Materials Letters 61 (2007) 3357 – 3360

www.elsevier.com/locate/matlet

Effects of Y2O3 addition on microwave dielectric characteristics

of Al2O3 ceramics
K.X. Song, S.Y. Wu, X.M. Chen ⁎
Department of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China
Received 28 June 2006; accepted 13 November 2006
Available online 30 November 2006

Abstract

Microwave dielectric characteristics of alumina ceramics with yttria addition were investigated. The sintering temperature was lowered, and the
dielectric constant (εr) did not remarkably change by adding yttria. The microwave dielectric loss (tan δ) increased from 8.4 × 10− 5 to 2.2 × 10− 4,
due to the presence of Al5Y3O12 secondary phase. The grain size had significant effects on the dielectric loss, and there was an optimum grain size
where the dielectric loss reached the minimum.
© 2007 Published by Elsevier B.V.

Keywords: Alumina; Microwave dielectric properties; Microstructures; Yttria

1. Introduction microcracks [10,11]. Furthermore, as revealed by far infrared

Recently, due to the rapid development of microwave com-
munication technology, the resonators and filters of dielectric
ceramics have received much scientific and commercial atten-
tion [1–5]. Alumina is an important electroceramic material
with ultra-low dielectric loss (tan δ b 10− 5) and low dielectric
constants (εr ∼ 9.8), which has applications in microwave and
millimeter-wave communication fields from 10 to 300 GHz
frequency band, and also has application as resonators for ultra-
stable oscillators in clocks and as substrates [6–9]. For these
applications, the most important issue is how to achieve the
ultra-low dielectric loss. So far, many papers have been pub-
lished to report the origins of dielectric loss, which fall into two
categories: intrinsic and extrinsic. Intrinsic loss is dependent on
the crystal structure and can be described by the interaction of
the phonon with the ac electric field. The ac electric field alters
the equilibrium of the phonon system and the subsequent
relaxation is associated with the energy dissipation. Extrinsic
losses are associated with imperfections in crystal structure,
e.g., lattice disorder, point defects, dislocations, grain bound-
aries, random crystalline orientation, impurities, porosity and
spectroscopy and later confirmed by microwave studies at
cryogenic temperatures, the major contribution to microwave
dielectric loss of commercial DRs is of extrinsic origin [12–15].
Alford et al. have made a profound investigation of the extrinsic
loss of polycrystalline alumina [6,7,16–18]. By doping alumina
with titanium dioxide, the dielectric loss was decreased from tan
δ = 2.7 × 10− 5 to tan δ = 2 × 10− 5. A dielectric absorption was
observed in magnesia doped alumina at about 100 MHz, and the
doping with iron did not change the dielectric spectrum of
alumina at high frequencies, where tan δ = 2.7 × 10− 4, and also
the humidity has obvious effects on microwave dielectric loss of
porous alumina [19–21].
It is well known that doping a little amount of Y2O3 can
inhibit the grain growth in alumina ceramics. To the best of the
author's knowledge, there are no reports on the effects of yttria
doping on microwave properties of alumina ceramics. In the
present paper, Y2O3 is doped in alumina ceramics to lower the
sintering temperature and to investigate the effects of secondary
phase and grain size on dielectric loss.
2. Experimental procedures

Y(NO3)3·6H2O (99.99%) solution was added into high-

⁎ Corresponding author. Tel./fax: +86 571 8795 2112. purity Al2O3 (99.99%) to yield the Y2O3 doped Al2O3 ceramics
E-mail address: xmchen@cmsce.zju.edu.cn (X.M. Chen). with nominal composition of (Al1−xYx)2O3 (x = 0.001, 0.005,
0167-577X/$ - see front matter © 2007 Published by Elsevier B.V.
doi:10.1016/j.matlet.2006.11.062
3358 K.X. Song et al. / Materials Letters 61 (2007) 3357–3360
0.01, 0.02, 0.03, 0.05). The mixtures are ground for 24 h in a
polyethylene bottle with distilled water and alumina balls. The
wet slurries were dried and calcined at 1200 °C in air for 3 h,
and then ground again. The powders added with PVA organic
binder (4 wt.%) were palletized into cylindrical compacts of
12 mm in diameter and 2–5 mm in thickness under uniaxial
pressure of 98 MPa. The green compacts were firstly heated at
600 °C in air for 3 h to expel the organic binder, and sub-
sequently sintered at 1600–1725 °C in air for 3 h.
The density of the samples was measured using Archimedes'
method. The sintered samples were crushed and the phase
constitutions were studied using powder X-ray diffraction
analysis (XRD, RIGAKU D/max 2550 PC) using Cu Kα radia-
tion. The polished samples were thermally etched at a tempera-
ture 100 °C below that of sintering temperature and the surface
morphology was studied by taking Scanning Electron Micro-
scopic (SEM) pictures (FEI SLR10N, Netherlands). The micro-
wave dielectric characteristics were evaluated at about 15 GHz
by dielectric resonator method [22].
3. Results and discussion
The bulk density of Al2O3 ceramics with various x as the function
of sintering temperature is shown in Fig. 1. Alumina ceramics can be
sintered at 1700 °C to approach theoretical densities (3.9862 g/cm3).
With increasing x, the densification temperature decreases from
1700 °C to 1600 °C. The XRD patterns shown in Fig. 2 indicate the
phase evolution of yttria doped alumina ceramics with various x. For
all samples of yttria doped alumina, the secondary phase of Al5Y3O12
is detected, and the amount of the secondary phase increases with
increasing x. This indicate that Y3+ can not replace Al3+ in corundum
alumina to form a solid solution of (Al1−xYx)2O3, and it tends to form
Al5Y3O12 secondary phase. Fig. 3 shows the Rietveld refinement
results for the sample with x = 0.001, where a slow step scan is em-
ployed with a total collection time 12 h over the 2–θ ranges 20–130°.
The Al5Y3O12 is detected, and the (Al1−xYx)2O3 solid solution can
never be formed even for such a small x because of the large difference
between the ionic radius of Al3+ and Y3+. Moreover, a minor amount
of quartz is observed in all ceramic samples, and it is introduced by
agate mortar because the hardness of alumina is higher than that of
quartz.
Fig. 1. Bulk density of Al2O3 ceramics doped with various amounts of Y2O3
as a function of sintering temperature.
Fig. 2. XRD patterns of Al2O3 ceramics doped with various x, indicating Al2O3
major phase combined with the secondary phase. a) Al2O3 powders calcining
at 1200 °C, b) Al2O3 ceramics, c) Al2O3 ceramics doping 0.1 mol% yttria,
d) Al2O3 ceramics doping 0.5 mol% yttria and e) Al2O3 ceramics doping 1 mol%
yttria.
Fig. 4 shows the SEM micrographs of Y2O3 doped Al2O3
ceramics with various x. The grain size is about 20 μm for the dense
ceramic samples without Y2O3 doping. With the addition of Y2O3,
the grain size generally becomes fine, and the Al5Y3O12 secondary
phase with different morphologies is uniformly distributed along
grain boundaries of alumina major phase. Doping Y2O3 can inhibit
grain growth in alumina ceramics during sintering, and this is similar
to those reported previously [23,24]. The only exception is observed
for x = 0.03, where the excess grain growth is caused by the over
sintering.
The microwave dielectric characteristics of Y2O3 doped Al2O3
ceramics are shown in Table 1 and Fig. 5. The dielectric constant
of Al2O3 ceramics with various x varies within 9–10. The dielec-
tric loss increases from 8.4 × 10− 5 to 2.2 × 10− 4, while the Qf at
about 13 GHz decreases from 160,000 GHz to 58,320 GHz. With
increasing Y2O3 doping, the increased amount of secondary phase
brings harmful effects to the microwave properties. But compared
with the samples of x = 0.005, 0.01, 0.03 and 0.05, the lowest dielec-
tric loss and the highest Qf is observed for x = 0.02, where the
grain size is about 7–8 μm. It is known that the grain size has
significant effects on the dielectric loss. The larger grain size may
Fig. 3. XRD pattern of sintering alumina doping 0.1 mol% yttria refined by
Rietveld fitness.
 K.X. Song et al. / Materials Letters 61 (2007) 3357–3360 3359

Fig. 4. SEM micrographs of Al2O3 ceramics with various x: (a) x = 0, (b) x = 0.001, (c) x = 0.005, (d) x = 0.01, (e) x = 0.02, (f) x = 0.03 and (g) x = 0.05.

cause oxygen vacancy of grains not easy to expel during cooling. Al5Y3O12 secondary phase is observed. The dielectric loss
On the other hand, the smaller grain size, the more grain bound- increases generally from 8.4 × 10− 5 to 2.2 × 10− 4, with yttria
aries, which will lead to higher dielectric loss. Correspondingly, doping. The secondary phase increases the dielectric loss, and
the optimum grain size has been also reported about 7–8 μm, which
has less dielectric loss [16,18]. Here, the secondary phase primar-
ily dominates the dielectric loss, and the grain size is the secondary Table 1
factor. Microwave dielectric characteristics of Al2O3 ceramics with various x
x f0 (GHz) εr Qf (GHz) tan (δ)
0 13.38 9.21 159,280 0.000084
4. Conclusion
0.001 14.05 9.91 100,350 0.00014
0.005 14.46 9.70 76,100 0.00019
The dielectric loss of alumina ceramics doped with various 0.01 14.88 9.68 64,700 0.00023
amount of yttria was investigated. It is hard to put the Y3+ ion 0.02 14.42 9.85 80,110 0.00018
into the Al–O octahedron of corundum structure of alumina to 0.03 12.60 10.00 66,320 0.00019
0.05 12.81 9.98 58,230 0.00022
form a solid solution of intermission and substitution, and the
3360 K.X. Song et al. / Materials Letters 61 (2007) 3357–3360
Fig. 5. Dielectric constants and Qf of Al2O3 ceramics as functions of x.
the optimum grain size is beneficial to oppress the dielectric
loss.
Acknowledgements
The present work was partially supported by the National
Science Foundation of China (Grant No. 50332030), and the
Chinese National Key Project for Fundamental Researches
(Grant No. 2002 CB613302).
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