Iran J Sci Technol Trans Sci

https://doi.org/10.1007/s40995-020-00990-5 (0123456789().,-volV)(0123456789().
,- volV)

RESEARCH PAPER

Synthesis and Microwave Dielectric Characterization of Ca1-xSrxTiO3,

Low-Loss Ceramics
Abid Zaman1 • Sarir Uddin2 • Nasir Mehboob1

Received: 31 March 2020 / Accepted: 16 September 2020

Ó Shiraz University 2020

Abstract
Microwave dielectric ceramics in the Ca1-xSrxTiO3 (0 B x B 0.7) composition series were fabricated via conventional
solid state, mixed oxides route. The structural, microstructural and microwave dielectric properties of the sintered samples
were investigated. The XRD patterns revealed the formation of a single-phase perovskite-structured compositions calcined
at 1000 °C for 3 h in air. The structure was observed to be transformed from noncentrosymmetric orthorhombic (Pnma) to
centrosymmetric cubic (Pm3m) at 0.5 B x. Microwave dielectric properties like relative permittivity (er), quality factor
(Qxf) and dielectric loss (tan d) were measured at relatively lower frequency for millimeter (mm) wave wireless
applications.

Keywords Microwave dielectrics
Perovskites
Solid state route
Structural transition

1 Introduction Russia by Gustav Rose in 1839 and named after a Russian

Microwave dielectric materials are frequently used in
wireless communication devices and broadcasting systems
(Sebastian 2008; Chen et al. 2015; Iqbal et al. 2011). The
dielectric component used in these electronic devices for
receiving and transmitting of signals is termed as dielectric
resonator (DR) reported first by Richtmyer in 1939
(Richtmyer 1939). A dielectric material to be used as a
resonator or dielectric antenna must satisfy three major
criteria such as high relative permittivity (er * 50) required
for miniaturization, high quality factor (Q 9 f * 5000
GH) for better selectivity and low temperature coefficient
of resonant frequency (sf * 0 ppm/°C) required for thermal
stability of the component (Sebastian 2008).
Among oxides microwave dielectric materials, CaTiO3-
based compositions possess relatively better microwave
dielectric properties (Sebastian 2008). Perovskite-struc-
tured CaTiO3 was discovered in the Ural Mountain of
& Sarir Uddin
sariruddin@uop.edu.pk
1
Department of Physics, Riphah International University,
Islamabad 44000, Pakistan
2
Department of Physics, Government College Hayatabad,
Peshawar 25000, Pakistan
mineralogist Count lev Aleksevich Von perovski
(1792–1856) (Sebastian 2008). At temperature above
1580 K, CaTiO3 exits in ideal cubic perovskite structure
with space group Pm3m, whereas at temperature below
1380 K, it is orthorhombic with space group of Pbnm (Ali
and Yashima 2005). The existence of a tetragonal phase
(I4/mcm) and of a body-centered orthorhombic phase
(Cmcm) has also been reported at intermediate tempera-
tures (Redfern 1996). CaTiO3 exhibits high relative per-
mittivity (er * 160), better quality factor
(Qxf * 7000 GHz) and an undesired large positive tem-
perature coefficient of resonant frequency (sf * 850 ppm/
°C) (Zheng et al. 2005; Liao et al. 2011). The dielectric
properties of CaTiO3 ceramics can be further improved by
introducing isovalent substitution such as Sr?2, Mg?2 or
Ba?2 at A-site of ABO3 perovskite-structured CaTiO3
(Yoshida et al. 1997; Lin et al. 2005; Yan et al. 2007; Hsu
and Chang 2012). Masashi Yoshida et al. (1997) fabricated
CaTiO3-based ceramics by substituting Nd for Ca and
obtained relatively better microwave dielectric properties
(er = 108, Q 9 f = 17,200 GHz). Xiangjun Lu et al. (2005)
obtained er = 78, tan d = 0.0006 and sf = ? 7 ppm/°C for
0.8Ca0.67(Nd,Mg)0.22TiO3-0.2(Li1/2Nd1/2)TiO3 ceramics.
Bassoli et al. (2008) investigated the defect chemistry of
Yb3?-doped CaTiO3 solid solutions both theoretically and

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Fig. 1 a XRD patterns of Ca1-

xSrxTiO3 (0 B x B 0.7)
ceramics sintered at 1300 °C in
air, b shifting of (121) peak to
lower 2h values with increasing
x

experimentally and revealed enhanced temperature-de-
pendent dielectric properties.
In the present study, structural, microstructural and
microwave dielectric properties of Ca1-xSrxTiO3 (0 B x
B 0.7) compositions at relatively lower frequency (MHz)
were investigated for mm wave applications.
(MD 300 s) using the Archimedes principle. The micro-
wave dielectric properties of the fabricated ceramic pellets
were measured by vector network analyzer (Agilent-
R3767CH).
3 Results and Discussion

2 Experimental 3.1 Phase and Microstructural Analyses

Solid solutions of Ca1-xSrxTiO3 (0 B x B 0.7) were fabri- Figure 1a shows the room-temperature XRD patterns of
cated via solid state, mixed oxides technique with an Ca1-xSrxTiO3 (0 B x B 0.7) ceramics sintered at 1300 °C
experimentally acceptable substitution of Sr2? from 0 to for 3 h in air. XRD analysis revealed the formation of the
70% for Ca2? ion. Precursor chemicals of CaCO3, SrCO3 single-phase base composition of CaTiO3 matched with pdf
and TiO2 with research grade purity of 99.5% were mixed card # (22–153) indicating orthorhombic structure with
according to the stoichiometric ratios. The powders were space group of Pnma (Ali and Yashima 2005; Redfern
ball milled in a polymer bottle with distilled water as 1996). The (1 2 1) peaks were observed to shift toward the
lubricant and zirconia balls as grinding media for 12 h. The lower 2h values (Fig. 1b) with increasing Sr2? contents in
slurry was poured into a beaker and dried in oven at 90 °C Ca1-xSrxTiO3. This shifting may be attributed to the sub-
and then calcined in alumina crucible at 1000 °C for 3 h stitution of relatively larger cation of Sr2? (RSr = 1.61 Å)
with 5 °C/min of heating and cooling rates in air. The for Ba2? (RBa = 1.44 Å) at the 12-fold coordinated A-site
calcined powder was pulverized with pestle and mortar in of the perovskite structure following the Bragg’s diffrac-
order to avoid agglomeration. The fine powder was pressed tion law (2dsinh = nk) (Shannon 1976). The variation in
in pellets of 10 mm diameter at 100 MPa with a uniaxial
pressure. The green pellets were sintered at 1300 °C for 3 h Table 1 Structural properties of Ca1-xSrxTiO3 (0 B x B 0.7) obtained
with 5 °C/min of heating and cooling rates in air. The from XRD Analysis
sintered pellets were polished and electroded for further x Structure Space group a(Å) b(Å) c(Å)
dielectric and microstructural characterizations.
The phase and microstructural analyses were carried out 0 Orthorhombic Pnma 5.4405 7.6436 5.3812
by using X-ray diffractometer (XRD) (JDX-3532, JEOL, 0.1 Orthorhombic Pnma 5.3800 5.4400 7.6390
Japan) with Cu Ka radiation of wavelength (k = 0.154 nm) 0.3 Orthorhombic Pnma 5.4750 5.4863 7.7579
and scanning electron microscope (SEM) (JSM-5910, 0.5 Cubic Pm3m 3.9050 3.9050 3.9050
JEOL Japan), respectively. The apparent bulk densities of 0.7 Cubic Pm3m 3.8980 3.8980 3.8980
sintered ceramic pellets were measured by densitometer

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Iran J Sci Technol Trans Sci

Fig. 2 SEM images of Ca1-

xSrxTiO3 (0 B x B 0.7)
ceramics sintered at 1300 °C for
3 h in air; a x = 0, b x = 0.1,
c x = 0.3, d x = 0.5, e x = 0.7,
indicating a slight decrease in
grain sizes with increase in x

Table 2 MW dielectric properties of Ca1-xSrxTiO3 samples sintered at

1300 °C with the previous reported structural change from
X S.T q (g/cm3) (er) tan d Q 9 f (MHz) orthorhombic (Pbmn) of pure CaTiO3 to cubic (Pm3m)
structure of SrTiO3 (Guevarra et al. 2007; Drews et al.
0.0 1300 °C/3 h 2.924 63.73 0.00018 85,144.51
1996).
0.1 1300 °C/3 h 3.284 68.67 0.00021 75,869.83 The cross-sectional SEM images of Ca1-xSrxTiO3
0.3 1300 °C/3 h 3.742 76.65 0.00027 58,340.47 (0 B x B 0.7) crashed ceramics sintered at 1300 °C for 3 h
0.5 1300 °C/3 h 3.611 86.62 0.00024 66,061.08 in air are shown in Fig. 2. The samples have almost round-
0.7 1300 °C/3 h 4.010 66.53 0.00064 24,807.36 shaped grains in the range of 0.5 9 0.5 lm2 to 2 9 2 lm2
ST sintering temperature, q mass density, er dielectric constant, sizes. A slight decrease in grain sizes was observed with
Q quality factor, f frequency, tan d dielectric loss increases in Sr2? indicating grain growth inhibition. The
obvious pores in the microstructure may result the
observed lower densities of the samples as listed in Table 2
the lattice parameters of the Ca1-xSrxTiO3 ceramics with which certainly affected the dielectric properties of the
the increase in Sr?2 content is shown in Table 1. The lattice samples. The density of samples may be increased by
parameters a, b and c abruptly decrease for 0.5 B x B 0.7, optimizing the sintering temperature and dwell time.
and the structure is transformed from noncentrosymmetric However, the presented observed morphology is consistent
orthorhombic to centrosymmetric cubic. This is consistent

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Fig. 3 a Variation of relative permittivity (er) and mass density (q) with increase in Sr?2 content b Variation of quality factor (Q9f) and
dielectric loss (tan d) with increase in Sr?2 content
with previously reported for CaTiO3-based ceramic com-
positions (Xiangjun et al. 2005; Jinfeng et al. 2006).
3.2 Microwave Dielectric Properties
The variation in microwave dielectric properties of Ca1-
2?
xSrxTiO3 (0 B x B 0.7) ceramics with Sr content sin-
tered at 1300 °C for 3 h is shown in Fig. 3. The dielectric
constant (er) of Ca1-xSrxTiO3 increased from 63.73 to 86.62
with increase in Sr?2 content from x = 0 to x = 0.5 and
drops to 66.53 with further increase in Sr?2 for x = 0.7.
The decrease in er for higher value of Sr?2 may be
attributed to the structure transformation from noncen-
trosymmetric orthorhombic to centrosymmetric cubic
structure as listed in Table 1. Pure SrTiO3 at room tem-
perature exhibited a centrosymmetric cubic structure with
tolerance factor of one (Howard and Zhang 2003; Guo
et al. 2012). The quality factor (Q) is frequency-dependent
dimensionless quantity and quantitatively expressed as a
product with frequency (f) (Sebastian 2008). The product
of quality factor and frequency (Q 9 f) decreases from
85,144.51 to 24,807.36 MHz with increase in Sr?2 content,
which may be attributed to the increase in dielectric loss as
listed in Table 2. The substitution of multi-ions at A-site of
perovskite structure may increase the movement of B-site
cations leading to an increase in dielectric losses and hence
a decrease in Q 9 f (Tohdo et al. 2006). Microwave
engineers find it helpful to characterize a microwave
dielectric material by the product Q 9 f (f measured in
GHz) which is assumed to be constant (Hao 2013; Moulson
and Herbert 1990). The theoretical justification for this is
as in the case of an ionic solid the optical mode of the
lattice vibration resonates at frequencies in the region
around 1013 Hz.
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Iran J Sci Technol Trans Sci
4 Conclusions
The phase, microstructural and microwave dielectric
properties of Ca1-xSrxTiO3 (0 B x B 0.7) ceramics fabri-
cated via mixed oxides, solid state route were investigated.
The phase analysis revealed the formation of single-phase
perovskite-structured compositions calcined at 1000 °C for
3 h. The samples exhibited orthorhombic structure for
0 B x B 0.0.3 and transform to cubic structure for
0.5 B x. The ceramics samples sintered at 1300 °C for 3 h
exhibited a maximum density of 4.010 g/cm3. The maxi-
mum value of dielectric constant (er ) observed was 86.62
for x = 0.5. The quality factor (Q 9 f) decreases from
85,144.51 MHz for x = 0 to 24,807.36 MHz for x = 0.7.
Acknowledgments The authors acknowledge the technical support
provided by Materials Research Laboratory (MRL) and Centralized
Research Laboratory (CRL), University of Peshawar, Pakistan.
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