Pergamon Materials Research Bulletin 35 (2000) 15–24

Effect of niobia on the crystal structure and dielectric

characteristics of Pb(Zr0.45Ti0.55)O3 prepared from
polymeric precursor
C.O. Paiva-Santos*, C.F. Oliveira, W.C. Las, M.A. Zaghete, J.A. Varela,
M. Cilense
Instituto de Quı́mica, UNESP, Caixa Postal 355, 14801-970 Araraquara, SP, Brazil

(Refereed)
Received 16 February 1999; accepted 24 March 1999

Abstract

The influence of niobia addition on the phase formation and dielectric properties of
Pb(Zr0.45Ti0.55)O3 powder prepared from polymeric precursor was analyzed. The weight fraction
and unit-cell volume of the tetragonal phase decreased, and the mass fraction of the rhombohedral
phase increased, with increasing niobia concentration. The rhombohedral unit-cell volume
increased up to 5 mol% of added Nb and then decreased. Small amounts of pyrochlore and
tetragonal zirconia phases were observed in PZT powder with more than 10 mol% Nb. These
results were interpreted as an indication that the Nb ion was substituted for the zirconium ion in
the tetragonal phase. For sintered PZT samples at 1100°C, no free-zirconia phase was observed.
The dielectric constant increased with the niobia addition up to 5 mol% and decreased for higher
concentrations. The Curie temperature decreased with niobia addition up to 10 mol% before the
formation of pyrochlore phase. © 2000 Elsevier Science Ltd. All rights reserved.

Keywords: A. Ceramics; B. Chemical synthesis; C. X-ray diffraction; D. Crystal structure; D. Dielectric

properties

* Corresponding author. Tel.: ⫹55-16-201-6640; fax: ⫹55-16-222-7932.

E-mail address: copsanto@iq.unesp.br (C.O. Paiva-Santos).

0025-5408/00/$ – see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 2 5 - 5 4 0 8 ( 0 0 ) 0 0 1 9 2 - 6
16 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24

1. Introduction

Pb(ZrxTi1⫺x)O3 (PZT) is a perovskite-type ABX3 structure material, with high piezoelec-

tric and dielectric characteristics (piezoelectric constant d33 ⬇ 150 –250 ␮m/V; dielectric
constant at room temperature ⬇ 500 –700) and a Curie temperature (Tc) higher than 300°C,
when x is in the morphotropic phase boundary (MPB), about 0.53 [1].
The dielectric characteristics of PZT change with its stoichiometry. Dai et al. [2] changed
the PZT Zr/Ti ratio from 95/5 to 55/45 and observed that the maximum dielectric constant
changed from 10000 to 14000, and the Curie temperature changed from 250 to 380°C.
However, the best dielectric and piezoelectric properties of PZT have been found in MPB
[3].
It has been demonstrated that the PZT piezoelectric characteristics can be improved with
the use of additives during powder calcination. Recent examples are Mg-doped PZT pre-
pared by conventional mixing of oxides (CMO) [4], where Rietveld analysis shows that the
magnesium was substituted for the lead ion in samples showing great compositional fluc-
tuation. Kanai et al. [5] prepared PZT by CMO doped with alkaline earth and observed an
improvement in the dielectric constant. Gelfuso and Eiras [6] improved the PZT dielectric
constant by 42% when the PZT was doped with La and by 75% when doped with Nb.
The sample preparation method is fundamental to the characteristics of the resulting
powder. Zaghete et al. [7] prepared pure PZT by citrate solution method, seeded with
tetragonal or rhombohedral PZT, and observed an epitaxial growth on the crystalline phases.
In contrast to the CMO results, the rhombohedral PZT phase was observed to form first,
directly from the citrates, with no intermediates phases, and independent of the Zr/Ti ratio.
Cerqueira et al. [8], prepared calcium- and strontium-doped PZT by chemical routes and
observed larger values for remnant polarization and smaller values for coercive field. Krishna
et al. [9] observed by Rietveld refinement [10] that the calcium ion occupies the same
crystallographic sites as Ba and Ti when BaTiO3 is prepared by CMO, and occupies only the
Ba site when prepared by a chemical route, changing drastically the properties of the
material. Rimoldi et al. [11] observed larger values of remnant polarization and a smaller
coercive field for Nb-doped PZT prepared by the citrate solution method.
The aim of this work was to understand the effects of niobium addition on PZT crystal
structure and the amounts of phases formed. PZT (Zr/Ti ⫽ 45/55) was prepared by using
organic citrate solutions with the addition of 5 to 15 mol% niobium. To identify the most
probable site occupied by the additive in the crystal structure of PZT, and its influence on the
formation of non-PZT crystalline phases, such as tetragonal ZrO2 (Z-t) and pyrochlore
Pb2(Zr1⫺xTix)NbO6.5 (Py), the Rietveld method was applied. Dielectric constants and Curie
temperature of the sintered samples were measured to verify the influence of Nb on the PZT
dielectric characteristics.

2. Experimental

A series of four samples of Pb(Zr0.45Ti0.55)O3 was prepared from organic solutions of Pb,
Zr, and Ti citrates and calcined at 800°C for 2 h, with the following conditions: (a) without
additive, (b) with 5 mol% niobium, (c) with 10 mol% Nb, and (d) with 15 mol% Nb. The
 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24 17

Fig. 1. Scattering factors of Zr4⫹ (—䊐—), Ti4⫹ (---⫹---), and Nb5⫹ (—‚—).

additives were added to pure PZT, e.g., 100% PZT ⫹ y% Nb (y ⫽ 5, 10, 15). The preparation
method is described elsewhere [7].
X-ray diffraction data were collected with a Siemens D5000 diffractometer under the
following experimental conditions: 40 kV, 30 mA; 20° ⫽ 2␪ ⫽ 120°, ⌬2␪ ⫽ 0.02°; ␭(Cu
K␣) monochromatized by a graphite crystal; divergence slit, 2 mm; reception slit, 0.6 mm;
step time ⫽ 10 s.
The Rietveld analysis [10] was performed with the Rietveld refinement program DBWS-
9411 [12]. The profile function used was the modified Thompson–Cox–Hasting pseudo-
Voigt, in which ␩ (the Lorentzian fraction of the function) varies with the Gauss and Lorentz
components of the full-width at half-maximum.
The scattering factors for Nb5⫹ and Zr4⫹ are very similar (Fig. 1), and their effects on the
X-ray diffraction peak intensities are indistinguishable, e.g., if the Nb occupies the Zr site in
the structure of PZT, no changes in the relative peak intensities can be observed. On the other
hand, Ti4⫹ has a different scattering factor than Nb5⫹. If the Ti4⫹ ion were substituted for
the Nb5⫹ ion, a perceptible variation in the relative peak intensity would be observed,
depending on the amount of sites being substituted.
The ionic radius of Nb5⫹ is significantly smaller than that of Zr4⫹, but is practically the
same as that of Ti4⫹. If the Nb5⫹ ion were substituted for the Zr4⫹ ion, a decrease in the
unit-cell volume would occur; whereas, if substituted for the Ti4⫹ ion, no variations in the
unit cell would be observed. Thus, the site(s) occupied by Nb ions in the crystal structure of
PZT can be identified by analyzing the unit-cell volume and/or relative intensity variations.
Quantitative phase analysis (QPA) [13] can be of great help in this regard, considering that
non-PZT phases are formed with the inclusion of Nb and the relative proportion of tetragonal
and rhombohedral phases varies.
For the electrical characterization, the powders were isostatically pressed and sintered at
1100°C for 2 h. Measurements of capacitance, as a function of temperature, were performed
with an HP 4192 impedance analyzer operating at a frequency of 100 kHz.
18 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24

Table 1
Final Rietveld indexes and the identification codes used in this work for all samples
Sample Rwp S Code
Undoped 9.23 1.48 PZTN0
5 mol% 9.65 1.64 PZTN5
10 mol% 9.01 1.56 PZTN10
15 mol% 8.74 1.50 PZTN15

3. Results and discussion

The tetragonal and rhombohedral PZT phases were observed in all powder samples. For
samples with 10 and 15 mol%, the pyrochlore phase was also observed. This phase was
formed due to the large inclusion of smaller size Nb5⫹ ion in the perovskite PZT lattice,
substituting the Zr4⫹ ion. The pyrochlore structure was supposed to be isomorphic of the
Pb2[TiSb]O6.5 (PTS) with space group P4̄3m [14]. In this case, the Ti site was considered to
be shared with Zr, and the Sb site in the PTS was considered to be occupied by Nb ions in
the PZT pyrochlore phase of the type Pb2(Zrx⫺yNbyTi2⫺x)O6⫹y/2. By supposing that the
zirconium ion was substituted for the niobium ion in the tetragonal or rhombohedral PZT
phases, no changes occurred in the refinements, but when supposing that the Nb ion was
substituted for the titanium ion, the refinements diverged to absurdly high Rwp indexes. The
final Rietveld indexes for the samples are given in Table 1. The definitions of the Rietveld
indexes can be found in the reference of Young and Wiles [15].
The quantitative phase analysis results for powders can be observed in Fig. 2. The unit cell
volumes for the tetragonal and rhombohedral phases are given in Fig. 3, and those for all
observed phases in all samples are in Table 2. Final Rietveld plots for the refinements of the
pure, 5, 10, and 15 mol% Nb samples are given in Fig. 4 a– d, respectively.
In Fig. 2, the proportion of tetragonal phase decreases and of rhombohedral phase

Fig. 2. Quantitative phase analyses of PZT samples as functions of Nb concentration.

 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24 19

Fig. 3. Tetragonal and rhombohedral unit cell volumes for tetragonal and rhombohedral phases in all samples as
functions of Nb concentration.

increases, with the increase of additive addition. The tetragonal phase decreases from about
79 wt% for pure PZT, to about 31 wt% for the sample with 15 mol% of Nb. The
rhombohedral phase increased from approximately 21 wt% (undoped sample) to 52 wt%
(PZTN15). Tetragonal zirconia (Z-t) was determined to be about 5 wt% in the PZTN10 and
3 wt% for PZTN15. Pyrochlore phase was determined in PZTN10 (3 wt%) and PZTN15 (13
wt%).
The tetragonal unit-cell volume decreased systematically with the increase of additive
amount in the sample (Fig. 3) from ⬇66.9 Å3 (undoped samples) to ⬇63.4 Å3 (PZTN15).
The rhombohedral unit-cell volume varied according to the amount of non-PZT phases
formed, i.e., the rhombohedral unit-cell volume decreased when the amount of (Py ⫹ Z-t)
phases increased. For the pyrochlore phase, the unit-cell volume appeared to decrease with
the addition of Nb and for tetragonal zirconia, the unit-cell volume appeared to increase with
increasing niobium concentration. The variations in the unit cell for these phases are
attributed to the niobium addition in their lattices.
If one supposes that Zr4⫹ is substituted for the Nb5⫹ in the tetragonal unit cell, it is

Table 2
Unit-cell volume (Å3) for all phases in all samples
Sample Tetragonal Rhombohedral ZrO2 Py
a
PZTN0 66.896(5) 201.61(5) NO NO
PZTN5 65.85(1) 207.8(2) NO NO
PZTN10 64.706(1) 206.54(8) 67.7(1) 1210.0(6)
PZTN15 63.36(2) 203.8(2) 68.18(6) 1207.3(2)
Esd’s are given in parentheses.
a
NO ⫽ phase not observed.
20 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24

Fig. 4. Rietveld plot for (a) pure PZT(45/55), (b) PZT(45/55) with 5 mol% Nb addition, (c) PZT(45/55) with 10
mol% Nb addition, and (d) PZT(45/55) with 15 mol% Nb addition.

possible to explain these observations. Considering that the ionic radius of Zr4⫹ is greater
than the ionic radius of Ti4⫹ and Nb5⫹, if the niobium substitutes for the zirconium, it would
cause a decrease in the unit-cell volume. Further, zirconium ions not in the tetragonal phase
would be incorporated into the rhombohedral phase, which would cause an increase in the
amount of rhombohedral phase and unit-cell volume. By adding more than 10 mol% Nb5⫹,
the pyrochlore phase would also form and, in this case, the Zr4⫹ would be preferentially
incorporated into the pyrochlore phase. As a consequence, there would be a decrease in the
rhombohedral phase amount and in the unit-cell volume; that is, these values would be lower
than those in PZTN5.
 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24 21

Fig. 4. (Continued)

In the Rietveld plots for PZT powders with different Nb concentration (Fig. 4a– d), one
can observe that only the tetragonal and rhombohedral phases of PZT are present in the pure
and 5 mol% Nb samples and that the tetragonal zirconia and pyrochlore phases are present
in the 10 and 15 mol% Nb samples. In Fig. 4d, a strong peak at about 29° corresponding to
the Py phase is observed.
The XRD patterns for the sintered samples at 1100°C for 2 h are given in Fig. 5. The
pyrochlore phase is clearly observed in the 15 mol% Nb sample. For all other samples, only
the perovskite PZT phases were observed. The absence of zirconia phase in the sintered
samples can be explained in the following way: For a large concentration of niobium
addition, the excess of zirconium ions being substituted was precipitated as tetragonal
22 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24

Fig. 5. XRD patterns for the sintered PZT (45/55) samples with several Nb concentrations.

zirconia at the calcining temperature (800°C), together with the pyrochlore phase
Pb2(Zrx⫺yNbyTi2⫺x)O6⫹y/2. The tetragonal zirconia is unstable and for higher temperatures
can react with PZT and the zirconium ions being incorporated, causing an increase in the
amount of the rhombohedral phase. Moreover, the zirconium ions can be incorporated into
the pyrochlore phase Pb2(Zrx⫺yNbyTi2⫺x)O6⫹y/2.
The dielectric constant was measured as function of temperature at 100 kHz frequency for
all considered samples; the results are depicted in Fig. 6. The maximum dielectric constant
for pure PZT was found to be 7,800 at Tc ⫽ 410°C. The addition of 5 mol% of Nb increases
this maximum value to 10,220 at 373°C. This increase in the dielectric constant can be
related to the favoring of rhombohedral PZT phase in detriment of tetragonal phase due to
inclusion of Nb5⫹ for Zr4⫹ in the PZT lattice. However, higher Nb concentration leads to
formation of pyrochlore phase, which decreases the maximum dielectric constant for the PZT

Fig. 6. Plot of dielectric constant vs. temperature for sintered PZT(45/55) samples with several Nb concentrations.
 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24 23

ceramics (6,700 for 10 mol% Nb and 3,300 for 15 mol% Nb). Note that, although pyrochlore
phase was not observed in the XRD pattern of the sintered sample containing 10 mol% Nb
(Fig. 5), the dielectric constant at the Curie temperature decreased substantially, compared
with that for samples containing 5 mol% Nb. Probably a small amount of pyrochlore phase,
not detectable by XRD, was formed and was sufficient to cause such large modification in
the dielectric characterization of the PZT samples.

4. Conclusions

Quantitative phase analysis by using the Rietveld method and dielectric characterization
of PZT samples with addition of niobium lead to the following conclusions:
1. Nb5⫹ ions are probably incorporated mainly into the tetragonal PZT phase, substituting
for Zr4⫹ ions.
2. Addition of more than 5 mol% Nb causes the formation of a pyrochlore phase of the
type Pb2(Zrx⫺yNbyTi2⫺x)O6⫹y/2, which degrades the dielectric constant of the PZT
samples.
3. Curie temperature decreased with increasing Nb concentration (up to 10 mol%) and the
dielectric constant at Curie temperature reached its maximum value for 5 mol% Nb.

Acknowledgments

The authors acknowledge FAPESP, CNPq, and FINEP/PRONEX, all Brazilian agencies,
for financial support of this work.

References

[1] B. Jaffe, W.R. Cook, H. Jaffe, Piezoelectric Ceramics, Academic Press, London, 1971.
[2] X. Dai, Z. Xu, D. Viehland, J Am Ceram Soc 78 (1995) 2815–2827.
[3] K. Kakegawa, J. Mohri, T.H. Takahashi, S. Shirasaki, Solid State Commun 28 (1977) 769 –772.
[4] C.O. Paiva-Santos, M. Cerqueira, E. Longo, J.A. Varela, Y.P. Mascarenhas, in: Annals of the 35th Congress
of the Brazilian Ceramic Society and 3rd Ibero-American Congress of Ceramic, Glass and Refractories, Vol.
2, Brazilian Ceramic Society, Sao Paulo, 1991, pp. 616 – 622.
[5] H. Kanai, O. Furukawa, H. Abe, Y. Yamashita, J Am Ceram Soc 77 (1994) 2620 –2624.
[6] M.V. Gelfuso, J.A. Eiras, in: Annals of the 36th Congress of the Brazilian Ceramic Society, Vol. 2, Brazilian
Ceramic Society, Sao Paulo, 1992, p. 594.
[7] M.A. Zaghete, C.O. Paiva-Santos, J.A. Varela, E. Longo, Y.P. Mascarenhas, J Am Ceram Soc 75 (1992)
2088 –2093.
[8] M. Cerqueira, R.S. Nasar, E. Longo, C.O. Paiva-Santos, J.A. Varela, in: Annals of the 36th Congress of the
Brazilian Ceramic Society, Vol. 2, Brazilian Ceramic Society, Sao Paulo, 1992, pp. 617– 624.
[9] P.S.R. Krishna, D. Pandey, V.S. Tiwari, R. Chakravarthy, B.A. Desannacharya, Appl Phys Lett 62 (1993)
231–233.
[10] H.M. Rietveld, J Appl Cryst 2 (1969) 65–71.
[11] L.C. Rimoldi, M.A. Zaghete, J.A. Varela, M. Cilense, C.O. Paiva-Santos, Ceramica 42 (1996) 483– 486.
24 C.O. Paiva-Santos et al. / Materials Research Bulletin 35 (2000) 15–24

[12] R.A. Young, A. Sakthivel, T.S. Moss, C.O. Paiva-Santos, J Appl Cryst 28 (1995) 366 –367.
[13] R.J. Hill, C.J. Howard, J Appl Cryst 20 (1978) 467– 474.
[14] J. A. Alonso, C.I. Cascales, I. Rasines, Acta Crystallogr C 45 (1989) 3–7.
[15] R.A. Young, D.B. Wiles, J Appl Cryst 15 (1982) 430 – 438.