0.0026 0.0026
ε″ – 0.235 0.38 0.87 7.0 31.612 – – – 21.58 2.0 1.640
c′ 106 J m− 3 K− 1 3.2 2.3 2.5 2.5 2.5 2.5 2.5 3.2 2.5 2.5 3.2
Tc °C 620 49 200 225 – 455 394 480 – – –
FV 10− 6 µC J− 1 m 1.19 3.2 0.524 0.25 0.124 0.00039 at Tc 0.0004 at Tc 0.0003 at Tc 0.131 0.213 0.15
FI 10− 6 µC J− 1 m 56.25 121.74 152 180 140 5.28 at Tc 2.45 at Tc 1.72 at Tc 151.8 163.4 93.75
FD 10− 6 µC J− 1 m 116.05 197.5 162.96 68.18 24.9 – – – 32.675 115.83 73.2

direct effect on the figures-of-merit (F) of the pyroelectric
materials.
Various perovskite ferroelectric ceramics such as PbTiO3
(PT)-based and Pb(ZrxTi1 − x )O3 (PZT)-based have been
reported to possess high figures-of-merit as materials for pyro-
electric infrared sensors [7-14]. Whatmore and Bell [7] have
proposed lead iron niobate–lead titanate ceramics modified by
the addition of uranium based ceramics for IR sensing appli-
cations. Czekaj et al. [9] investigated the pyroelectric properties
of the multi-component ferroelectric ceramic materials at
room temperature, on the basis of solid solutions of: PbTiO3–
PbZrO3–PbNb2/3Zn1/3O3–PbSb2/3Mn1/3O3–PbW1/2Mg1/2O3
(system I) and PbTiO3–PbZrO3–PbNb2/3Zn1/3O3–PbSb2/3
Mn1/3O3–PbNb2/3Mn1/3O3 (system II), prepared using hot
pressing technique. Suaste-Gomez et al. [10] reported the
pyroelectric properties of Pb0.88Ln0.08Ti0.98Mn0.02O3 (Ln = La,
Sm, and Eu) ferroelectric system. Nevertheless, there remains
immense interest in the improvement of the quality and per-
formance of these materials as requirements for future applica-
tions, in particular for military, space, and medical applications.
In the present investigation the results of lanthanum-
modified lead zirconate titanate (PLZT), denoted as STPZT-1
and MnO2 doped PLZT denoted as STPZT-2 and commer-
cially available modified lead zirconate titanate ceramic
(BM740) from Sensor Technology Limited, Canada [15] are
reported. BM 740 has been chosen as it exhibits low
frequency drift over normal working temperature and the
aging of permittivity is low [15]. This sample is also
understood to be a potential candidate for pyroelectric
applications. Due to the proprietary reasons the exact cation
(s) modified recipe of BM740 remained unknown. It is
worthy to mention that these ceramics have been prepared
using optimized recipe and proprietary processing technology.
Their usefulness in pyroelectric infrared detectors is compared
with the results of other candidate pyroelectric materials. The
properties and materials' figures-of-merit of modified lead
zirconate ceramics [7-10] are listed in Table 1 adapted from
Refs. [7-14] along with the results obtained in the present
research for comparison purposes.
2. Experimental
Smart electroceramic samples were prepared using con-
ventional ceramic processing technique [16,17] as depicted in
the flowchart of Fig. 1. There may be some minor variations
to the processing steps involving partial or full batch
calcining stages but again may be called as the conventional
processing steps. It is not a constant practice to achieve nano-
particles for the smart electroceramics through ball milling.
Usually conventional balling limits the size on the order of
micron(s). Since commercial facilities have been used to
obtain the samples in this study, it is confidently asserted that
conventional processing steps outlined in Fig. 1 is the most
appropriate flowchart for the end systems used in this study.
Due to the severe proprietary reasons the exact fabrication
processes used in making commercial products (Sensor
Technology Ltd., Canada) [15] having a more detailed
flowchart is restricted. However, some variations in the
processing steps are possible in any manufacturing facility.
The manufacturing facilities usually adopt the minimum

Fig. 1. Flowchart of conventional ceramic sample preparation.

 P. Guggilla et al. / Materials Letters 60 (2006) 1937–1942
handling but low-cost processing route in order to satisfy
customer demands within the budget for the end products. The
end products always satisfy a minimum level of consistent
performance having a set of established or reproduced
satisfactory properties.
The samples STPZT-1 and STPZT-2 are not commercial
samples but laboratory recipe fabricated using production
equipment facility and proprietary technology of Sensor
Technology. The BM740 samples are commercially prepared
by the same organization. It is apprehended that these three
kinds of samples employed identical equipment facility to
achieve the end samples. The recipe for STPZT-1 and STPZT-2
has been designed such that each sample can be represented as
Pb 0.94La0.06Zr 0.65Ti 0.35O 3, and Pb0.94 La0.06Zr 0.65Ti 0.35O 3
+ 0.5 wt.% MnO2, respectively.
The electrical measurements are conducted on a disc having
13.75 mm in diameter and 0.9 mm in thickness. Silver electrode
is screen printed on two opposite sides of each disc sample.
After that each sample is poled at an appropriate electric field.
The dielectric permittivity values (ε′ and ε″) were obtained by
measuring terminal parallel capacitance Cp and loss tangent (ε″/
ε′) at a fixed measurement frequency of 1kHz using QuadTech
1920 LCR meter. The amplitude of the peak-to-peak ac signal
voltage (Vac) used for this purpose was 10 V/cm. This set-up
employed an in-house designed and constructed three-terminal
cell to accomplish the terminal capacitance measurement. For a
polycrystalline material, a large portion of the ac signal voltage
is experienced across the grain boundaries than the grains due to
the high resistance of the grain boundaries. The high resistance
of the grain boundaries is caused from the discontinuity in the
crystalline structure of the grains demarcated by the grain
boundaries and often having space charge region at equilibrium
condition across them.
The pyroelectric current Ip was measured using Byer and
Roundy method [18], and the pyroelectric coefficient (p) was
calculated using a relationship:
   
=
Ip dT
p¼ ; ð1Þ
A dt
where A is the electrode area (identical areas for the opposite
electrodes used in each sample), and dT/dt is the rate of change
of temperature. The pyroelectric current is measured using a
6517 Keithley electrometer, and temperature is measured by the
HP34970 digital multi-meter using type K thermocouple. The
automated data acquisition was accomplished using LabVIEW
6i software. Thus, the entire raw data were collected in a PC by
storing in a file. The schematic of the complete set-up is shown
in Fig. 2 and details are described elsewhere [19].
By using the foregoing electrical parameters the following
materials' figures-of-merit [1,7] for assessing the characteristics
of single element pyroelectric detector, operating in optimum
manner, were calculated as follows:
FI = p/c′ for high current responsivity,
FV = p/(c′ε′) for high voltage responsivity, and
FD = p/(c′√ε″) for high detectivity,
1939
Fig. 2. Block diagram of the pyroelectric and dielectric response measurement
set-up.
where p, c′, ε′, and ε″ are the pyroelectric coefficient, the
volume specific heat, and the real and imaginary parts of the
dielectric constant, respectively.
3. Results and discussion
Fig. 3 shows the variation of pyroelectric coefficient (p), dielectric
constant (ε′) and loss tangent (tan δ) of STPZT-1, STPZT-2 and BM740
ceramic samples with temperature. In general, all these parameters
increase with temperature which is typical of ferroelectrics due to
atomic displacements. In ferroelectric ceramics, increase in ε′ and loss
tangent with temperature can be attributed to the change in the space
charge regions across the grain boundaries involving consecutive
grains in addition to the charge trapping processes at the grain
boundary interfaces [20].
3.1. Dielectric and pyroelectric behavior
In the case of STPZT-1, ε′ increases with temperature while tan
δ(ε″/ε′) remained nearly in the same range of values. Combining
these two observations in a concurrent manner it is unlikely to have
the space charge region nearly unaltered indicating generation of
carriers in the grains. Also the ε′ (or Cp) has increased presumably
from the charge trapping at the grain boundary interfaces. If none of
these two conditions (carrier generation and trapping) are ruled out
then both mechanisms are the dominant behaviors in a polycrystalline
material regardless of the ferroelectric properties. This is primarily a
consideration from the polycrystalline nature of the ceramic materials
as a whole. If the carrier concentration increases in the grain with
increasing temperature, then this situation imposes a reduction in the
space charge regions causing the terminal capacitance (or Cp) to
increase. Thus, space charge region contributes to only Cspace-charge
term regardless of the trapping effect. Considering the influence of
the charge storage process or trapping in the space charge region
across the grain boundaries then the frequency dependent term arises
as dQ/dVac to the terminal capacitance under the ac small-signal
measurements. Further this behavior is attributed to the trapping and
de-trapping behavior under applied ac condition. In this case the
terminal capacitance (ε′ or Cp) reflects geometric contribution as well
as trapping (or de-trapping) contribution to the terminal capacitance.
The geometric contribution is essentially associated with the space
1940 P. Guggilla et al. / Materials Letters 60 (2006) 1937–1942
Fig. 3. The variation of pyroelectric coefficient and dielectric constants (ε′, tan δ) with temperature.
charge region and the terminal capacitance can be expressed [21-23]
as:
Cp ¼ Cspacecharge þ dQ=dVac :
When the contribution of the trapping dominates without affecting
geometric capacitance only then tan δ can nearly remain unchanged
assuming the increment of Cp taking place only via the dQ/dVac term.
In the event if the conductance increased via thermal generation of
the carriers for the same temperature range then ε′ will increase
indicating increase in ε″. The carrier enhancement is more likely a
feasible concept as the piezoelectric material system contains multiple
cations that can ionize at elevated temperatures to contribute as
carriers in the grains. The increase in the carrier concentration in the
grains, thus, gives rise to the shrinking of the Cspace-charge term while
dQ/dVac increases at a faster rate for the same range of temperature
due to the trapping process at the grain boundary interfaces. Overall,
this is a complicated two-fold simultaneously operative mechanism
for the polycrystalline systems. Nevertheless, these concepts need
subsequent investigation as a future task.
In the case of STPZT-2 and BM740 samples, there is an indication
of the donor enhancement due to the thermal ionization of the cations
causing increase in terminal capacitance (ε′ or Cp). Accordingly tan δ
has also increased reflecting enhanced conductance without affecting
the charge storage contribution at the grain boundary interfaces or
within the space charge regions. Foregoing analogy holds in this case
as Cspace-charge term increases with or without the frequency dependent
ð2Þ term dQ/dVac contributing toward terminal ε′. The tan δ term increases
reflecting the ratio of ε″/ε′ increases wherein the growth of ε″ may be
faster or moderate rate while shrinking of ε′ is a faster process causing
an eventual increase of tan δ or ε″/ε′. The plausible mechanism(s)
operative for STPZT-2 sample has caused faster rise both for ε′ and ε″/
ε′ (or tan δ) while the same mechanism(s) may dominate in the BM740
sample having a little slower rise (or enhancement) for both the
parameters.
3.2. Figures-of-merit
Table 1 lists the values obtained for dielectric constants and loss,
pyroelectric coefficient and calculated material figures-of-merits for
STPZT-1, STPZT-2 and BM 740 ceramic samples at 50 °C along with
published data of other important materials [1-14] including PZT type
ceramics for comparison. For calculations of figures-of-merit of the
samples fabricated and investigated in the present work, the default
values of volume specific heat (c′) were chosen from the literature. The
values obtained for the figures-of-merit for high voltage responsivity in
the STPZT-2 (PLZT) sample is higher than reported value of PLZT
based ceramic as listed in Table 1 [8,9,14] except for FI reported by
 P. Guggilla et al. / Materials Letters 60 (2006) 1937–1942
Kobune et al. [8]. The values obtained for all the figures-of-merit for
STPZT-2 (PLZT + MnO2) is higher than the STPZT-1 sample due to
achieving low dielectric constant and high pyroelectric coefficient
values. This observation may be attributed to the effect of Mn-doping,
in that the recharging (Mn4+ → Mn3+ → Mn2+) of Mn ions partially
substituted at the B-site (for Zr4+ or Ti4+ ions) compensates for
excessive charge of La3+ to the A-site (Pb2+ ions) caused by La-
substitutions in the A-sites, as has been reported by Glinchuk et al. [24].
This type of situation in a high resistivity and low dielectric loss case is
important for the IR sensors. Furthermore, in ceramic oxide ferro-
electrics, the values of the dielectric constants (ε′ and ε″) and
pyroelectric coefficient (p) depend on grain size, grain size distribution,
degree of porosity in the microstructure [25,26] and on the domain
structure including the dynamics along with the defect structure or
defect chemistry of the lattice sites formed during sintering.
The doping process of the grains occurs via cation interstitials or
anion vacancies during the sintering dynamics of the piezoelectric
ceramic bodies. Since the resulting composite constitutes cations, it is
more than likely that the cation interstitials is a plausible concept for
ionizing and subsequent donor enhancement in the grains. Again anion
vacancies are also not ruled out. Additional studies will be conducted to
ascertain the possible underlying mechanism(s). Their effect in
reducing the dielectric constants and enhancement of pyroelectric
coefficient cannot be ruled out too. The reduction in dielectric constant
and loss is also due to the low frequency polarizability in these
materials. This may be because once the oxygen vacancies generated
(in order to maintain the overall electro-neutrality due to Mn3+ for B-
site modification) are locked into defect dipole pairs, they are much
more immobile in STPZT-2 than STPZT-1. Suaste-Gomez et al. [10]
reported the pyroelectric properties of Pb0.88Ln0.08Ti0.98Mn0.02O3
(Ln = La, Sm, and Eu) ferroelectric system represented as PLMTM,
PSTM and PETM respectively in Table 1. The values obtained for
pyroelectric coefficients, even at Tc, are lower than values obtained in
our samples. Pyroelectric properties of the multi-component ferroelec-
tric ceramic materials, on the basis of solid solutions of: PbTiO3–
PbZrO3–PbNb2/3Zn1/3O3–PbSb2/3Mn1/3O3–PbW1/2Mg1/2O3 (system
I) and PbTiO3–PbZrO3–PbNb2/3Zn1/3O3–PbSb2/3Mn1/3O3–PbNb2/3
Mn1/3O3 (system II), prepared using hot pressing technique, have been
investigated at room temperature by Czekaj et al. [9] for both tetragonal
(T) and rhombohedral (R) phase areas as well as morphotropic (M)
phase boundary. The average value of the pyroelectric coefficient
obtained in the M-region was 500µC m− 2 K− 1 and 400µC m− 2 K− 1
for system II and system I respectively. The maximum value of dielec
tric permittivity obtained in the M-region was 1380 and 1440,
respectively.
The value obtained for pyroelectric coefficients of system I and
system II make them prospective candidate for practical applications as
materials for pyroelectric detectors for high current responsivity
however the values obtained for FV in samples studied are better. Based
on investigation of Suaste-Gomez et al. [10] and Czekaj et al. [9], the
samples investigated in the present study, in particular STPZT-2 and
BM740, are more attractive for use in IR sensors. Furthermore, in the
present work complete study was undertaken in terms of evaluation of
dielectric constant and loss, and pyroelectric coefficient along with
their variation with temperature. The proprietary modified PZT
(BM740) which has high figures-of-merits for current responsivity
due to low loss and dielectric constant is also attractive for use in
infrared sensing applications compared with known materials such as
lithium tantalate [13]. It is worthy to mention that properties (Fig. 3) of
ceramic studied do not change greatly up to 100°C, thus their
performance in infrared detectors shall not degrade with much change
in ambient or operating temperatures.
1941
4. Conclusions
Pyroelectric and dielectric properties of various ceramics
such as STPZT-1 (PLZT), STPZT-2 (PLZT + MnO2) and
BM740 (modified PZT) for their applications in infrared
sensors are extensively studied and compared with other
candidate materials including PZT-type ceramic studied by
other researchers. The material figures-of-merits at 50 °C are
calculated from measured parameters (dielectric constants and
pyroelectric coefficient) for their use in pyroelectric infrared
detectors. From the viewpoint of pyro-sensor applications,
investigated ceramics, namely STPZT-2 and BM740, are
remarkably attractive due to their large pyroelectric coefficient
and low dielectric loss. It is worthy to mention that the materials
investigated are also capable of high operating temperature (up
to 100°C) applications. However, their actual use in infrared
detector shall determine if proposed enhancement can be
realized in practice. It can also be concluded that the proprietary
technology used in fabrication of ceramics is appropriate for the
fabrication of ferroelectric ceramic oxides. Further work is in
progress to use these materials in thick films fabrication so that
there performance can be assessed for their use in thermal
imaging devices.
Acknowledgments
This work is supported by US Army SMDC Grant #
DASG60-03-1-0003 and NSF Grant HRD-0236525. Authors
sincerely thank Mr. G. Sharp for the fabrication of the sample
holder for capacitance measurements. Thanks are also due to the
staff members of Sensor Technology Ltd., Canada for
cooperation and providing relevant suggestions. Keen interest
of Drs. D. Frazier and B. Penn of NASA-MFSC in the uncooled
infrared detector work are greatly appreciated.
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