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CERAMICS
INTERNATIONAL
Ceramics International 39 (2013) 579–583
www.elsevier.com/locate/ceramint

Phase structure, band gap and microwave dielectric properties

of Ba8Ti3Nb4  xSbxO24 ceramics
Liang Fangn, Congxue Su, Zhenhai Wei, Huanfu Zhou, Hui Zhang
State Key Laboratory Breeding Base of Nonferrous Metals and Specific Materials Processing, Key laboratory of Nonferrous Materials and
New Processing Technology, Ministry of Education, Guilin University of Technology, Guilin 541004, China
Received 4 June 2012; received in revised form 21 June 2012; accepted 21 June 2012
Available online 29 June 2012

Abstract

High dielectric constant and low loss ceramics in the Ba8Ti3Nb4  xSbxO24 (x¼ 0–2) system were prepared by conventional solid-state
ceramic route. As x increased from 0 to 1.5, a single phase with hexagonal 8H perovskite structure was formed and the band gap values
increased from 3.38 to 3.47 eV. However, the Sb2O3 secondary phase was detected as the x reached 2. The optimum sintering
temperature was reduced from 1460 to 1380 1C, the quality factors (Q  f) were effectively enhanced from 22,900 to 38,000 GHz and tf
was significantly lowered from 110 ppm/1C to 2 ppm/1C, whereas the dielectric constant decreased from 49 to 35. A good combined
microwave dielectric properties with er ¼37.5, Q  f ¼38,000 GHz, tf ¼15 ppm/1C were obtained for x¼ 1.5.
& 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Sintering; C. Dielectric properties; D. Perovskites; D. Niobates

1. Introduction et al. [5]. classified AnBn  1O3n hexagonal perovskites into

shifted and twinned structures, depending on the stacking
The recent advances in the telecommunication systems sequences of their AO3 layers. Shifted perovskites can be
have attracted considerable attention towards the micro- represented by a packing sequence (hhccyc) while twinned
wave ceramic dielectric resonators. Dielectric resonators perovskites can be represented by the packing sequence
(DRs) are extensively used in microwave devices such as (hccyc) which is favored by high values of n (number of
filters, oscillators, and DR antennas. To meet the require- octahedra layers within a perovskite blocks) and t (Gold-
ments of DRs applications, the materials should have high schmidt tolerance factor). The microwave dielectric prop-
dielectric constant er, relatively high quality factor Q, (Q  f erties of some B-site deficient twinned perovskites such as
value is usually used as a figure of merit) and near zero Ba8Ti3Nb4O24, Ba8MTa6O24 (M ¼ Mg, Zn, Ni, Co, Cu)
temperature coefficient of resonant frequency (tf). Among and Ba8Ga4  xTa4 þ 0.6xO24 were reported successively
current commercial microwave dielectric materials, exten- [6-12]. These materials exhibit high er in the range of
sive attention has been focused on perovskite type structure 27–49, high quality factors Q  f up to 90,000 GHz, but
materials, especially the tantalite and niobate perovskites a relatively large tf over 30 ppm/1C. Among them,
due to the high polarizability of Ta5 þ and Nb5 þ [1]. Ba8Ti3Nb4O24 possesses an encouraging high er of 49
Recently, there has been a growing interest in the and a high Q  f (23,500 GHz), but its relatively high tf
dielectric properties of hexagonal perovskites [2–4], and ( 120 ppm/1C) precludes its use as DRs device [6,7].
many researches have been focused on B-site cation defi- Recently, Yokoi et al. [13] reported the substitution of
cient hexagonal perovskites with the formula AnBn  1O3n Ta for Nb in Ba8Ti3Nb4  xTaxO24 solid solutions could
(n=4–8) which are based on cubic close packing (c) and reduce the tf from 125 to 76 ppm/1C and increase Q  f
hexagonal close packing (h) of the AO3 layers. Trolliard value. Therefore, the substitution of the other elements in
this system is necessary in order to further adjust the tf
n
Corresponding author. Fax: þ 86 773 5896436. values. The ionic radius of Sb5 þ (0.6 Å) is very similar to
E-mail address: [email protected] (L. Fang). that of Nb5 þ (0.64 Å) [14]. Moreover, Sb substitution for

0272-8842/$36.00 & 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
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580 L. Fang et al. / Ceramics International 39 (2013) 579–583

Nb has been reported to effectively reduce tf in the

Ba8M(Nb6  xSbx)O24 (M ¼ Zn, Mg) and Mg4(Nb2  xSbx)
O9 (x ¼ 0–1) ceramics [1,15,16]. In this paper, the
Ba8Ti3Nb4  xSbxO24 solid solutions were prepared, and
the influences of the Sb substitution for Nb on the
structures, sintering behaviors and the microwave dielec-
tric properties of Ba8Ti3Nb4  xSbxO24 (x=0–2) ceramics
have also been investigated.

2. Experimental procedure

Ba8Ti3Nb4 xSbxO24 (x=0–2) ceramics were prepared by

conventional mixed oxide route by using high-purity powders Fig. 1. X-ray diffraction pattern of Ba8Ti3Nb4  xSbxO24 (x¼ 0–2) cera-
of BaCO3 (99.9%), TiO2 (99.99%), Nb2O5 (99.99%), and mics sintered at 1420 1C for 6 h.
Sb2O3 (99%). Stoichiometric proportions of the above raw
materials were milled in alcohol using zirconia balls for 4 h.
The mixtures were dried and subsequently calcined at 1350 1C Table 1
for 12 h. The calcined powders were milled for 6 h and the The unit cell parameters of Ba8Ti3Nb4  xSbxO24 (x¼ 0–2) ceramics.
slurry was dried in agate mortar and ground well. Polyvinyl x c/a
a (Å) c (Å) Vm (Å3)
alcohol (5 wt%) was added to the powders as binder, again
ground well and dried. The powders were then pressed into 0 5.7941 18.8674 3.2563 548.55
cylindrical disks with 12 mm diameter and 7 mm height under 0.3 5.7929 18.8648 3.2565 548.16
0.6 5.7918 18.8630 3.2568 547.99
a pressure of 200 MPa. The samples were fired at 550 1C for
0.9 5.7905 18.8593 3.2570 547.63
4 h to remove the organic binder and then sintered in air on a 1.2 5.7892 18.8559 3.2571 547.28
Pt foil at 1360–1480 1C for 6 h. The sintered samples were 1.5 5.7871 18.8503 3.2573 546.72
pulverized in agate mortar and pestle and ground into powder
2.0 5.7869 18.8472 3.2569 546.60
for XRD. An X-ray diffractometer (CuKa1, 1.54059 Å, Model
XPert PRO, PANalytical, Almelo, the Netherlands) was used
for phase analysis. In order to investigate the band gap energy Ba8Ti3Nb4O24 (PDF files 00-054-1170), which has a hex-
of Ba8Ti3Nb4 xSbxO24(x=0–1.5) solid solutions, the room agonal perovskite structure (space group P63/mmc) based
temperature UV–vis absorption spectra of the Ba8Ti3Nb4 x on 8H (hccc)2 closed-packed arrangement of BaO3 layers
SbxO24 powders were measured in the range of 200–800 nm [5]. The fully indexed XRD patterns confirmed that
using UV–vis spectrophotometer (UV-3600,Shimadzu) with Ba8Ti3Nb4  xSbxO24 ceramics are single phase as x r 1.5,
BaSO4 coated integration sphere. The apparent densities of the and the presence of Sb2O3 phase was detected at x ¼ 2.
sintered samples were measured by the Archimedes method. With increase in x from 0 to 1.5, diffraction peaks of the
The theoretical densities of the samples were calculated using samples were slightly shifted to higher angles, which was
the least-square method. The surface microstructures of the due to the difference in the ionic radii between the Sb5 þ
samples were examined using a field emission scanning and Nb5 þ [14]. The lattice parameters of the samples were
electron microscope (FE-SEM, Model S4800, Hitachi, Japan). refined by least squares method and are shown in Table 1.
The microwave dielectric properties were obtained using a It is obvious that the lattice constants a, c and V decrease
network analyzer (Model N5230A, Agilent Co., Palo Alto, with increasing substitution of Sb content, which is mainly
Canada) and a temperature chamber (Delta 9039, Delta attributed to smaller ionic radius of Sb5 þ than that of
Design, San Diego, CA). The temperature coefficient of Nb5 þ .
resonant frequency (tf) was measured in the temperature The room temperature UV–vis absorption spectra are
range from 25 1C to 85 1C. The tf value was calculated as shown in Fig. 2, the ultraviolet absorption edge of Ba8Ti3-
follows: Nb4  xSbxO24 (x ¼ 0–1.5) has a small blue shift with
increasing concentration of Sb. The energy gap of the
f85 f25
tf ¼ ð1Þ samples can be calculated as follows [17]:
60  f25
ðahuÞ1=n ¼ AðhuE g Þ ð2Þ
where f85 and f25 are the resonant frequencies at 85 1C and
25 1C, respectively. where A is absorption constant, hu is the photon energy, Eg
is the energy gap and n depends on the nature of transition.
3. Results and discussion In addition, absorption coefficient a is proportional to the
quantity F(RN) and thus a can be substituted with F(RN).
The X-ray diffraction (XRD) patterns of Ba8Ti3Nb4  x The reflectance spectra are according to the Kubelka–
SbxO24 (x=0–2) ceramics sintered at 1420 1C for 6 h are Munk theory. Based on the best linear fit in the lower
given in Fig. 1. All the peaks can be indexed according to absorption region [18,19], n=1/2 is used for these samples.
 L. Fang et al. / Ceramics International 39 (2013) 579–583 581

Fig. 2. The room temperature UV–vis absorption spectra of Ba8Ti3 Fig. 4. The variations of apparent density of Ba8Ti3Nb4  xSbxO24
Nb4  xSbxO24 (x¼ 0–1.5). ceramics with different sintering temperatures.

promoted grain growth, and a relatively dense microstruc-

ture with grains size in the range from 15 to 20 mm in
length was achieved for the specimen sintered at 1380 1C.
Denser microstructure without pores and a relatively
uniform plate-like grains with size in the range of 25–
40 mm has been achieved at 1400 1C, and exaggerated grain
growth with large grains (4 40 mm) was observed in the
ceramic sintered at 1440 1C due to over-sintering.
Upon sintering at the optimized temperature, the cera-
mics can have excellent microwave dielectric properties.
The variations in the dielectric constants and quality
factors of the ceramics as a function of compositions x
are shown in Fig. 6. The dielectric constant linearly
decreased from 49 to 35 as x increased from 0 to 2. In
general, er can be well interpreted by the sum of ionic
polarizabilities of individual ions ðaTD Þ and per molar
Fig. 3. hu–(F(RN)hu)2 curve of the samples. volume (Vm) according to Clausius–Mossotti equation:
1 þ 2baTD =Vm
2
The graph between (F(RN)hu) and hu is shown in Fig. 3. er ¼ ð3Þ
1baTD =Vm
It can be observed that the band gap energies increase
from 3.38 eV for x ¼ 0 to 3.47 eV for x ¼ 1.5. The band gap where b ¼ 4p/3. The decreasing dielectric constant was
of Ba8Ti3Nb4O24 is very close to the previous report mainly due to the decreasing value of aTD/Vm from 0.192
(3.4 eV) obtained by impedance spectroscopy measure- for x ¼ 0 to 0.182 for x ¼ 2 since the ionic dielectric
ments [7]. In the microwave frequency, the dielectric loss polarizability (aD) (1.18 7 0.49 Å3) of Sb5 þ ions [20] is
is proportional to the conductivity, which is decreased as lower than that of Nb5 þ ions [21]. The quality factor Q  f
the band gap increased, then the increase of band gap values increased gradually from 22,900 to 38,000 GHz as x
might reduce the intrinsic dielectric loss and hence the increased to 1.5, and then decreased at x ¼ 2. Ogawa et al.
Q  f values increase. [16] suggested that the Sb substitution for Nb enhances the
Fig. 4 presents the apparent densities of the Ba8Ti3 covalency of Sb–O bond and hence the Q  f values
Nb4  xSbxO24 (x¼ 0–2) ceramics as a function of sintering increase and er decreases. The lower quality factor for
temperature. The apparent densities of ceramics increase the samples with x ¼ 2 may be attributed to the formation
with increasing sintering temperature, reach a maximum of secondary phases as mentioned above.
value and then decrease. The maximum values of density The temperature coefficients of resonant frequency (tf) was
for Ba8Ti3Nb4  xSbxO24 (x ¼ 0–2) ceramics are more than adjusted from 110 to 2 with increasing Sb content from 0 to 2
95% of theoretical density. The optimum sintering tem- (as shown in Fig. 7), which is also similar to those of
perature of Ba8Ti3Nb4  xSbxO24 ceramics was slightly Ba8M(Nb6 xSbx)O24 (M¼ Zn, Mg) (x¼ 0–2.4) [1,15] and
reduced from 1460 to 1380 1C with increase in x value Ba3MNb2 xSbxO9 (M=Mg, Ni, Zn) [22]. Two mechanisms
from 0 to 2. Fig. 5(a–d) shows the FE-SEM micrographs [23–25] determine the tunability of tf in perovskites and related
of the surfaces of samples with x ¼ 1.5 sintered at different compounds: one is dilution of the average ionic polarizability
temperatures for 6 h. A porous microstructure and small and the other is the onset of octahedral tilt transitions induced
grains below 15 mm were observed in the specimen sintered by decreasing tolerance factor. Tolerance factors (t) are greater
at 1360 1C. The increase of the sintering temperature than 1 in Ba8Ti3Nb4 xSbxO24 solid solutions, which rules out
582 L. Fang et al. / Ceramics International 39 (2013) 579–583

Fig. 5. FE-SEM images of the surfaces of Ba8Ti3Nb2.5Sb1.5O24 ceramics sintered at different temperatures: (a) 1360 1C; (b) 1380 1C; (c) 1400 1C;
(d) 1440 1C.

the possibility for an octahedral tilting transition. So the

primary mechanism of tf tunability is attributed to the
reduction of the average ionic polarizability. Zhou et al.
[26,27] reported a linear relationship between tc and er
and therefore also between tf and er. In this work, a similar
linear trend (shown in Figs. 6 and 7) is apparent for
Ba8Ti3Nb4 xSbxO24 samples, also implying that tf decreases
as the er diminishes.

4. Conclusion
Fig. 6. The variations of er and Q  f of Ba8Ti3Nb4  xSbxO24 ceramics
Ba8Ti3Nb4 xSbxO24 (x¼ 0–2) ceramics were prepared
with x.
through a mixed oxide solid state sintering route at 1360–
1480 1C. A single phase with hexagonal 8H perovskite
structure was formed in the range 0rxr1.5, while second-
ary phase appeared at x¼ 2. The optimized sintering tem-
perature was reduced from 1460 to 1380 1C. The substitution
of Sb for Nb could effectively improve the quality factor and
reduce tf values. As the x values increased to 1.5, the band
gap values increased from 3.38 to 3.47 eV, quality factor
Q  f effectively enhanced from 22,900 to 38,000 GHz. In the
range of x¼ 0 to 2, tf value improved from 110 to 2 ppm/1C,
whereas er decreased from 49 to 35.

Acknowledgment

This work was supported by Natural Science Founda-

Fig. 7. The variations of tf of Ba8Ti3Nb4  xSbxO24 ceramics with x. tion of China (nos. 50962004, 21061004 and 51102058),
 L. Fang et al. / Ceramics International 39 (2013) 579–583 583

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