Investigation of thickness dependence of the ferroelectric properties of Pb ( Zr 0.

6 Ti
0.4 ) O 3 thin-film capacitors
R. Bouregba, G. Le Rhun, G. Poullain, and G. Leclerc

Citation: Journal of Applied Physics 99, 034102 (2006); doi: 10.1063/1.2170414

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 JOURNAL OF APPLIED PHYSICS 99, 034102 共2006兲

Investigation of thickness dependence of the ferroelectric properties

of Pb„Zr0.6Ti0.4…O3 thin-film capacitors
R. Bouregba,a兲 G. Le Rhun, G. Poullain, and G. Leclerc
Laboratoire CRISMAT-ENSICAEN et Université de Caen, CNRS UMR 6508, Boulevard du Maréchal Juin,
14050 Caen Cedex, France
共Received 28 March 2005; accepted 21 December 2005; published online 8 February 2006兲
The ferroelectric properties of Pt/ Pb共Zr0.6Ti0.4兲O3 / Pt/ TiO2 / SiO2 / Si thin-film capacitors with
different thicknesses are investigated. According to the literature data, tilting of the hysteresis loops
and marked increase of the coercive fields are observed when the thickness of the film is reduced.
The degradation of the switching properties is fully reproduced by simulations including
nonferroelectric space-charge layers at both ferroelectric/electrode interfaces. Based on the
theoretical results, a converse model is constructed from which the overall interface capacitance, the
total interface built-in potential, and both dielectric permittivity and polarization of the bulk
ferroelectric layer are determined for each film. Remarkably the polarization loop due to the
switching domains, calculated for each Pb共Zr, Ti兲O3 共PZT兲 capacitor, exhibited a squarelike shape
with coercive fields in agreement with the bulk value. Moreover, a unique set of parameters was
found whatever the film thickness. From our results it is concluded that the degradation of the
ferroelectric properties of metal-PZT thin-film-metal capacitors, often encountered when their
thickness is reduced, probably arises from a mechanism of modulation of density and sign of the
space charge at both interfaces. © 2006 American Institute of Physics. 关DOI: 10.1063/1.2170414兴

I. INTRODUCTION
For two decades, lead zirconate titanate Pb共Zr, Ti兲O3
共PZT兲 ferroelectric thin films have been extensively investi-
gated due to their great potential for integration in silicon
devices.1 However, it has been widely demonstrated that re-
ducing the thickness of PZT films comes with a significant
increase of the coercive field 共Ec兲,2–4 especially when metal-
lic electrodes, such as platinum, are used. On the other hand,
a simultaneous decrease of the dielectric permittivity is
observed.2,5,6 The possible presence, at the ferroelectric-
electrode interfaces, of thin nonferroelectric layers with low
dielectric permittivity was suspected to provoke the degrada-
tion of the dielectric and ferroelectric properties of PZT
films. Different mechanisms have been invoked to explain
the origin of such degraded layers including formation of
Schottky depletion layers,6,7 possible damages caused at the
surface of the PZT film during deposition of the top
electrode,3 or development of a nonferroelectric layer at the
initial stage of PZT growth.5 Typically the effects of inter-
face layers may be included by modeling the ferroelectric
capacitor as a stacked structure, formed by the bulk ferro-
electric layer in series with a linear interface capacitance.
Such a serial disposition is suitable to explain the apparent
decrease of the dielectric permittivity as it correctly predicts
the observed linear variations of the reciprocal capacitance of
the film versus its thickness.3 Moreover this kind of plot
allows the determination of the interface capacitance and the
dielectric permittivity of the bulk ferroelectric layer.
Concerning the ferroelectric properties, simulations of
hysteresis loops including nonswitching dielectric layers re-
a兲
Electronic mail: rachid.bouregba@ensicaen.fr
produced quite well the increasing tilt often observed when
the thickness of the ferroelectric film is reduced.8–10 This is
consistent with the serial capacitance model since the voltage
drop across the interface capacitance is expected to yield a
reduction of the field applied to the bulk ferroelectric layer,
hence a decrease of the polarization. However, the observed
thickness dependence of Ec cannot be recovered if the inter-
face dielectric layers are considered as insulating or passive
layers.11,12 This argument can be verified by adding a capaci-
tor in series with a ferroelectric capacitor.12 However, it was
suggested that thin surface dielectric layers account for the
experimental variations of the coercive field when consider-
ing charge injection.12,13
In this article, the ferroelectric properties of PZT films
with thicknesses ranging from 100 to 320 nm are investi-
gated. The observed increase of the coercive field with de-
creasing thickness is qualitatively reproduced by simulations
based on a model in which the interface layers are treated as
nonferroelectric but uniformly charged layers. We assumed
indeed that injected charge leads to the build up of potential
barriers at the ferroelectric-electrode interfaces. The main in-
teresting point is that the model enables the estimation of the
effects of surface charged layers over the entire hysteresis
loop, and not only on the coercive fields. Afterwards, a
method is constructed allowing the determination, from ex-
perimental data, of the total interface built-in potential, the
overall interface capacitance, and the dielectric permittivity
of the bulk ferroelectric layer. Then we demonstrate the pos-
sibility to compute the actual polarization due to the switch-
ing domains from the measured hysteresis loops. The calcu-
lated polarization loops are essentially identical, whatever
the film thickness. In particular, the extracted coercive elec-

0021-8979/2006/99共3兲/034102/7/$23.00 99, 034102-1 © 2006 American Institute of Physics

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 034102-2 Bouregba et al. J. Appl. Phys. 99, 034102 共2006兲

FIG. 1. ␪-2␪ XRD patterns of the PZT films with different thicknesses FIG. 2. Hysteresis loops of the PZT capacitors with different thicknesses:
grown on Pt/ TiO2 / SiO2 / Si substrate. 320 nm 共circles兲, 250 nm 共squares兲, 200 nm 共triangles兲, and 100 nm
共diamonds兲.

tric fields are found to be independent of the film thickness

which the ferroelectric bulk layer 共thickness d f 兲 is sand-
and in remarkable agreement with the PZT bulk value.
wiched by two nonferroelectric space-charge layers 共thick-
nesses di1 and di2 assumed constant whatever the electric-
II. MODEL FOR SIMULATION OF THICKNESS field strength兲 共see Fig. 3兲. The validity of this approach is
EFFECTS justified as increase of positive and negative coercive fields
Pb共Zr0.6Ti0.4兲O3 films were grown on Pt/ TiO2 / SiO2 / Si may be demonstrated by connecting precharged standard ca-
substrate by in situ rf magnetron sputtering using a multitar- pacitors in series with a PZT capacitor, on condition, how-
get chamber. The thickness of the films was controlled with a ever, to correctly add diodes.16
Dektak profilometer. PZT capacitors with an area of 5.29 In Fig. 3, ␧i1,2 and Ni1,2 are, respectively, the dielectric
⫻ 10−8 m2 were patterned by lift off from platinum sputtered permittivity and the concentration of charges per volume unit
on the surface of the films and using UV photolithography. 共assumed uniformly distributed兲 of each interface layer, ␧ f is
All the hysteresis measurements were performed using a Ra- the dielectric permittivity of the ferroelectric layer. The
diant Technology Standard Precision Workstation. P f -E f loop represents the nonlinear variation of the polariza-
Figure 1 shows the typical x-ray-diffraction 共XRD兲 pat- tion due to the switching domains as a function of the elec-
terns of the PZT films. All the films were highly 共111兲 ori- tric field applied to the ferroelectric layer. We assumed that
ented with no pyrochlore phase. In situ growth of the perov- the direction of the applied voltage Vappl along the 共0 , x兲 axis
skite phase and control of the crystallographic orientation corresponds to positive values of the E axis of the D-E plots,
were possible by sputtering a thin TiOx layer on the platinum as the applied electric field is calculated from E = Vappl / d. It
electrode prior to PZT deposition. More details about the
preparation and the structural characterization of our PZT
films may be found elsewhere.14,15
Figure 2 displays the D-E hysteresis loops measured at
the frequency F = 500 Hz. The amplitude of the applied volt-
age was systematically adjusted in order to get the same
maximum polarization. It can be observed that positive and
negative coercive fields increase when the thickness of the
PZT capacitors is decreased. For each film the positive Ec
value 共noted E+c 兲 is larger than the negative one 共E−c 兲. E+c
increases from 70 to 143 kV/ cm and E−c from −48.5 to
− 98 kV/ cm as the thickness decreases from 320 to 100 nm.
At the same time, higher maximum electric fields are re-
quired to reach the same maximum polarization, leading to
hysteresis loops with elongated shape.
To simulate the observed thickness effects, we modeled FIG. 3. The PZT capacitors are modeled as stacked structures with a ferro-
the PZT capacitor 共total thickness d兲 as a stacked structure in electric layer and a nonferroelectric space-charge layer at each surface.
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 034102-3 Bouregba et al.
must be noted that, with this definition, E represents only the
apparent or the average electric field in the ferroelectric ca-
pacitor.
In a recent article we investigated an oxygen deficient
epitaxial PZT film which exhibited strong “imprint.”17 The
shifting of the hysteresis loop along the electric-field axis
was simulated with a model taking into account the effects of
interface space-charge layers. The formulation of the prob-
lem is detailed in the Ref. 17–19, which themselves are
based on a previous work by Miller et al.8 By using the same
approach it can be shown
冋 冉 冊册
␧0␧f di1 + di2
D= 共Vappl − Vbi1 + Vbi2兲 + P f 1 −
d d
with
␳i1di1
2
␳i2di2
2
Vbi1 = , Vbi2 =
2␧0␧i1 2␧0␧i2
and
冉 冊
di1 + di2 ␧ f di1 di2
␣=1− + + .
d d ␧i1 ␧i2
␧0 is the permittivity of free space. ␳i1 and ␳i2 represent the
charge per volume unit at both space-charge layers, given by
␳i1,2 = eNi1,2 where e is the electron charge. Vbi1 and Vbi2
stand for the potential barriers in these layers. To simulate
the thickness dependence of the external or apparent D-E
hysteresis loop of the ferroelectric capacitor, the electric dis-
placement D is calculated with the relation 共1兲. The compu-
tations start from an arbitrary P f -E f polarization loop in the
ferroelectric layer, generated with the hyperbolic tangent
function.8 The numerical algorithm is based on an iterative
procedure that is detailed in the Ref. 8 and requires the elec-
tric field E f in the ferroelectric layer to be expressed. From
Fig. 3 and previous works,8,17–19 it can be shown
冋
E f = Vappl − Vbi1 + Vbi2 − 冉
P f di1 di2
+
␧0 ␧i1 ␧i2
冊册 1
d␣
. 共2兲
One important point to be considered for a correct simulation
of the observed variations of Ec concerns the sign of the
charge per volume unit ␳i1 and ␳i2. An apparent positive
coercive field E+c larger than the positive coercive field E+fc in
the bulk ferroelectric layer is obtained if one assumes posi-
tive potential barriers at both interface layers, i.e., Vbi1 and
Vbi2 oriented in the same direction as Vappl. In that case in-
deed, the voltages in the three layers of the stacked structure
add up. But this may appear restrictive as in fact an infinite
number of combinations is possible. For example, the same
result may be obtained when Vbi1 is positive and Vbi2 nega-
tive on condition that Vbi1 ⬎ 兩Vbi2兩. However, for simplicity of
our simulations we assumed that Vbi1 and Vbi2 are both posi-
tive. Hence we infer that the sign of the charge at the left-
hand interface and that of the charge at the right-hand inter-
face are different, that is ␳i1 and ␳i2 are positive and negative,
respectively. Note that for the experimental implementation
described in Sec. III below, the sign of Vbi1 and Vbi2 will be
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J. Appl. Phys. 99, 034102 共2006兲
of minor importance as we will then consider the total
built-in potential.
In our previous work devoted to investigation of imprint
phenomenon, the properties of the interface layers were kept
constant throughout the simulation, i.e., whatever the sign
and the amplitude of the alternating applied voltage.17 How-
ever, simulation of the observed thickness dependence of Ec
now requires the physical properties of both interface layers
to be modulated during one cycle of Vappl. One obvious rea-
son for this is that when Vappl is negative, Vbi1 and Vbi2 have
to be reversed to obtain an apparent 兩E−c 兩 larger than 兩E−fc兩 in
the bulk ferroelectric layer. Hence, at that time ␳i1 and ␳i2
1 must be negative and positive, respectively.
,
␣ In the present work, to define the moments at which ␳i1
共1兲 and ␳i2 change sign, we adopted the sequence proposed by
Tagantsev and Stolichnov in the framework of the near-by-
electrode charge injection model.13 These authors explained
the thickness dependence of E+c value by assuming that
charge is injected at the interfaces when the polarization
changes from its maximum negative value 共−P fm兲 to its
maximum positive one 共+P fm兲. Reciprocally, increase of 兩E−c 兩
was explained by assuming that charge injection happens
again when the polarization changes from +P fm to −P fm.
Accordingly we infer that both interfaces are likely to store
charge with different sign, and that the charge stored at each
interface changes sign according to the sequence above.
Finally, the two following sequences were adopted for
our simulations:
⳵Vappl
␳i1 ⬎ 0 and ␳i2 ⬍ 0 when ⬎ 0,
⳵t
⳵Vappl
␳i1 ⬍ 0 and ␳i2 ⬎ 0 when ⬍ 0,
⳵t
while the other parameters of the interface layers 共di1, di2,
␧i1, and ␧i2兲 were kept constant. We assumed that ␳i1 and ␳i2
change sign according to the time derivative of Vappl instead
of the time derivative of polarization. However, this is not
contradictory with the analysis by Tagantsev and Stolichnov
as +P fm and −P fm values are obtained at the same times as
when Vappl reaches its maximum positive 共+Vapplm兲 and nega-
tive 共−Vapplm兲 values, respectively. Moreover, it must be
noted that such sequence is consistent with the preceding
analysis according to which ␳i1 has to be positive and ␳i2
negative when the instantaneous apparent electric field E
equals E+c , i.e., when Vappl is positive. Indeed at that time E+c ,
hence Vappl, belongs to that part of the polarization loop
switching from −Pm to +Pm. As ␦Vappl / ␦t is then positive,
the signs of ␳i1 and ␳i2 are in agreement with those defined
with the first of the two sequences above. The same agree-
ment is found for the second sequence when considering the
signs of ␳i1 and ␳i2 leading to the increase of E−c .
Figure 4 shows the result of the simulations. The follow-
ing values were adopted for the parameters of both interface
layers: di1 = di2 = 5 nm, ␧i1 = ␧i2 = 100, and Ni1 = Ni2
= 3 ⫻ 1026 m−3. For simplicity of the analysis, we assumed
that both layers present the same properties. Though the
charge concentrations used for the simulations appear very
 034102-4 Bouregba et al. J. Appl. Phys. 99, 034102 共2006兲

冋
Pf = D −
␧ 0␧ f
␣
冉
E−
Vbi
d
冊册 ␣, 共3兲

with
␧ 0␧ f A
␣=1+ , 共4兲
dCi
where A is the area of the ferroelectric capacitor. Vbi and Ci
stand for the total built-in potential and the overall interface
capacitance, respectively. They are given by
␳i1di1
2
␳i2di2
2
Vbi = Vbi1 − Vbi2 = − , 共5兲
2␧0␧i1 2␧0␧i2

1
=
1
+
1
=
1 di1 di2
+
Ci Ci1 Ci2 ␧0A ␧i1 ␧i2
. 冉 冊 共6兲

From expression 共2兲 and using the assumption above, one

obtains for E f the following simplified expression:17,18

FIG. 4. Simulation of thickness effect on the D-E hysteresis loops of

stacked ferroelectric capacitors. The concentration of charges per volume
冋 冉
Ef = E −
1
d
Vbi +
AP f
Ci
冊册 1
␣
. 共7兲

unit at each interface layer was Ni1 = Ni2 = 3 ⫻ 1026 m−3 and the sign was
modulated according to the sequence described in the text. The total thick-
ness d was 320 nm 共thin continuous line兲, 250 nm 共short broken line兲,
200 nm 共mixed broken line兲, and 100 nm 共long broken line兲. In thick con-
tinuous line is the polarization loop due to the switching domains.
large, such values turned out, however, to be essential to
yield large variations of Ec, as observed experimentally. Con-
cerning the bulk ferroelectric layer, we took ␧ f = 300 and the
arbitrary P f -E f loop from which we started the computations
is plotted in thick line. The maximum applied voltage was
systematically adjusted to yield the same maximum polariza-
tion whatever the film thickness, as during measurements. As
The relations 共3兲–共7兲 enable the computation of the
P f -E f polarization loops of a given PZT capacitor from the
measurement of the electric displacement D and the applied
electric field E. However, for a correct implementation, the
values of Vbi 共including its sign兲, Ci, and ␧ f have to be de-
termined first, and this according to whether dVappl / dt is
positive or negative. This may be accomplished as follows.
As the electric displacement is conservative, we can
state that the electric displacement in the ferroelectric layer,
given by D f = ␧0␧ f E f + P f , equals the electric displacement D
measured on the electrodes of the stacked capacitor. Then
from either expression 共3兲 or 共7兲, it can be shown

it can be seen, a marked increase of Ec with decreasing thick-
ness is obtained, associated with significant horizontal
stretching out of the D-E loops. Though remaining qualita-
tive, the agreement with the measured hysteresis loops is
satisfying as all in all the thickness dependence is recovered.
III. MODEL FOR EXPERIMENTAL IMPLEMENTATION
To get furthermore quantitative analysis, we examined
the possibility, based upon the model described in Sec. II, to
take out from hysteresis measurements, the physical proper-
ties of bulk ferroelectric layer and those of interface layers in
the four studied PZT capacitors. Especially we focused on
the computation of the polarization due to the switching do-
mains in the bulk ferroelectric layer. The underlying idea is
to establish that the P f -E f loops of all the studied PZT ca-
pacitors are actually similar and that the experimentally ob-
served thickness dependence of the ferroelectric properties is
provoked by interface effects such as those simulated before.
It must be noticed that for simplicity of the analysis, the
effects of possible leakage currents have been neglected,
though it is possible to take them into account.18,19 Moreover
we assumed di1 Ⰶ d and di2 Ⰶ d as the thickness of both in-
terface layers is expected to be much smaller than that of the
ferroelectric layer. Then from expression 共1兲 it can be
shown17,18
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冉 冊
AD
+ Vbi
Ci
E = Ef + . 共8兲
d
Note that this relation is very similar to that found by
Tagantsev and Stolichnov.13 In the special case where D = 0,
the relation 共8兲 reveals how the potential barriers at both
interfaces contribute to the increase of the apparent coercive
fields: increase from E+fc to E+c arises from a positive total
built-in potential, whereas increase from 兩E−fc兩 to 兩E−c 兩 requires
a negative total potential barrier. This is evidenced on Fig. 5
showing the result of simulations performed as for Fig. 4,
except that ␳i1 and ␳i2 were kept null all the time of the
computations.
But the main interest of the relation 共8兲 stems from the
fact that if Vbi, Ci, and E f are assumed independent of the
thickness, then one expects that the plot of E vs 共1 / d兲 should
lead to a straight line where slope is related to Vbi and Ci.
Furthermore, the intercept with the ordinate axis should give
the electric field in the bulk ferroelectric layer. However,
such prediction is valid only if all the films present the same
electric displacement D. This is why we paid special atten-
tion, during the hysteresis measurements, to adjust Vappl in
order to get the same maximum polarization Dm. On the
other hand, this also returns to set all the PZT capacitors in
 034102-5 Bouregba et al. J. Appl. Phys. 99, 034102 共2006兲

FIG. 5. Same simulation as for Fig. 4 except that the concentration of

charges per volume unit at each interface layer was cancelled.

the same state of polarization, that is essential for a correct

comparison of the different P f -E f polarization loops at the
end of the computations. Figure 6共a兲 shows two E − 共1 / d兲
plots on considering D = + Dm and D = 0+ 共the superscript
+ means that this D zero value belongs to that part of the
D-E loop switching from −Dm to +Dm兲. In Fig. 6共b兲 are
reported the same plots on considering D = −Dm and D = 0−.
The linear character of the plots confirms the prediction of
the model.
From Fig. 6共a兲, we found E+fc ⬇ 36.5 kV/ cm and the
maximum positive electric field applied to the bulk ferroelec-
tric layer E+fm was 274 kV/ cm. From Fig. 6共b兲, E−fc
⬇ 25 kV/ cm and E−fm ⬇ 283 kV/ cm. We cannot state whether
the difference between the positive and the negative coercive
fields in the ferroelectric layer arises from the precision of
the plots or is an intrinsic property of the film. However,
these values are in good agreement with the bulk PZT
value20 and with other works.3,12,13 In both cases where D FIG. 6. Plots of the electric field 共E兲 applied to each PZT capacitor as a
= 0, the slope of the plots directly gives Vbi values: V+bi function of the reciprocal thickness 共1 / d兲 for different electric displace-
ments: 共a兲 D = + Dm = 46 ␮C / cm2 and D = 0+, 共b兲 D = −Dm = −46 ␮C / cm2,
= 1.1 V and V−bi = −0.7 V. and D = 0−. The expression of each straight line is reported according to the
The determination of C+i and C−i may be achieved as axis units.
follows. At the moments when ␳i1 and ␳i2 change sign, it is
likely that the total built-in potential first cancels before
of Vbi and Ci found previously when D = 0 and D = Dm, re-
changing sign at the beginning of the next sequence. This is
spectively, will be assumed constant during each sequence.
because the sign of the total stored charge cannot change
The last parameter to determine is the dielectric permit-
instantaneously, whatever the actual mechanism of injection.
tivity ␧ f of the bulk ferroelectric layer. By assuming di1 Ⰶ d
This returns to consider that ␳i1 = 0 and ␳i2 = 0, hence that
and di2 Ⰶ d, it can be shown in the framework of the stacked
Vbi = 0, each time dVappl / dt = 0. Abrupt cancellation was as-
ferroelectric capacitor model18
sumed for convenience and simplicity of our investigation
though actually the cancellation of the total built-in potential ␧app
probably occurs progressively as D approaches its maximum ␧f = , 共9兲
1 − ␧0␧appA/dCil
values. Then from the slope of E − 共1 / d兲 plots performed for
D = + Dm and D = −Dm 关Figs. 6共a兲 and 6共b兲, respectively兴, one where ␧app represents the apparent or the overall dielectric
can readily estimate Ci by assuming Vbi = 0 关see relation 共8兲兴. permittivity of the stacked ferroelectric capacitor. ␧app may
We found C+i = 7.4 nF and C−i = 7.6 nF, in agreement with the be estimated from the high field slope of the D-E loops,
values proposed by Larsen et al.3 In what follows the values taking care, however, that the films are saturated during the
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 034102-6 Bouregba et al.
FIG. 7. P f -E f polarization loops computed from the D-E hysteresis loops
measured on the PZT capacitors: 320 nm 共circles兲, 250 nm 共squares兲,
200 nm 共triangles兲, and 100 nm 共diamonds兲. The D-E loops measured on
the 320 nm 共dashed line兲 and the 100 nm 共continuous line兲 thick PZT ca-
pacitors are also reported for comparison.
hysteresis measurements. By assuming that, during each se-
quence, Vbi is independent of the electric-field strength and
by considering a saturated film 共the polarization of the
switching domains reaches the constant spontaneous value兲,
then the slope of the hysteresis loops at high fields may be
expressed from the expression 共3兲 as follows:18
⳵Dsat ␧ 0␧ f
= = ␧0␧app . 共10兲
⳵E 1 + ␧0␧ f A/dCi
We found for the four films, ␧+f = ␧−f = 330. Finally by
using the values of V+bi, V−bi, C+i , C−i , ␧+f , and ␧−f determined
above, the P f -E f polarization loop of each PZT film was
computed with the expressions 共3兲, 共4兲, and 共7兲. The result is
shown on Fig. 7. It can be seen that all the polarization loops
+ − +
are almost identical. Moreover the values of Efm , Efm , Efc ,
−
and Efc coincide with those previously determined from Figs.
6共a兲 and 6共b兲. We emphasize that the polarization loops were
computed without any adjustment of the parameters. Since
all the loops present a squarelike shape with almost vertical
variation of the polarization at both coercive fields, this im-
plies that the model is physically justified and also that the
values found for Vbi, Ci, and ␧ f are realistic. Indeed, it has
been established that an inaccurate estimation of Ci and ␧ f
leads to straightforward rotation shifts of the polarization
loops.18,19 Another direct implication of the results above is
that the computed P f -E f loops and the parameters Vbi, Ci,
and ␧ f certainly form a unique and actual set of values shared
by the four studied PZT films.
From the values of V+bi, V−bi, C+i , and C−i , it is possible to
approximately calculate the charge concentration per volume
unit, the thickness, and the dielectric permittivity of both
interface layers. For this purpose we assumed di1 = di2, ␧i
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J. Appl. Phys. 99, 034102 共2006兲
= ␧i1 = ␧i2, and ␳i = ␳i1 = −␳i2, whether Vappl is positive or nega-
tive. Then from the expressions of Vbi and Ci it can be shown
d iC i 4␧0␧i兩Vbi兩
␧i = and Ni = ,
␧ 0A ed2i
where di = di1 + di2 stands for the total thickness of the inter-
face layers. One can estimate ␧i and Ni from arbitrary values
of di. However, as both interface layers were assumed non-
ferroelectric, the latter probably exhibits degraded dielectric
properties compared to the bulk ferroelectric layer. Hence
one expects a maximum for ␧i共␧+i = ␧−i 艋 330兲, so a maximum
for di and a minimum for Ni. Finally we found N+i = N−i
艌 1026 m−3 and di 艋 20 nm.
IV. SUMMARY
The thickness dependence of the hysteresis loops of PZT
films grown on platinum coated Si substrate is investigated.
Increase of coercive fields and horizontal stretching out of
the loops with decreasing thickness are fully explained by
simulations including nonferroelectric charged layers at both
ferroelectric-electrode interfaces. An original method was
constructed with efforts aimed at developing a model ready
to implement. The latter enables the determination of the
overall interface capacitance, the total interface built-in po-
tential, and the polarization in the bulk ferroelectric layer
from hysteresis measurements.
Remarkably, all the polarization loops extracted from the
experimental data of each PZT capacitor displayed a square-
like shape and presented coercive fields 共36.5 and
−25 kV/ cm兲 in agreement with the PZT bulk value. On the
other hand it was found that the values of Ci共#7.5 nF兲, Vbi
共−0.7 and 1.1 V兲, and ␧ f 共330兲, and also the P f -E f loops, form
a unique set of parameters shared by all the films. These
results give direct experimental evidence that the developed
model is physically justified. One important conclusion of
this work is that the interface charge, of a few 1026 m−3, is
probably modulated in sign and density according to the sign
of the instantaneous variation of the polarization.
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