Materials Research Bulletin 38 (2003) 1091–1099

Improved high-Q microwave dielectric resonator using

CuO-doped MgNb2O6 ceramics
Cheng-Shing Hsua, Cheng-Liang Huanga,*, Jing-Fang Tsenga,
Chi-Yuen Huangb
a
Department of Electrical Engineering, National Cheng Kung University,
No. 1 University Rd., Tainan 70101, Taiwan
b
Department of Resources Engineering, National Cheng Kung University,
No. 1 University Rd., Tainan 70101, Taiwan
Received 6 December 2002; accepted 28 January 2003

Abstract

The microwave dielectric properties and the microstructures of MgNb2O6 ceramics with CuO additions
(1–4 wt.%) prepared with conventional solid-state route have been investigated. The sintered samples exhibit
excellent microwave dielectric properties, which depend upon the liquid phase and the sintering temperature. It is
found that MgNb2O6 ceramics can be sintered at 1140 8C due to the liquid phase effect of CuO addition. At
1170 8C, MgNb2O6 ceramics with 2 wt.% CuO addition possesses a dielectric constant (er) of 19.9, a Q
f value
of 110,000 (at 10 GHz) and a temperature coefficient of resonant frequency (tf) of 44 ppm/8C. The CuO-doped
MgNb2O6 ceramics can find applications in microwave devices requiring low sintering temperature.
# 2003 Published by Elsevier Science Ltd.

Keywords: A. Ceramics; D. Dielectric properties

1. Introduction

Recently, researchers have been focusing on developing dielectric materials with high quality factor
(Q
f ), high dielectric constant (er) and zero temperature coefficient of resonant frequency (tf) for the
use of dielectric resonator and microwave device substrate. High dielectric constant material can
effectively reduce the size of resonators since that the wavelength (l) in dielectrics is inversely
pffiffiffiffi pffiffiffiffi
proportional to er (l ¼ l0 = er where l0 is the wavelength in vacuum). The inverse of the dielectric
loss (Q ¼ 1/tand) is required to be high for achieving prominent frequency selectivity and stability in

*
Corresponding author. Tel.: þ886-6-2757575; fax: þ886-6-2345482.
E-mail address: huangcl@mail.ncku.edu.tw (C.-L. Huang).

0025-5408/03/$ – see front matter # 2003 Published by Elsevier Science Ltd.

doi:10.1016/S0025-5408(03)00058-8
1092 C.-S. Hsu et al. / Materials Research Bulletin 38 (2003) 1091–1099

microwave transmitter components. Moreover, small temperature coefficient of resonant frequency

ensures high stability of the microwave components at different working temperatures. Several
compounds such as (Zr,Sn)TiO4, Ba(Mg1/3Ta1/3)O3 and (Mg,Ca)TiO3 have therefore been developed
[1–3].
The MgNb2O6 ceramics having the columbite crystal structure, had been investigated by Lee et al.
[4,5]. Based upon the microwave dielectric properties (er  21:4, Q
f  93,800 GHz and
tf  70 ppm/8C at 1300 8C; [5]), it proposed possible applications in dielectric resonators. However,
a modification in tf is necessary due to the coefficient’s large negative value. In addition, sintering
temperatures also need to be lowered for applications with low-temperature co-fired ceramics.
In the producing miniaturized devices, multilayer structures with low sintering temperatures are
needed to co-fire with low melting point electrodes. Low melting glass addition, chemical processing
and small particle sizes of the starting materials are generally advantageous to reduce the sintering
temperature of dielectric materials [6–9]. Moreover, using low melting glass additions is generally the
most effective and least expensive technique. Since CuO is one of the most popular sintering fluxes, it
was chosen as a sintering aid to lower the firing temperature of the MgNb2O6 ceramics in this paper.
The microwave dielectric properties and the microstructures of CuO-doped MgNb2O6 ceramics were
also investigated.

Fig. 1. X-ray diffraction patterns of 2 wt.% CuO-doped MgNb2O6 ceramics at different sintering temperatures.
 C.-S. Hsu et al. / Materials Research Bulletin 38 (2003) 1091–1099 1093

2. Experiment procedure

Samples of MgNb2O6 were synthesized by conventional solid-state method. The starting materials were
mixed according to a stoichiometric ratio. High purity oxide powders MgO, Nb2O5 and CuO were
weighted and mixed for 24 h with distilled water. The mixture was dried at 100 8C, and thoroughly milled
before it was calcined at 1150 8C for 2 h. The calcined powder MgNb2O6 was ground and sieved through
100-mesh screen. Phase formation of MgNb2O6 was confirmed using X-ray diffraction. The calcined
powder was then re-milled for 24 h with 2 wt.% of a 10% solution of PVA as a binder. The milled powders
were pressed into disk 11 mm in diameter and 5 mm in thickness. A pressing pressure of 2000 kg/cm2 was
used for all samples. The pellets were sintered at temperatures 1140–1290 8C for 3 h in the air.
The X-ray diffraction (XRD, Rigaku D/Max III. V) data of powder and bulk samples were collected
using Cu Ka radiation (at 30 KV and 20 mA) and a graphite monochromator in the 2y range of 20–608.
The microstructural observations and analysis of sintered surface were performed using a scanning
electron microscopy (SEM, Philips XL40FEG) and an energy dispersive X-ray spectrometer (EDS).
The dielectric constants (er) and Q
f values at microwave frequencies were measured using the
Hakki-Coleman dielectric resonator method, as modified and improved by Courtney. The dielectric
resonator was positioned between two brass plates such like cavity. Microwave dielectric properties
of sintered samples were measured by HP8757D network analyzer and HP8350B sweep oscillator.

Fig. 2. X-ray diffraction patterns of MgNb2O6 ceramics with different amount of CuO addition sintered at 1170 8C.
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For temperature coefficient of resonant frequency (tf), the technique is the same as that of quality factor
measurement. The test cavity is placed over a thermostat and the temperature range used is þ25 to
þ80 8C. The tf (ppm/8C) is calculated by noting the change in resonant frequency (Df) by,
f2  f1
tf ¼ (1)
f1 ðT2  T1 Þ
where f1 is resonant frequency at T1 and f2 is the resonant frequency at T2.

3. Results and discussions

Fig. 1 shows the X-ray diffraction patterns of 2 wt.% CuO-doped MgNb2O6 ceramics produced at
different sintering temperatures (1140–1290 8C). Similar X-ray diffraction patterns were detected for
the MgNb2O6 ceramics with 2 wt.% CuO addition at sintering temperatures 1140–1290 8C. Second
phase was not observed at the level of 2 wt.% CuO addition since detection of a minor phase by X-ray
is extremely difficult. The X-ray diffraction patterns of MgNb2O6 ceramics with different amount of

Fig. 3. SEM photographs of MgNb2O6 ceramics with (a) 1 wt.%, (b) 2 wt.% and (c) 4 wt.% CuO additions at different
sintering temperatures.
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Fig. 3. (Continued ).

CuO addition sintered at 1170 8C are illustrated in Fig. 2. Identical XRD patterns were observed for the
ceramics irrespective of the amount of CuO additions.
The surface microstructural photographs of CuO-doped MgNb2O6 sintered at temperatures
1140–1290 8C are presented in Fig. 3. The grain size increased with the increase of sintering
temperature as well as amount of CuO addition due to liquid phase effect. However, rapid grain growth
appeared for MgNb2O6 specimen with CuO additions at sintering temperatures higher than 1170 8C.
These may directly affect the microwave dielectric properties of the MgNb2O6 samples. For liquid
phase sintering of ceramics, the liquid would be either resident or disappear in the final stages. In the
experiments, boundary phases were clearly observed at high CuO-doping levels ( 2 wt.%).
Fig. 4 shows the EDS spectra of grain boundaries of CuO-doped MgNb2O6 specimen. It revealed that
the grain boundaries of the MgNb2O6 ceramics with various amount of CuO additions exhibit Cu rich
liquid phases. The formations of the liquid phases were attribute to the additions of CuO. In addition,
high CuO additions also produce more liquid phase, which is believed to significantly affect the
microwave dielectric properties of the ceramic samples. With 2 wt.% CuO addition, a Cu atomic
percentage of 25.74 was obtained for MgNb2O6 ceramics sintered at 1170 8C.
The density of the CuO-doped MgNb2O6 ceramics at different sintering temperatures is shown in
Fig. 5. The density initially increased with increasing sintering temperature. After reaching the
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Fig. 4. EDS spectra of MgNb2O6 ceramics with (a) 1 wt.%, (b) 2 wt.%, (c) 4 wt.% CuO additions at 1290 8C and (d) 2 wt.%
CuO addition at 1170 8C.
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Fig. 5. Dependence of sintering temperature of MgNb2O6 ceramics on density with various CuO additions.

maximum at 1170 8C, it decreased thereby owing to the rapid grain growth as well as the liquid
boundary phases. It seemed that CuO did contribute to the densification of MgNb2O6 ceramics at low
temperatures. The maximum density was found to be 4.85 g/cm3 for specimen with 1 wt.% CuO
addition at 1170 8C. It is difficult to synthesize ceramics with ultra-high relative density by the
conventional solid-state method unless it is augmented by other methods, such as chemical processing.
The plots of dielectric constant of MgNb2O6 ceramics with different amounts of CuO additions as
functions of sintering temperature were illustrated in Fig. 6. The relationships between dielectric
constant and sintering temperature reveal the same trend as that for density and sintering temperature
since higher density represents lower porosity. Highest dielectric constant was obtained for CuO-doped
MgNb2O6 ceramics at 1170 8C. Moreover, the dielectric constant slightly decreased with increasing
CuO content. It varied from 20.5 to 19.4 as the amount of CuO addition increased from 1 to 4 wt.% at
1170 8C. The variation of the Er value was mainly a result from the density of the specimen.

Fig. 6. Dependence of sintering temperature of MgNb2O6 ceramics on dielectric constant with various CuO additions.
1098 C.-S. Hsu et al. / Materials Research Bulletin 38 (2003) 1091–1099

Fig. 7. Dependence of sintering temperature of MgNb2O6 ceramics on quality factor value (Q
f ) with various CuO
additions.

Fig. 7 shows the Q
f value of CuO-doped MgNb2O6 ceramics at different sintering temperatures.
The microwave dielectric loss is mainly caused not only by the lattice vibrational modes, but also by
the pores and the second phases. With increasing sintering temperature, the Q
f increased to a
maximum value at 1170 8C and thereafter decreased. The decrease in Q
f value was due to the rapid
grain growth as observed in Fig. 3. However, highest Q
f values were obtained for specimen at
2 wt.% CuO-doping level, which was not consistent with the variation of density. Density plays an
important role in controlling the dielectric loss and has been shown for other microwave dielectric
materials. The Q
f value, however, was independent of the density for highly densified ceramics [10].
As observed in Fig. 3, the grain of MgNb2O6 ceramics with 2 wt.% CuO addition was more uniform
than others. Which revealed a reduction in lattice imperfection and dielectric loss was then reduced.

Fig. 8. Dependence of sintering temperature of MgNb2O6 ceramics on tf value with various CuO additions.
 C.-S. Hsu et al. / Materials Research Bulletin 38 (2003) 1091–1099 1099

The decrease in Q
f values for highly CuO-doped MgNb2O6 ceramics could be a result from the
grain morphology as well as the low Q
f value of liquid phase. With 2 wt.% CuO addition, an
excellent Q
f value of 110,000 (at GHz) was obtained for MgNb2O6 ceramics sintered at 1170 8C for
3 h. The quality factors of CuO-doped MgNb2O6 ceramics at low sintering temperature were relatively
higher than that of pure MgNb2O6 ceramics due to the addition of CuO.
Fig. 8 shows the temperature coefficient of the resonant frequency (tf) of the CuO-doped MgNb2O6
ceramics at different sintering temperatures. The temperature coefficient of resonant frequency (tf) was
known related to the composition and the second phase of the ceramic samples. No significant change
was observed in the tf value for specimen at different sintering temperatures. However, the tf value
varied toward positive direction with increasing CuO content due to the formation of liquid phase. It
implies that the tf value of MgNb2O6 ceramics can be adjusted by controlling the amount of CuO
addition.

4. Conclusion

The dielectric properties of CuO-doped MgNb2O6 ceramics have been investigated. The flux CuO
was employed as a sintering aid to lower the firing temperature of the MgNb2O6 ceramics. A large
sintering temperature reduction (100–200 8C) can be achieved by adding CuO to the MgNb2O6
ceramics. Significant improvements in the Q
f and tf values have also been accomplished. With
2 wt.% CuO addition, a dielectric constant of 19.9, a Q
f value of 110,000 (at 10 GHz) and a tf value
of 44 ppm/8C were obtained for MgNb2O6 ceramics sintered at 1170 8C for 3 h. The dielectric
properties of MgNb2O6 ceramics with CuO additions are strongly dependent on the densifications and
the microstructures. The decrease in Q
f value at high CuO addition level (4 wt.%) was owing to the
inhomogeneous grain growth as well as the low Q
f value of liquid phase.

Acknowledgements

This work was supported by the National Science Council of the Republic of China under grant NSC
91-2213-E-006-119.

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