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F/ P⫽E⫽ ␣ P⫹  P 3 ⫹ ␥ P 5 ⫹¯ 共2兲
and we can get
E/ P⬇1/共 0 r 兲 ⫽ ␣ ⫹3  P 2 ⫹5 ␥ P 4 ⫹¯ . 共3兲
174109-2
dc ELECTRIC-FIELD DEPENDENCE OF THE . . . PHYSICAL REVIEW B 69, 174109 共2004兲
FIG. 3. 共a兲–共c兲 Fitting to the dc electric-field dependence of the FIG. 4. 共a兲–共c兲 Fitting to the dc electric-field dependence of the
relative dielectric constant ( r ) of KTaO3 at 60 K 共first run兲 using relative dielectric constant ( r ) of KTaO3 共the fifth run兲 at 14 K
the even-power equation 共9兲, Johnson’s relation 共7兲, and Eqs. 共2兲 using the even-power equation 共9兲, Johnson’s relation 共7兲, and Eqs.
and 共3兲 共symbols, experimental data; solid curves, fitting results兲. 共2兲 and 共3兲 共symbols, experimental data; solid lines, fitting results兲.
1/共 r 0 兲 ⫽1/关 r 共 0 兲 0 兴 ⫹3  共 r 0 E 兲 2 ⫹5 ␥ 共 r 0 E 兲 4 .
共8兲 and 3共b兲 from 0 to 60 kV/cm. The fitting looks reasonable
and there is not much difference for the fitting between the
Solving this implicit equation, we can obtain the dielectric two equations. The fitting parameters are 1 ⫽938, 2
constant as a function of electric field. ⫽1.27⫻10⫺11 (V/m) ⫺2 , and 3 ⫽1.38⫻10⫺25 (V/m) ⫺4 for
the even-power term Eq. 共9兲; ⫽3, ⫽3.010 10, (V m5 /C3 )
3. Even-power relation at low fields
for Johnson’s relation.
For the Johnson relation, a prerequisite (0) 3 E 2 ⬍1 can The fitting to the data for the fifth run at 14 K with a
be met in most practical cases. For example, for KTaO3 and higher r shows that the even-power relation seems only
SrTiO3 , ⫽3  ⫽⬃1010 (V m5 /C3 ), 14 and the relative per- reasonable below 20 kV/cm, as shown in Fig. 4共a兲; but the
mittivity r (0)⭐1000, then 关 0 r (0) 兴 3 E 2 ⭐0.007 at E fitting with Johnson’s relation 关Eq. 共7兲兴 is more reasonable
⭐10 kV/cm, and 关 0 r (0) 兴 3 E 2 ⭐0.25 at E⭐60 kV/cm. up to 60 kV/cm, as shown in Fig. 4共b兲. The fitting parameters
Hence, Johnson relation Eq. 共7兲 can be expanded as a poly- are 1 ⫽1716, 2 ⫽1.71⫻10⫺10 (V/m) ⫺2 , and 3 ⫽1.39
nomial consisting of even-power terms of E to high orders, ⫻10⫺23 (V/m) ⫺4 for the even-power term Eq. 共9兲;
⫽3  ,  ⫽4.23⫻1010 (V m5 /C3 ) for Johnson’s relation.
r 共 E 兲 ⫽ r 共 0 兲 / 兵 1⫹ 关 0 r 共 0 兲兴 3 E 2 其 1/3⫽ 1 ⫺ 2 E 2 ⫹ 3 E 4
For the dielectric data obtained at the first run at 14 K
⫺ 4 E 6 ⫹ 5 E 8 ⫺¯ , with an even higher r (0) 共⬃2800兲 for paraelectric KTaO3 ,
the even-power relation fitting is only reasonable below ⬃10
where 1 ⫽ r (0), 2 ⫽ 31 (0) 4 , 3 ⫽ 92 2 (0) 7 , 4 kV/cm, as shown in Fig. 5共a兲. The fitting to Johnson’s rela-
⫽ 14
81 (0) , 5 ⫽ 243 (0) , etc.
3 10 35 4 13
tion is reasonable up to 60 kV/cm, but with a large fitting
In fact, the even-power relation error, as shown in Fig. 5共b兲. The fitting parameters are 1
r 共 E 兲 ⫽ 1 ⫺ 2 E 2 ⫹ 3 E 4 ⫺ 4 E 6 ⫹ 5 E 8 ⫺¯ 共9兲 ⫽2761, 2 ⫽7.24⫻10⫺10 (V/m) ⫺2 , and 3 ⫽9.78
⫺23
⫻10 (V/m) ⫺4 for the even-power term; ⫽3  ,  ⫽3.8
is a common relationship for analyzing the electric-field de- ⫻1010 (V m5 /C3 ) for Johnson’s relation.
pendence of the dielectric constant in the literature. It should
be emphasized that this treatment is strictly limited to 共i兲 a
2. Limitation of the approximate treatments
small dc electric field and 共ii兲 a small polarization case 共near-
paraelectric state兲. Under these two prerequisites, Eq. 共9兲 de- The fitting results show that the even-power Eq. 共9兲 only
scribes the dielectric constant under dc electric field for works for a low dielectric constant and at low electric fields.
many materials. This is not surprising because Eq. 共9兲 is assumed to hold
only for low electric fields and small polarizations.
B. Fitting results for paraelectric KTaO3 Johnson reported that Eq. 共7兲 can describe the dielectric
behavior of (Sr,Ba)TiO3 up to a high dc electric field 共40
1. Paraelectric KTaO3
kV/cm兲.10 In the present work, the experimental data from
For the data with a relatively smaller dielectric constant paraelectric KTaO3 can be described by the Johnson relation
关 r (0)⫽⬃1000兴 at 60 K, the fitting to the even-power Eq. Eq. 共7兲, but the accuracy for the case of a high dielectric
共9兲 and Johnson’s relation 关Eq. 共7兲兴 is shown in Figs. 3共a兲 constant is not satisfactory.
174109-3
CHEN ANG AND ZHI YU PHYSICAL REVIEW B 69, 174109 共2004兲
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dc ELECTRIC-FIELD DEPENDENCE OF THE . . . PHYSICAL REVIEW B 69, 174109 共2004兲
from mode B, and the rest of the dielectric constant from the
QPB of SrTiO3 . Under dc bias, the two dielectric modes are
easily suppressed, while the dielectric background sustained
under high dc bias, although decreased, is from more ‘‘in-
trinsic’’ QPB contributions.6,18 Thus the field dependence of
the dielectric constant at a certain temperature reflects such a
multipolarization mechanism. Therefore, the field depen-
dence of the dielectric constant of Bi:SrTiO3 cannot be de-
scribed by the single polarization mechanism using Eqs. 共2兲
and 共3兲, or the approximate treatments Eq. 共7兲 and Eq. 共9兲.
This is reminiscent of the dielectric response in the ferro-
electric state of PZT at room temperature, which has been
recognized as containing both intrinsic and extrinsic
contributions.15 Moreover, polar clusters are reported to be
superimposed on a paraelectric background. For instance, the
dielectric temperature spectra of SbSI can be decomposed
into a dielectric peak superimposed on a so-called quantum
paraelectric background under pressure.19
On the other hand, recent efforts on applying LGD theory
to a ferroelectric relaxor seem rather difficult,20 although the
theory has been successfully applied to the description of
BaTiO3 共Ref. 21兲 and Pb(Zr,Ti)O3 . 22 This might be mainly
due to the existence of some nanopolar clusters in the ferro-
electric relaxor, which are superimposed on the dielectric/
ferroelectric polarization background of the material. The
single polarization mechanism is found to be insufficient to
FIG. 7. Schematic diagrams of the temperature dependence of
describe the whole polarization picture.
polarization species for ferroelectric relaxors, ferroelectrics, and
Therefore, the dielectric spectra observed in polar dielec- paraelectrics.
trics, including paraelectrics, ferroelectrics, and ferroelectric
relaxors, may generally include many possible polarization
physically, although fitting may be in good agreement with
contributions from different polarization mechanisms.23 The
the experimental data because Eqs. 共2兲 and 共3兲 are infinite
schematic diagrams of the structure of the dielectric spectra
series in mathematics, and the combination of these two
of these three types of polar dielectrics are summarized in
equations can provide a powerful fitting regardless of any
Fig. 7. For paraelectric and dielectric relaxors, the structure
physical mechanisms or details.
of dielectric temperature spectra consists of the paraelectric
background and possible micropolar-cluster walls.
One typical example of ferroelectrics is the dielectric B. Description of the ‘‘extrinsic’’ polarization mechanism
spectrum of the ferroelectric and ferroelastic Cd2 Nb2 O7 as According to the above analysis of dielectric spectra, a
reported in Ref. 24. Around the paraelectric-ferroelectric question is how to describe the field dependence of the di-
phase-transition temperature, the dielectric spectrum consists electric constant in polar dielectrics with more than one po-
of polarization contributions from electrons, phonons, larization mechanism. One scenario is using two sets of or-
ferroelectric-ferroelastic effect, ferroelectric macrodomain- der parameters, for example for the LGD free-energy
wall motions, polar microclusters, etc. At a fixed tempera- expansion,
ture, the dielectric constant is gradually suppressed with in-
creasing dc bias due to the different response of these F 共 P,T 兲 ⫽F 共 0,T 兲 ⫹ ␣ 1 / 2 P 21 ⫹  1 / 4 P 41 ⫹ ␥ 1 / 6 P 61 ⫹ ␣ 2 / 2 P 22
polarization mechanisms at different bias levels. Thus, mul-
tipolarization mechanisms are reflected in the r (E) profile. ⫹  2 / 4 P 42 ⫹ ␥ 2 / 6 P 62 ⫹¯ . 共10兲
For the ferroelectric relaxor, in addition to the electron,
phonon, and the polar microcluster contributions, the polar The parameters P 1 and P 2 represent two order parameters.
microcluster wall motions may become important at low fre- More terms may be added when considering the interaction
quencies. between the two order parameters.
In addition, in the so-called soft-mode dielectrics, such as An alternative scenario is to decompose the different po-
SrTiO3 and KTaO3 , the possible coupling between unavoid- larization mechanisms and to describe their contributions,
able defects/impurities and the soft mode may lead to a large respectively. As is discussed above, it is observed that there
contribution to the dielectric constant. The possible existence is more than one polarization contribution to the dielectric
of microclusters and their wall motion may greatly enhance response for many nonlinear polar dielectrics. One comes
the dielectric constant. In a material with more than one po- from an intrinsic contribution of the lattice phonon polariza-
larization mechanism, fitting using single-polarization- tion, which can be described by the principal order param-
mechanism equations, like Eqs. 共2兲 and 共3兲, makes no sense eters of the phenomenological theory. The other comes from
174109-5
CHEN ANG AND ZHI YU PHYSICAL REVIEW B 69, 174109 共2004兲
r ⫽ 共 P 0 x/ 0 兲关 1/共 xE 兲 2 ⫺1/sinh2 共 Ex 兲兴 , 共13兲 D. Fitting of the dielectric behavior of Bi:SrTiO3 and KTaO3
under dc bias
where x⫽ P 0 V/k B T.
Bi:SrTiO3
A similar relationship can also be derived from the
‘‘double-well’’ model for the reorientational polarization,5 Two cluster terms are used in Eq. 共17兲 due to the two
polarization mechanisms modes A and B superimposed on
⫽ 0 tanh共 0 E eff /k B T 兲 . 共14兲 the quantum paraelectric background. The fitting to experi-
mental data using Eq. 共17兲 at several temperatures is shown
The effective field is E eff⫽E⫹P, where is a generalized in Fig. 8. It can be seen that the fitting curves 共solid lines兲 are
Lorentz factor depending on the geometry of the dipole lat- in good agreement with the experimental data in Fig. 8.
tice. Generally speaking, P is small for the ‘‘extrinsic polar- From the fitting,  is in the range from ⬃1.5⫻1010 to 2.7
ization,’’ and we have an approximation E eff⫽E. Then Eq. ⫻1010 共V m5/C3兲 in the temperature range of 13– 65 K; this
共14兲 can be rewritten as is in good agreement with the data reported in Ref. 14.
From Fig. 8, the polar clusters contribute significantly to
P⫽ P 0 tanh共 0 E/k B T 兲 ⫽ P 0 tanh共 P 0 VE/k B T 兲 , 共15兲
the dielectric constant up to ⬃20 kV/cm for both clusters A
where P 0 is the effective polarization of one cluster. and B. Without dc bias, the contribution to the dielectric
Based on Eq. 共15兲, the dielectric constant is derived as constant is about 24% for cluster B 共mode B兲 at 40 K around
which mode B reaches its maximum in the r versus T pro-
⫽ P/ E, file, and the contribution to the dielectric constant is ⬃16%
174109-6
dc ELECTRIC-FIELD DEPENDENCE OF THE . . . PHYSICAL REVIEW B 69, 174109 共2004兲
Fig. 10. It can be seen that the fitting curves 共solid lines兲 fit
well to the experimental data. For Johnson’s term,  is
⬃5.5⫻1010 共V m5/C3兲 for both cases. The cluster size of 2.5
FIG. 8. Electric-field dependence of the dielectric constant ( r ) nm at the first run decreases down to 2.1 nm at the fifth run
of Bi:SrTiO3 at 13, 25, 40, and 55 K at 10 kHz. Open circles, for the cluster term, which is in good agreement with the size
experimental data; solid lines, fitting results according to Eq. 共17兲
of five to six unit cells 共⬃2–3 nm兲 of ferroelectric microre-
including the contribution from the Johnson term J 共dash line兲, the
gions suggested by the study of Raman spectra in Ref. 16.
contribution from cluster A 共dash-dot兲, and that from cluster B 共dot兲.
The polar-cluster polarization of ⬃0.7 C/cm2 is obtained
for cluster A 共mode A兲 at 25 K around which mode A reaches for both runs.
its maximum in the r versus T profile. Although the fitting data by using Eq. 共17兲 are similar to
The cluster polarizations of the two polar clusters corre- those results reported in Ref. 17, where a combination of the
sponding to modes A and B obtained by fitting to Eq. 共17兲 are even-power equation and the cluster term was used, Eq. 共17兲
shown in Fig. 9. It can be seen that clusters A and B reach in the present work is more physically reasonable for the
their maximum at 25 and 40 K, respectively, with polariza- fitting because of the limitation of the validation of the even-
tions P A ⫽0.39 C/cm2 and P B ⫽0.80 C/cm2 , which cor- power equation at high electric fields.
respond to the temperature at which r maximum occurs. It
is interesting to notice that slim hysteresis loops are observed
V. CONCLUSIONS
for this sample although it acts as a ‘‘dielectric relaxor’’.6
The remnant polarization is of ⬃0.2, 0.6, and 1.2 C/cm2 at The theoretical treatment of Landau-Ginzburg-
10, 20, and 30 kV/cm, respectively. The cluster polarization Devonshire 共LGD兲 theory and its approximate treatments of
values obtained from the calculation by Eq. 共17兲 are compa- the electric-field dependence of the dielectric constant in po-
rable to these measured data within the same order of mag- lar dielectrics are discussed. It is found that a treatment of
nitude. The calculated size of the polar cluster is ⬃4 –7.5 nm LGD-group equations 共2兲 and 共3兲 can describe the field de-
for both modes A and B in the whole tempera-ture range,
pendence of the dielectric constant very well for a single-
which is also in the same order of magnitude as observed in
polarization-mechanism process. On the other hand, the
Ca-doped SrTiO3 . 26
semiempirical Johnson relation 共7兲, which is an explicit func-
KTaO3 tion of the electric field, is a reasonable approximate descrip-
tion for the field dependence of the dielectric constant in
The fitting to the experimental data at the first and fifth
replacing the rigorous theoretical treatment in many cases.
runs using Eq. 共17兲 with one polar cluster term is shown in
Furthermore, based on the empirical observation of the
structure of dielectric spectra, multipolarization processes
occur in many polar dielectrics. In this case, the treatment
based on a single order parameter of LGD theory is insuffi-
cient. A multipolarization-mechanism model is therefore sug-
gested in the present work, and
r 共 E 兲 ⫽ r 共 0 兲 / 兵 1⫹ 关 0 r 共 0 兲兴 3 E 2 其 1/3
⫹⌺ 共 P 0 x/ 0 兲关 cosh共 Ex 兲兴 ⫺2
FIG. 9. Temperature dependence of the polar-cluster polariza-
tion 共P兲 for clusters A and B obtained by the best fit to the dc is adopted to describe the field dependence of the dielectric
electric-field dependence of the dielectric constant to Eq. 共17兲. constant, where Johnson’s term represents the lattice polar-
174109-7
CHEN ANG AND ZHI YU PHYSICAL REVIEW B 69, 174109 共2004兲
ization induced from the LGD theory, and the latter repre- can be realized. For example, as P 0 ⫽1 C/cm2
sents the reorientational polarization contribution. The fitting ⫽0.01 C/m2 , V⫽10 nm3 , and k B T⫽0.026 eV at 300 K, we
to experimental data shows that the proposed have x⫽2.4⫻10⫺8 m/V. For E⫽10 kV/cm⫽105 V/m, xE
multipolarization-process model works well. ⫽2.4⫻10⫺3 Ⰶ1. Thus the relationship can be simplified as
It should also be mentioned that the Johnson relationship
r (0)/ 兵 1⫹ 关 0 r (0) 兴 3 E 2 其 1/3 and the reorientation polariza- 共 P 0 x/ 0 兲关 cosh共 Ex 兲兴 ⫺2 ⫽ 共 P 0 x/ 0 兲关 1⫹ 共 Ex 兲 2 /2兴 ⫺2 .
tion term ( P 0 x/ 0 ) 关 cosh(Ex)兴⫺2 can also be simplified to 共A1a兲
even-power polynomials when the electric field and/or di-
electric constant is small. Obviously, the condition (Ex) 2 /2⬍1 is also satisfied, and
Eq. 共A1a兲 can be written in an expanded form,
ACKNOWLEDGMENT
共 P 0 x/ 0 兲关 1⫹ 共 Ex 兲 2 /2兴 ⫺2
Acknowledgment is made to the Donors of the American
Chemical Society Petroleum Research Fund for support of ⫽ 共 P 0 x/ 0 兲关 1⫺2 共 Ex 兲 2 /2⫹3 共 Ex 兲 4 /4⫺4 共 Ex 兲 6 /8
this research, and to the Faculty Research Committee of the ⫹5 共 Ex 兲 8 /16⫺••• 兴
University of Akron for financial support.
⫽q 1 ⫺q 2 E 2 ⫹q 3 E 4 ⫺q 4 E 6 ⫹q 5 E 8 ⫺••• 共A1b兲
APPENDIX
where q 1 ⫽( P 0 x/ 0 ), q 2 ⫽ P 0 x 3 / 0 , q 3 ⫽ 43 P 0 x 5 / 0 , q 4
Now let us consider the cluster polarization relation Eq. ⫽ 12 P 0 x 7 / 0 , q 5 ⫽ 165 P 0 x 9 / 0 , etc. Equation 共16兲 also in-
共16兲. In most cases, a precondition, xE⫽( P 0 V/k B T)EⰆ1, cludes all even-power terms, as does Eq. 共9兲.
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