Materials Science and Engineering B 116 (2005) 104–108

Short communication

Effect of Cr2O3 addition on the structure and electrical properties of

Pb((Zn1/3Nb2/3)0.20(Zr0.50Ti0.50)0.80)O3 ceramics
Y.D. Hou, P.X. Lu, M.K. Zhu∗ , X.M. Song, J.L. Tang, B. Wang, H. Yan
The Key Laboratory of Advanced Functional Materials, Education Ministry of China, Beijing University of Technology, Beijing 100022, China

Received 12 July 2004; received in revised form 15 September 2004; accepted 19 September 2004

Abstract

The structure and electrical properties of Cr2 O3 -doped Pb(Zn1/3 Nb2/3 )0.20 (Zr0.50 Ti0.50 )0.80 O3 system (0.2PZN–0.8PZT) were described in
this paper. Materials with pure perovskite structure were fabricated by the columbite precursor method. Addition of Cr2 O3 stabilized the
tetragonal phase against the rhombohedral one, moving morphotropic phase boundary (MPB) composition toward the PbTiO3 -deficient side.
The grain size was steadily enhanced when small amounts of Cr2 O3 were added to system. However, addition of Cr2 O3 above the solubility
of 0.3 wt.% inhibited the grain growth due to accumulation of Cr ion at the grain boundary. The values of electromechanical coupling factor,
kp , piezoelectric constant, d33 are optimized for 0.3 wt.% Cr2 O3 -doped samples (kp = 0.70, d33 = 491 pC/N), which suggested that the effects
of grain size plays a dominant role on improving the piezoelectric properties than that of oxygen vacancies in the low Cr2 O3 doping region
of 0–0.3 wt.%.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Ferroelectrics; Phase transitions; Piezoelectricity

1. Introduction ture, higher density and more uniform grain structure [9–11].
Recently, it was found in our research work that both the di-
Lead zinc niobate (Pb(Zn1/3 Nb2/3 )O3 , PZN) in the per- electric and piezoelectric properties of PZN–PZT materials
ovskite structure is one of the most important relaxor ferro- are strongly improved by the addition of additives such as Mn
electrics, which can exhibit excellent piezoelectric as well and Cu [12–14]. The super electric properties made the doped
as dielectric properties [1–3]. However, pure PZN in the PZN–PZT system suitable for the piezoelectric transformer
perovskite structure is very difficult to prepare due to its application.
inherently low tolerance factor and small electronegativ- Cr doping is another one of the most adopted strategies
ity difference between cations [4]. To retain the perovskite to tailor the dielectric and piezoelectric properties of fer-
structure at sintering temperature, other perovskite materi- roelectrics to practical specifications. It is well known that
als, such as PZT, PbTiO3 or BaTiO3 , need to be incorpo- Cr is effective in decreasing the aging effect and increas-
rated with the PZN structure [5–8]. Conversely, the addi- ing mechanical quality factor Qm . Uchida and Ikeda have
tion of small amounts of PZN was found to be beneficial studied the solubility limit of Cr2 O3 in PZT and its tem-
for the electromechanical properties of PZT. Compared with perature, bias, aging characteristics [15]. Cheon and Park
the binary system of PZT, the ternary system of PZN–PZT have studied the effects of Cr2 O3 on the temperature sta-
shows higher piezoelectric activity, lower sintering tempera- bility of the resonant frequency in PZT ceramics [16]. Re-
cently, He et al. have reported the piezoelectric properties
∗ Corresponding author. Present address: Department of Materials Sci-
in Cr2 O3 -doped Pb(Mg1/3 Nb2/3 )O3 –PbZrO3 –PbTiO3 sys-
ence and Engineering, Beijing University of Technology, Chao Yang District,
tem and found Cr2 O3 addition was effective in increasing
Beijing 100022, China. Tel.: +86 106 739 2733; fax: +86 106 739 2412. both Qm and kp [17]. However, little information is available
E-mail address: [email protected] (M.K. Zhu). regarding the effects of Cr2 O3 addition on the properties of

0921-5107/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2004.09.015
 Y.D. Hou et al. / Materials Science and Engineering B 116 (2005) 104–108 105

the ternary system PZN–PZT. In the present study, various

quantities of Cr2 O3 were added into 0.2PZN–0.8PZT com-
positions and the resulting ceramics were characterized for
piezoelectric properties and microstructure characteristics.

2. Experimental

The general formula of the materials studied was

Pb((Zn1/3 Nb2/3 )0.20 (Zr0.50 Ti0.50 )0.80 )O3 + xCr2 O3 , where
x = 0–1 wt.%. The samples were prepared by the columbite
precursor method in order to acquire pure perovskite phase
[18]. Reagent-grade oxide powders, Pb3 O4 , ZrO2 , TiO2 ,
ZnO, Nb2 O5 , and Cr2 O3 were used as the starting materials. Fig. 1. XRD patterns of Cr2 O3 -doped 0.2PZN–0.8PZT specimens: (a)
0 wt.%, (b) 0.05 wt.%, (c) 0.10 wt.%, (d) 0.20 wt.%, (e) 0.30 wt.%, (f)
In the first stage, the powder of columbite precursor, 0.40 wt.%, (g) 0.50 wt.%, (h) 0.60 wt.%, (i) 0.80 wt.%, (j) 1.00 wt.%.
ZnNb2 O6 , was prepared by calcinations of ZnO with Nb2 O5
at 1100 ◦ C for 4 h. In the second stage, the above precursor
with Pb3 O4 , ZrO2 , TiO2 , and Cr2 O3 were weighed and phase, which rapidly transforms to pyrochlore phase that is
mixed through use of a polyethylene jar and ZrO2 milling highly detrimental to the dielectric and piezoelectric prop-
media. The mixture was then calcined at 850 ◦ C for 2 h in air, erties. The stability of modified PZN ceramics depends on
remilled, pressed into discs of 12.0 mm in diameter at around the amount of perovskite compound added and on the A-
120 MPa, and then sintered at 1200 ◦ C for 2 h in a sealed or B-site cation replacement [19–22]. For example, a PZN
alumina crucible with a PbZrO3 powder atmosphere. The ceramic solid solution with 100% perovskite structure can
sintered discs were lapped and electroded with a silver paste. be prepared by adding BaTiO3 > 7 mol%, PbTiO3 > 25 mol%
The specimens for the piezoelectric property measurements or PZT > 30 mol% [10]. In this work, the amount of PZT
were poled in a silicone oil bath at 120 ◦ C by applying a dc in PZN–PZT ternary system was as high as 80 mol%,
electric field of 3 kV/mm for 30 min. The specimens were which exceeded far from the minimum amount of PZT
aged for 24 h prior to testing. (30 mol%) and was favored to the stabilization of perovskite
The crystalline structure of the samples was analyzed us- phase.
ing an X-ray diffractometry (XRD, Model Bruker Advance In addition, effect of Cr2 O3 doping on the transforma-
D-8) with a 2θ range from 10◦ to 70◦ . A step scan with a step tion of 0.2PZN–0.8PZT crystal structure was also observed
size of 0.02◦ was used with a counting time of 1 s/step. Raman in Fig. 1. It is accepted that the integrated intensity ratio be-
spectroscopy measurements were performed on a Spex 1403 tween (2 0 0) and (0 0 2) plane is 2:1 for tetragonal phase,
Raman spectrometer under backscattering geometry. Excita- and the (2 0 0) plane of rhombohedral phase usually coin-
tion was taken as the 488 nm line of Ar+ laser with 100 mW cides with (2 0 0) plane of tetragonal phase, leading to the
output power. Microstructure evolution was observed using a broadening of diffraction profiles around 2θ = 45◦ for compo-
scanning electron microscopy (SEM, Model Hitachi S-4500, sitions containing both rhombohedral and tetragonal phase.
Japan). The piezoelectric constant (d33 ) was measured using In this work, the base composition is located near the MPB
a quasi-static piezoelectric d33 meter (Model ZJ-3d, Institute composition region; coexistence of rhombohedral and tetrag-
of Acoustics Academic Sinica, China). The planar coupling onal phases is readily reflected in the XRD profile. This phe-
coefficient (kp ) was determined from resonance and anti- nomenon corresponded well with the former experimental
resonance method on the basis of IEEE standards by using results for PZN–PZT composition close to MPB, reported by
an impedance analyzer (Model HP4294A, Hewlett-Packard, Vittayakorn et al. [23]. With increasing Cr2 O3 content, the
CA). relative amount of tetragonal phase dramatically increased
while that of rhombohedral phase greatly decreased, as re-
vealed by the splitting change of (0 0 2) and (2 0 0) peaks
3. Results and discussion in Fig. 1. Thermodynamically, incorporation of Cr ions into
the lattice of perovskite structure stabilizes the tetragonal
The XRD patterns of 0.2PZN–0.8PZT specimens with the phase against rhombohedral phase. In other words, addition
addition of 0–1.0 wt.% Cr2 O3 are shown in Fig. 1. In these of Cr2 O3 shifts MPB compositional region at room temper-
patterns, only peaks of perovskite phase could be identified ature toward low PbTiO3 concentration end.
and no pyrochlore or other second phase was detected. Poly- The lattice constant c and a, together with the tetrago-
crystalline PZN with a pure perovskite structure is very diffi- nal distortion c/a for Cr-doped 0.2PZN–0.8PZT ceramics,
cult to prepare because of the high polarizability of Pb2+ and were calculated using the least square method from XRD
its interaction with Zn2+ cations, resulting in both a steric and data, and results are shown in Fig. 2. With increasing Cr2 O3
an electrostatic interaction. This destabilizes the perovskite content, the lattice constant a decreased gradually, while the
106 Y.D. Hou et al. / Materials Science and Engineering B 116 (2005) 104–108

of Cr solved in the lattice. These inferences are obviously

consistent with changes mentioned above in XRD patterns.
Fig. 4 shows SEM photographs of fractured surface of
Cr-doped 0.2PZN–0.8PZT ceramics. It is obvious that the
fracture mode of all specimens is predominantly intergranu-
lar. The grain size in the undoped 0.2PZN–0.8PZT specimen
was about 2.5 ␮m, but grain size remarkably increased with
increasing amount of Cr2 O3 addition in the doping range
0 wt.% ≥ x ≥ 0.3 wt.%. The specimen doped with 0.3 wt.%
Cr2 O3 exhibited the largest grain size about 3.8 ␮m. How-
ever, further increasing amount of Cr2 O3 above 0.3 wt.%
reduced the grain size gradually. From above results, it is
expected that Cr2 O3 has solubility of about 0.3 wt.% in
Fig. 2. The lattice constant c, a and tetragonal distortion c/a of Cr2 O3 -doped 0.2PZN–0.8PZT system. The Cr ion is homogenously dis-
0.2PZN–0.8PZT specimens. solved in 0.2PZN–0.8PZT lattice structure when the Cr2 O3
addition is below 0.3 wt.%, but further addition of Cr2 O3 will
constant c increased slightly. In the Cr2 O3 doping range inhibit the grain growth due to accumulation of Cr ion at the
0 wt.% ≥ x ≥ 0.3 wt.%, the tetragonal distortion c/a of spec- grain boundary [14].
imens increased greatly with increasing Cr2 O3 content, but Except of the change in microstructure, the addition of
are almost constant for x ≥ 0.3 wt.%, which confirmed that Cr2 O3 also affects significantly the dielectric properties of
the limit of the solid solubility of Cr2 O3 in 0.2PZN–0.8PZT 0.2PZN–0.8PZT ceramics. Fig. 5 shows the variation of poled
was about x = 0.3 wt.% [24]. and unpoled dielectric constant of specimens at 1 kHz with
Fig. 3 shows Raman spectra of Cr-doped 0.2PZN–0.8PZT Cr2 O3 doping concentration. As seen from Fig. 5, both the
ceramics. All Raman modes were assigned according to poled and unpoled dielectric constant shows a tendency to
the literature [25]. Peaks around 210, 260, 440, 560, and decrease with increasing amount of Cr2 O3 . Cr would be ex-
703 cm−1 are attributed to the E(2TO), E(3) + B1, E(2LO) pected to take a valency of 3+ (it was added as Cr2 O3 ) and
and A1 (2LO), A1 (3TO), and E(3LO) modes, respectively. It thus might be expected to sit on the B site as an acceptor.
is well known that the distinguishable Raman features during There is the possibility of Cr existing as Cr5+ or even Cr6+ ,
the rhombohedral–tetragonal transition are presented in low but these would require very strongly oxidizing conditions
frequency region (below 180 cm−1 ). From Fig. 3, it could be [27]. As well known, the substitutions of (Ti, Zr)4+ by accep-
clearly seen that, with increasing Cr2 O3 content, one weak tor dopant of Cr ions would lead to the creation of oxygen va-
peak appeared at about 140 cm−1 and the intensity increased cancies, which pin the movement of the ferroelectric domain
gradually. This low frequency peak at around 140 cm−1 be- walls and result in the decrease of dielectric constant [28].
longed to A1 (1TO) mode, assigned as a result of tetragonal In piezoelectric ceramics, the dielectric constant may be
polarization characteristics, and the variation of this mode is increased or decreased through poling treatment. Wang have
believed to be indicative of the phase transition [25,26]. In reported that after poling, the dielectric constant increases for
Fig. 3, it is difficult to determine the peak position of un- the tetragonal compositions, but decreases for the rhombohe-
doped specimens, however, the strengthening of A1 (1TO) dral compositions [29]. From Fig. 5, the increase of the dielec-
mode with the increasing of Cr2 O3 content indicated that, tric constant of the poled tetragonal compositions was also
the relative amount of tetragonal phase increased as results observed in Cr-doped 0.2PZN–0.8PZT systems. This vari-
ation of dielectric constant was attributed that in tetragonal
phase, dipole switching and electrostriction inducing stress
(dielectric constant increasing factor) play the dominant role,
not the factor of dipole rotation to the poling direction (di-
electric constant decreasing factor) [30].
Fig. 6 shows the changes in kp and d33 as a function
of the amount of Cr2 O3 addition. As can be seen, both kp
and d33 show a similar variation with increasing Cr2 O3 con-
tent. When the amount of Cr2 O3 was lower than solubil-
ity of 0.3 wt.%, kp and d33 were increased with increasing
Cr2 O3 content. The optimized values for kp of 0.70 and d33
of 491 pC/N were obtained for 0.3 wt.% Cr2 O3 content. It is
known that the formed oxygen vacancies, resulting from the
substitutions of (Ti, Zr)4+ by acceptor Cr3+ ions, inhibited
Fig. 3. Raman spectra of Cr2 O3 -doped 0.2PZN–0.8PZT specimens: (a) the movement of ferroelectric domain walls and resulted in
0 wt.%, (b) 0.10 wt.%, (c) 0.30 wt.%, (d) 0.80 wt.%. the decrease of kp and d33 . Inversely, kp and d33 are also gen-
 Y.D. Hou et al. / Materials Science and Engineering B 116 (2005) 104–108 107

Fig. 4. SEM photographs of fractured surface of Cr2 O3 -doped 0.2PZN–0.8PZT specimens: (a) 0 wt.%, (b) 0.10 wt.%, (c) 0.30 wt.%, (d) 0.50 wt.%, (e) 0.80 wt.%.

erally known to increase with an increase in the grain size

[28]. Accordingly, the improvement of piezoelectric prop-
erties mentioned above may be caused by the fact that the
effects of an increased grain size in the range of 0–0.3 wt.%
became more dominant than that of oxygen vacancies, which
was also observed in our previous investigation in Mn-doped
0.2PZN–0.8PZT systems [14]. When the amount of Cr2 O3 is
above 0.3 wt.%, the grain size decreased and the grain bound-

Fig. 6. Electromechanical coupling factor kp and piezoelectric constant d33

of Cr2 O3 -doped 0.2PZN–0.8PZT specimens.

ary phases, which are directly related to the volume of space

charge regions, got larger and finally resulted in lowing kp
and d33 .

4. Conclusion

Fig. 5. Poled and unpoled dielectric constant of Cr2 O3 -doped The structure and electrical properties of Cr2 O3 -doped
0.2PZN–0.8PZT specimens at 1 kHz. 0.2PZN–0.8PZT ceramics have been studied in detail. The
108 Y.D. Hou et al. / Materials Science and Engineering B 116 (2005) 104–108

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