Polarization loop deformations of an oxygen deficient Pb ( Zr 0.25 , Ti 0.

75 ) O 3
ferroelectric thin film
G. Le Rhun, R. Bouregba, and G. Poullain

Citation: Journal of Applied Physics 96, 5712 (2004); doi: 10.1063/1.1789635

View online: http://dx.doi.org/10.1063/1.1789635
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 JOURNAL OF APPLIED PHYSICS VOLUME 96, NUMBER 10 15 NOVEMBER 2004

Polarization loop deformations of an oxygen deficient Pb„Zr0.25 , Ti0.75…O3

ferroelectric thin film
G. Le Rhun, R. Bouregba,a) and G. Poullain
Laboratoire CRISMAT-ENSICAEN et Université de Caen, CNRS UMR 6508, Boulevard du Maréchal Juin,
14050 Caen Cedex, France
(Received 8 March 2004; accepted 11 July 2004)
An epitaxial oxygen deficient Pb共Zr0.25 , Ti0.75兲O3 (PZT) thin film, which presented hysteresis loop
with significant shift along the electric field axis and apparent polarization suppression, is
investigated. Loop deformations are studied and entirely explained, both qualitatively and
quantitatively by simulations including the effect of an ultrathin interfacial layer uniformly charged.
The method developed in this paper is suitable to calculate not only the polarization due to the
switching domains, but also all the characteristics of the space charge layer. The determination of
the linear dielectric constant of the bulk ferroelectric layer does not require preparation of films with
different thicknesses, unlike most of the methods proposed to date. Linear dielectric constant and
thickness of the interfacial layer are in the range ␧il = 80– 130 and dil = 8 – 12 nm, respectively. On the
other hand, a very large interfacial charge concentration (Nil of few 1026 m−3) is obtained. For the
studied PZT sample, hysteresis deformations are not attributable to pinning of domain walls, despite
the large value of Nil, but rather to the interfacial space charge layer that screens the applied electric
field and prevents the full switching of the ferroelectric domains. © 2004 American Institute of
Physics. [DOI: 10.1063/1.1789635]

I. INTRODUCTION II. EXPERIMENT

Imprint is, like fatigue, an important source of failure of In a previous paper, we have reported preparation of
oxygen deficient PZT film on 共001兲Pt/ 共001兲MgO substrate
perovskite ferroelectric thin films which seriously restricts
by RF magnetron sputtering.9 In summary, c-axis epitaxial
their implementation in silicon-integrated circuits, particu-
growth was achieved at 500 ° C owing to an ultra thin titan-
larly for nonvolatile ferroelectric RAM memories
ate oxide upper layer that was sputtered on the Pt bottom
applications.1,2 This phenomenon, which manifests itself dur- electrode prior to PZT deposition. This was possible provid-
ing aging of ferroelectric capacitors by a shift of hysteresis ing the O2 / 共Ar+ O2兲 ratio in the sputtering gas to be pre-
loops along the electric field axis, is commonly attributed to cisely monitored during both depositions of TiOx upper layer
internal field in the film. Many works, both theoretical and and PZT layer. Then the effect of oxygen content on the
experimental, have been devoted to investigate the mecha- ferroelectric properties was investigated and a 250 nm thick
nism producing the internal field. As recently reviewed by Pb共Zr0.25Ti0.75兲O3 film was prepared using for the PZT sput-
Grossmann and co-workers,3 among all the mechanisms pre- tering a plasma gas without O2.
sented in the literature, two models seem to be able to ex- All hysteresis loops reported in the present paper were
plain imprint: the defect dipole alignment model4–6 and the measured at 200 Hz using a Sawyer-Tower 共S-T兲 circuit
bulk screening model.7 However, an alternative model has driven by the input voltage Vin共t兲 (see Fig. 1). The standard
been proposed in which imprint is attributed to a strong in- capacitor Cst was 22 nF and the area A of the Pt top electrode
ternal electric field produced, during aging, in a thin surface was 5.29⫻ 10−4 cm2. D-E loops were plotted using the two
layer.3,8 following relations:
In the present paper, we investigate ferroelectric proper-
ties of an oxygen deficient epitaxial Pb共Zr0.25 , Ti0.75兲O3
(PZT) thin film. Strong shift of the polarization loop along
electric field axis is observed at the virgin state, similar to
that encountered on ferroelectric capacitors undergoing im-
portant aging. However, for the investigated PZT film, the
shift was artificially induced, probably due to the important
lack of oxygen in the sample. From suitable expressions, we
develop an original approach that enables to show quantita-
tively how an interfacial nonferroelectric space charge layer
can produce imprint.

a)
Electronic mail: rachid.bouregba@ismra.fr FIG. 1. Scheme of the Sawyer-Tower circuit with the standard capacitor Cst.

0021-8979/2004/96(10)/5712/10/$22.00 5712 © 2004 American Institute of Physics

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 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
FIG. 2. Hysteresis loop measured on the PZT film while (a) using a sine
wave as input voltage. (b) Same measurement but after superposing a dc
voltage Vdc = −6.5 V (continuous line) and after artificially removing it when
determining E axis (dashed line).
CstVou共t兲
D共t兲 = , 共1兲
A = −250 kV/ cm, taking for Ecl and Ecr (−480 kV/ cm and
and
Vin共t兲 − Vou共t兲
E共t兲 = , 共2兲
d be estimated by Edc ⬵ Vdc / d, i.e., Edc = −260 kV/ cm. One can
where Vin共t兲 is a sine wave Vsin共t兲, D共t兲 is the instantaneous
electric displacement that represents the charge sheet density
on the armatures of the ferroelectric capacitor and E共t兲 the
electric field applied to it. Vou共t兲 is the instantaneous voltage
measured across Cst and d is the thickness of the ferroelectric
capacitor.
Figure 2(a) displays the polarization loop measured on
the PZT sample at the virgin state, the amplitude Vsinm of the
sine wave was 17 V. As it can be observed, the hysteresis
loop is strongly distorted, whereas x-ray diffraction pattern
revealed satisfying crystallization of the film.9 The right-
hand part of the loop appears well saturated, but not the left
one. The positive maximum polarization 共22 ␮C / cm2兲 ap-
pears much smaller than the negative one 共38 ␮C / cm2兲.
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Le Rhun, Bouregba, and Poullain 5713
Moreover, the loop is shifted toward negative values of elec-
tric field axis, probably due to the existence of an internal
field.
Very similar ferroelectric properties have already been
reported by Lee and co-workers who observed hysteresis de-
formations on PZT thin films prepared by sol-gel
method.10,11 Hysteresis shifts were related by the authors to
the presence of space charges trapped near the PZT/Pt inter-
faces probably induced by damages subsequent to sputtering
and reactive ion etching of the Pt top electrode. Polarization
suppression was attributed to the presence of ionic defect
levels or charge trapping centers within the film, which pre-
vent domain switching. In the works by Lee et al., symmetry
of hysteresis loops together with an increase of the switch-
able polarization were obtained after annealing treatment.
In Ref. 9 we have established that symmetry of hyster-
esis loops may be provisionally restored by applying a dc
field to the ferroelectric capacitor. This is shown in Fig. 2(b)
where hysteresis loop in continuous line was plotted while
superposing a dc voltage Vdc to the sine wave Vsin共t兲 (whose
amplitude was unchanged). In what follows we will call
Vin共t兲, the total input voltage given by: Vin共t兲 = Vsin共t兲 + Vdc.
Vdc was adjusted in such a way that 兩Ecl兩 ⬵ 兩Ecr兩, where Ecl
and Ecr corresponded to the left-hand and the right-hand co-
ercive fields of the hysteresis loop, respectively. These values
were measured after removing Vdc component by using the
ac function of the oscilloscope channel measuring the elec-
tric field, because otherwise the shift along E axis remains
[see the loop with dashed line on Fig. 2(b)]. Then one may
observe that Pr+ ⬵ 兩Pr−兩, i.e., the positive and the negative rem-
nant polarizations exhibit almost the same values. Two spe-
cial points were observed during the measurements.
The first one is that, for the sample investigated above,
the equality 兩Ecl兩 ⬵ 兩Ecr兩 was always obtained when Vdc
= −6.5 V whatever the amplitude of the input sine wave. The
second point that must be outlined concerns the internal field
Ebi, i.e., the field giving rise to the shift of the loops. Ebi can
be determined with Ebi = 关Ecl + Ecr兴 / 2. We found Ebi
−20 kV/ cm, respectively) the values extracted from the loop
in continuous line [Fig. 2(b)]. Changing the amplitude of the
driving voltage yielded the same Ebi. Now the applied dc
electric field Edc required to obtain symmetrical loops may
observe that Ebi ⬵ Edc, or Vbi ⬵ Vdc, where Vbi is a built-in
voltage, which constitutes the second point to note. In every
case the cancellation of the dc voltage systematically leads to
the original loops with asymmetrical shape.
Films prepared with similar sputtering conditions, how-
ever, under oxidizing atmosphere, displayed hysteresis loops
with symmetrical shape (see Fig. 3). Thus, one may reason-
ably link the behavior investigated above to the fact that the
sample was prepared under a pure argon atmosphere during
the PZT sputtering. The low content of oxygen in the film
was only supplied by the PZT ceramic target. Consequently,
the sample was poorly oxygenated and the internal field may
probably be attributed to oxygen vacancies. In what follows,
we shall assume that charges accumulate at electrode-PZT
interfaces during the growth of the film. With this hypoth-
 5714 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
FIG. 3. Hysteresis loop measured on a well oxygenated PZT sample
(150 nm in thickness). The latter was prepared on same substrate and at
same temperature except that the O2 / 共Ar+ O2兲 ratio was 0.2 in the plasma
gas during PZT sputtering. The film showed (001) preferred orientation with
epitaxial c-axis grains. For details see our previous article (see Ref. 9).
esis, some characteristic features of the hysteresis deforma-
tions described above may be qualitatively explained. A
more quantitative analysis will be performed in Secs. IV and
V.
III. QUALITATIVE ANALYSIS
In this work, S-T hysteresis measurements were per-
formed while applying Vin共t兲 to the bottom electrode, i.e., the
potential of top electrode was raised to the ground. More-
over, it should be noted that all hysteresis loops were plotted
with the positive side of the electric field axis corresponding
to an electric field vector directed toward the bottom elec-
trode, i.e., arbitrarily as the applied voltage [see relation (2)].
Let us now consider Fig. 4. The ferroelectric capacitor is
depicted by a stacked structure formed by the ferroelectric
layer and one interfacial layer. Note that Vou共t兲 has been
neglected for convenience. In practice, this is possible if Cst
value is large enough compared to the linear capacitance of
the ferroelectric capacitor. As during S-T hysteresis measure-
ments, the input voltage Vin共t兲 is oriented toward the bottom
electrode.
First, we shall consider the case where Vdc = 0 V, hence
Vin共t兲 is the pure sinus voltage Vsin共t兲. When saturated, the
FIG. 4. The ferroelectric capacitor under test is assumed to be formed by a
ferroelectric layer and a negatively charged space charge layer at the top
surface of the film.
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Le Rhun, Bouregba, and Poullain
switching domains in the ferroelectric layer are assumed to
exhibit a squarelike symmetrical hysteresis loop with respect
to the voltage V f across the ferroelectric layer. The interfacial
layers are supposed to behave as nonferroelectric space
charge layers, positively or negatively charged. For conve-
nience we will include their effects into one overall layer.
For instance, let us assume that this layer is negatively
charged at the top electrode-PZT interface. Then with el-
ementary electrostatics, one can show that the built-in volt-
age Vbi is oriented toward top electrode (and will be counted
positively in that direction), hence opposes the applied volt-
age Vin共t兲. In what follows we will assume that Vbi is con-
stant with respect to Vin共t兲, in agreement to experimental
value of Vbi that was found independent of the electric field
strength (see Sec. II above). The voltage V f applied to the
ferroelectric layer is given by
V f 共t兲 = Vin共t兲 + Vbi or V f 共t兲 = Vsin共t兲 + Vbi Vdc = 0.
共3兲
If one focuses on the maximum and minimum values of
V f 共t兲, i.e., V fmax and V fmin, respectively, one gets: V fmax
= Vinm + Vbi and V fmin = −Vinm + Vbi. Then, counting Vbi posi-
tively yields 兩V fmax兩 ⬎ 兩V fmin兩, i.e., an asymmetrical wave form
for V f 共t兲. In the case where Vsinm ⬎ Vbi, V f 共t兲 is still bipolar
but the amplitude of the positive alternation is larger than
that of the negative one. This implies that the hysteresis loop
D f − V f (internal loop) of the ferroelectric layer should be
more saturated when Vsin共t兲, hence Vin共t兲, is positive. This is
illustrated in Fig. 5(a).
Let us now roughly estimate the shape of the external or
apparent hysteresis loop, i.e., the D-Vin curve that should be
measured with a S-T circuit. For this purpose, it is suitable to
consider the coercive values Vinc+ and Vinc− of Vin to deter-
mine the effect of Vbi because we considered a squarelike
loop for the ferroelectric polarization. We will assume for the
simplicity of this qualitative description that the charged in-
terfacial layer does not change the polarization, i.e., for a
given Vin one gets for D the value reached by D f when V f
= Vin. The coercive values V fc− and V fc+ of internal loop are
assumed not to be affected by the existence of the interfacial
layer. Then, when V f is large enough to saturate the film, V fc−
and V fc+ are constant and one may write: Vinc+ = V fc+ − Vbi and
Vinc− = V−fc − Vbi. In that case, the external hysteresis loop has
the shape reported in Fig. 5(b). As it can be seen, the curve is
shifted toward the negative side of voltage axis by a quantity
equal to 共−Vbi兲. This is because as mentioned above, Vbi
opposes Vin共t兲. Unlike the internal loop, however, the shift
only concerns the coercive values. Moreover, though the ex-
tent of the applied voltage is the same in both cases, i.e., two
times Vinm (or Vsinm), only Vin axis is symmetrical around the
origin because determined by the input sine voltage. As a
result of the apparent shifting of external D-Vin loop toward
the negative side of voltage axis, a larger excursion along the
positive saturated branch (noted ⌬D) is predicted, as well as
a smaller excursion, by the same amount, along the negative
one. We will hark back to this point later on.
Obviously, the final shape of the external loop will de-
pend to a large extent on the Vbi value. For instance, for large
 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
FIG. 5. (a) Shape of hysteresis loop due to the switching domains in the
ferroelectric layer in presence of a potential barrier Vbi at the top interface.
V+fc and V−fc are the coercive values of the voltage V f . (b) Effect of Vbi on the
shape of external loop. The curve in thin continuous line corresponds to the
case where no space charge is present at the surface of the film. For a fixed
amplitude Vinm, a shift of −Vbi volt is expected for the coercive values, hence
for the beginning of both saturated branches. A corresponding change of
electric displacement given by ⌬D is expected as well (see the inset). If both
loops are arbitrarily shifted in such a way that their coercive values are lined
up, then ⌬D can be seen as an extra penetration of the loop inside the
positive saturated zone, and as a decrease of the penetration inside the nega-
tive one.
enough Vbi such that 兩V fmin兩 ⬍ 兩V fc−兩, only a small fraction of
the ferroelectric domains should switch and the left part of
the internal loop will not be saturated. Accordingly, the ex-
ternal loop should display an asymmetrical shape with an
apparent suppression of the switchable polarization, though
for positive Vin values the loop will appear well saturated.
This is what probably occurred during S-T hysteresis mea-
surements performed on the oxygen deficient sample [see
Fig. 2(a)].
To make the external loops symmetrical according to the
process presented above, one must apply a total voltage
Vin共t兲 to the ferroelectric capacitor in a way so as to ensure
symmetrical polarization reversal in the ferroelectric layer.
This requires V f 共t兲 to exactly follow the variations of the sine
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Le Rhun, Bouregba, and Poullain 5715
FIG. 6. Effect of the superposition of a dc voltage Vdc on the shape of
external loop. In thin continuous line is the loop while assuming Vsin共t兲 as
voltage axis, whereas in thick continuous line is the loop with Vin共t兲 (includ-
ing Vdc) as voltage axis. In each case, the extent of both saturated branches
becomes equal.
wave, that is, V f 共t兲 = Vsin共t兲. Examination of equality (3)
shows that this returns to exactly cancel the contribution of
Vbi by application of a dc voltage Vdc : V f 共t兲 = Vsin共t兲 + Vbi
+ Vdc or V f 共t兲 = Vin共t兲 + Vbi, where Vin共t兲 = Vsin共t兲 + Vdc and Vdc
= −Vbi ⬍ 0. A shift can, however, remain, or not, depending
on whether one utilizes Vin or Vsin to form the abscissa axis,
respectively (see Fig. 6).
Hence, the analysis above predicts a shift of hysteresis
loops toward negative values of voltage axis when consider-
ing a negatively charged layer at the top interface. This is
consistent with the experimental observations. One can show
that identical result may be obtained if one replaces the nega-
tive layer by a positively charged one, but at the other inter-
face. However, the analysis above remains quite qualitative.
In the following section we shall perform a quantitative in-
vestigation through numerical simulations including physical
characteristics of the interfacial space charge layer.
IV. QUANTITATIVE ANALYSIS—NUMERICAL
SIMULATIONS
A. Presentation
In this section, we shall use the algorithm developed by
Miller et al., which enables to simulate S-T hysteresis
measurements.12 Their model, including both physical pa-
rameters of the sample and circuit elements, simulates quite
well the loops deformations often observed at low frequen-
cies when performing S-T hysteresis measurements. More-
over, it allows to take into account the effects of nonferro-
electric layers at interfaces between electrodes and
ferroelectric layer. In that case, tilt of hysteresis loops, in-
creasing when decreasing thickness of the film, was demon-
strated, in agreement with results by other authors.13–15 How-
ever, unlike experimental data, the coercive fields are not
affected by interfacial layers when the latter are treated as
passive layers.12,15 This can be verified by adding a capacitor
in series with a ferroelectric capacitor.16 Surface dielectric
layers enable to account for variation of coercive fields pro-
viding a space charge is considered.16,17 In what follows, we
 5716 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
FIG. 7. Scheme of the S-T circuit with the stacked ferroelectric capacitor
(FECAP). The figure include the circuit elements and the main physical
parameters of the sample under test.
shall modify the Miller’s model by including space charge at
the interfaces. Thereby, the main interesting point is that we
will be able to estimate the effects of nonferroelectric inter-
facial space charge layers over entire hysteresis loops, and
not only on the coercive fields.
Figure 7 details all the parameters required for modeling.
The ferroelectric capacitor has one space charge layer at the
top electrode-PZT layer interface. As assumed previously,
the combined effects of the two interfaces are included in
one overall interfacial layer. ⑀il, dil, and ␳il are the linear
dielectric constant, the thickness, and the charge per volume
unit in this layer, respectively. ␳il is given by ␳il = e Nil, where
e is the electron charge and Nil is the charge concentration
per volume unit. For simplicity, we will assume that Nil,
hence ␳il, is uniform and that dil is constant, whatever the
electric field strength. Let us call d f the thickness and ␧ f the
linear dielectric constant of the bulk ferroelectric layer. Psd
-E f is a nonlinear electric field dependent polarization, where
Psd is the switchable polarization due to the switching do-
mains and E f the driving electric field. The resistors R f and
Rosc 共1 M⍀兲 represent the leakage currents in the ferroelec-
tric capacitor (assumed constant for convenience) and the
input resistance of the oscilloscope channel measuring
Vou共t兲, respectively. V is the total voltage across the sample.
The Miller’s algorithm requires to start computations
from arbitrary Psd-E f loops in the ferroelectric layer (see Fig.
8). The latter were generated by using the hyperbolic tangent
function12 and by choosing for the remnant polarization
共Psdr兲, the spontaneous polarization 共Psds兲, and the coercive
field 共E fc兲, the values that are reported in Table I. They were
set in a way to be close enough to the experimental values.
Then, the instantaneous voltage Vou共t兲 across Cst is computed
using an iterative procedure. The main lines of the method
may be summarized as follows. First, one must express the
instantaneous electric field E f 共t兲 and the instantaneous elec-
tric displacement D共t兲 as a function of the physical param-
eters of the ferroelectric capacitor. Second, because the cal-
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Le Rhun, Bouregba, and Poullain
FIG. 8. Arbitrary Psd-E f loops used for the computations of external D-E
loops.
culation of Vou共t兲 at each iteration utilizes an integration
method, one must express the time derivative dVou / dt as a
function of the parameters of both ferroelectric sample and
S-T circuit, which in turn requires the knowledge of the time
derivatives dE f / dt and dD / dt. However, unlike work by
Miller and co-workers, expressions of E f and D are expected
to include the charge per volume unit ␳il in the interfacial
layer (see below). Accordingly, if one assumes that ␳il, hence
Nil, is time independent, then one finds for dE f / dt and
dD / dt, hence for dVou / dt, exactly the same relations as in
Ref. 12. Therefore, the only changes resulting from including
the presence of a space charge layer concern expressions (3)
and (4) of E f and D given in the above-mentioned work. The
latter may now be expressed as follows.
The electric field E f in the ferroelectric layer is given by
D f − Psd
Ef = , 共4兲
␧ o␧ f
where D f is the electric displacement and ␧o is the permit-
tivity of free space. The electric field Eil in the interfacial
layer may be determined by integrating the Poisson’s equa-
tion,
⳵Eil ␳il
= . 共5兲
⳵x ␧o␧il
The integration constant, giving the value of Eil at x = 0,
must be such to ensure the conservation of electric displace-
ment at the interface between space charge and ferroelectric
layers, i.e., at x = dil,
␧o␧ilEil共x = dil兲 = ␧o␧ f E f + Psd ,
which yields,
␳il Df
Eil = 共x − dil兲 + . 共6兲
␧o␧il ␧o␧il
As electric field corresponds to spatial derivative of the
potential, one may express the total voltage V across the
ferroelectric capacitor as a function of Eil and E f , hence of
 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004 Le Rhun, Bouregba, and Poullain 5717

FIG. 9. Effect of increasing the charge concentration Nil in the space charge
layer on the shape of computed external D-E loops. Clear shifting toward
the negative side of electric field axis is visible.
D f . On the other hand, we have D f = D because the electric
displacement is conservative at the interface between the bot-
tom electrode and the ferroelectric layer. Finally, using Eqs.
(4) and (6), it can be shown,
the film 共␳il ⬍ 0兲. All other parameters were kept constant
and are reported in Table I. Shifting of the loops toward the
negative values of E axis is observed, in agreement with the
experimental observations and as expected from the previous
qualitative analysis. The shifts increase with Nil because the
built-in potential Vbi is reinforced.
The calculations above allow to anticipate some physical
properties that must verify both interfacial and ferroelectric
layers. Indeed, simulation of significant hysteresis shifts,
similar to those displayed by the studied PZT film, requires
the different parameters to be set in a limited range of values.
For instance expression of Vbi suggests that, for this purpose,
one must either increase Nil or dil values, or decrease ␧il.
However, choosing large dil values or small ␧il values returns
to dramatically reduce the linear capacitance Cil of the inter-
facial layer, given by Cil = ␧o␧ilA / dil. Now, if the latter has
values not much larger than that of the linear capacitance C f
of the ferroelectric layer 共C f = ␧o␧ f A / d f 兲, then the calcula-
tions lead to markedly tilted loops with significant loss of
polarization, similar to that reported when interfacial layers
are treated as passive dielectric layers.12,15 This is because a
large part of the applied alternating field drops across these
layers. Thereby, additional computations revealed that, to en-

冋 冉 冊册
sure full switching of the ferroelectric domains, very large
␧ o␧ f dil 1 and unrealistic amplitudes of the driving voltage are required
D= 共V − Vbi兲 + Psd 1 − , 共7兲 to compensate for Cil effect and therefore to obtain visible
d d ␣
shift of hysteresis loops. Now, well oxygenated PZT samples
where displayed spontaneous polarization values comparable to

V = Vin − Vou, Vbi =

␳ildil2
2␧o␧il
, and ␣ = 1 +
dil ␧ f
d ␧il
冉 冊
−1 .
those of the oxygen deficient film investigated in this paper,
except that hysteresis loops of the former did not shift at all9
[see Figs. 2(b) and 3]. Moreover, in both cases the maximum
To express E f one just has to put expression (7) in (4). This electric field required for saturating the films were nearly of
yields the same order of magnitude. Therefore obtaining strong

冋
E f = V − Vbi −
Psddil 1
␧o␧il d␣
册.
The relations (7) and (8) above are very similar to those
presented earlier,12 except that they includes now an addi-
tional term calling out ␳il, i.e., the built-in potential Vbi of the
space charge layer.18
B. Results
Once Vou共t兲 files are calculated, one can plot external
D-E loops as measured during S-T hysteresis measurements,
i.e., by using for D and E the expressions (1) and (2) above.
It should be noted that, with this definition, E represents only
the apparent electric field in the ferroelectric capacitor. Fig-
ure 9 shows D-E loops computed with different values of Nil
and assuming negatively charged layer at the top surface of
共8兲
shifts implies extremely large values of Nil. But to avoid
unrealistic charge concentrations while verifying the condi-
tion above 共Cil Ⰷ C f 兲, one must markedly reduce the linear
dielectric constant ␧ f of the ferroelectric layer. This suggests
that appearance of imprint during aging should be promoted
on c axis oriented tetragonal PZT films because smaller ␧ f
are expected in that case.19 This seems to be confirmed by
our observations since the PZT film investigated in this paper
presented c axis tetragonal microstructure and a small linear
dielectric constant. The compromise above led us to choose
for ␧il, dil, and ␧ f the values reported in Table I. Under these
conditions, we found that the shifts become significant only
when Nil is larger than 1026 m−3 (see Fig. 9). We will see in
the following section that these values are in agreement with
those extracted from experimental data.
Now, let us turn our attention on the problem of symme-
trization of the loops. Following the analysis of Sec. III we

TABLE I. Summary of the main parameters used for the numerical calculations of external D-E loops. Only Nil value was changed to produce the different
loops. Total thickness, area, and leakage resistance of the ferroelectric capacitor were d = 200 nm, A = 5.29⫻ 10−4 cm2, and R f = 1 G⍀, respectively. Unless
specified, Vdc = 0.

Ferroelectric layer Interfacial layer Sawyer-Tower circuit

Psdr Psds E fc ␧f df ␧il dil Vsinm F Rosc Cst

20 ␮C / cm2 25 ␮C / cm2 150 kV/ cm 100 190 nm 50 10 nm 30 V 1 kHz 1 M⍀ 22 nF

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 5718 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
FIG. 10. (a) D-E loops computed with the same parameters as for Fig. 9,
except that for each charge concentration Nil the dc voltage Vdc was set to
the corresponding Vbi value. (b) Same computations as (a), however by
determining E axis with E共t兲 = 关Vsin共t兲 − Vou共t兲兴 / d. Note that the three curves
are then perfectly identical.
have simulated the effect of a dc voltage application during
S-T measurements. Figure 10(a) presents D-E loops calcu-
lated with the same parameters values as those of Fig. 9,
except that the additional dc voltage was each time set in
such a way that Vdc = Vbi, i.e., Vbi = −18 V, −9 V, and −1.8 V,
when Nil = 1027 m−3, 5 ⫻ 1026 m−3 and 1026 m−3, respectively.
The hysteresis loops are now symmetrical, although they re-
main shifted. This is because the E axis, as determined with
relation (2), now includes Vdc through Vin 共Vin = Vsin + Vdc兲.
The shifts only vanish when Vin is replaced by Vsin in relation
(2) [see Fig. 10(b)]. Moreover, one can verify that Vbi
⯝ 关Ecl + Ecr兴d / 2, where Ecl and Ecr are the coercive fields as
defined in Sec. II. This confirms that, once the loops become
symmetrical, then one can determine the built-in potential of
the interfacial layer, in agreement with both experimental
and qualitative analysis above. To end this section, we have
examined the effect of the charge concentration Nil on the
switchable polarization in the ferroelectric layer by plotting
Psd-E f loops before and after application of the dc voltage
[see Fig. 11(a) and 11(b)]. Clearly, the presence of a space
charge layer affects the electric field distribution in the ferro-
electric layer and prevents the polarization reversal to oper-
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Le Rhun, Bouregba, and Poullain
FIG. 11. (a) Effect of increasing the charge concentration Nil in the space
charge layer on the shape of Psd-E f loops in the ferroelectric layer. The loops
have been arbitrarily shifted vertically from each others to distinguish them.
(b) The application of a suitable dc voltage enables symmetrical switching
of the ferroelectric domains whatever the interfacial charge concentration.
ate in a symmetrical manner, even if the sample is driven by
a sine wave. This is why external D-E loops of Fig. 9 ap-
peared more saturated for positive values of E and thus ap-
peared shifted toward the negative side of E axis.
V. INVESTIGATION OF THE PZT SAMPLE
In the preceding section, we have simulated the effect of
a space charge layer on external D-E loops as they should be
measured with a S-T circuit. For this purpose, we have cal-
culated Vou共t兲 files [Vin共t兲 file is a known parameter as it
corresponds to the driving voltage] starting from Psd-E f
loops that were arbitrarily determined at the beginning of
iterations. Now, we shall demonstrate the feasibility to per-
form the reciprocal process: computing the polarization due
to the switching domains in the ferroelectric layer, i.e., Psd
-E f loops, from the measured Vin共t兲 and Vou共t兲 files. The pro-
cedure will simultaneously enable to realistically estimate
the physical properties of the investigated PZT sample, i.e.,
␧il, dil, Nil, ␧ f , and R f . The approach is to consider that, to a
certain extent, S-T hysteresis measurements are self consis-
tent and may provide enough data for separating both effects
 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004 Le Rhun, Bouregba, and Poullain 5719

of interfacial and ferroelectric layers, hence for estimating all

parameters characterizing them. For this purpose we shall
now express Psd共t兲 as a function of Vin共t兲 and Vou共t兲, expres-
冋
E f = V − Vbi − 册
PsdA 1
Cil d␣
, 共14兲

sion of E f 共t兲 being already determined [see relation (8)

above]. Note that such a way to proceed has already been
investigated, however, by considering passive interfacial
Psd共t兲 = 冋冉 Cst ␧o␧ f
A
+
d␣
冊
Vou共t兲 −
␧ o␧ f
d␣
关Vin共t兲 − Vbi兴 + ␥共t兲 册
layers.20 1
⫻ , 共15兲
By performing the balance of all the charges involved ␧ o␧ f A
during S-T hysteresis measurement (see Fig. 7), it can be 1−
dCil␣
shown that
where ␥共t兲 is unchanged and
Q f 共t兲 + 冕共t兲
Vin共t兲 − Vou共t兲
Rf
dt = Qst共t兲 + 冕 共t兲
Vou共t兲
Rosc
dt, 共9兲
Cil =
␧o␧ilA
dil
, 共16兲

where Q f 共t兲 and Qst共t兲 are the instantaneous charges stored

␧ o␧ f A
by the ferroelectric and the standard capacitors, respectively, ␣=1+ . 共17兲
dCil
Q f 共t兲 = D共t兲A, 共10兲
Now it remains only two parameters to fit: the interfacial
capacitance Cil and ␧ f . Many works have been devoted in the
Qst共t兲 = CstVou共t兲. 共11兲 past to the determination of Cil and ␧ f of ferroelectric
films.14,22,23 Typically the same approach has always been
Then, using for D共t兲 its expression given by Eq. (7), one
proposed that requires preparation of ferroelectric capaci-
finds
tors with different thicknesses. Then Cil and ␧ f may be found

Psd共t兲 = 冋冉 Cst ␧o␧ f

A
+
d␣
冊
Vou共t兲 −
␧ o␧ f
d␣
关Vin共t兲 − Vbi兴 + ␥共t兲 册 after plotting the reciprocal capacitance as a function of
thickness. Another recent method has been proposed based
on S-T hysteresis measurements,20 but requires samples with
1 different thicknesses as well. In what follows we shall dem-
⫻ , 共12兲 onstrate that the D-E loop measured on only one PZT sample
dil␧ f
1− is enough for estimation of the linear dielectric constant ␧ f of
d␧il␣
the bulk ferroelectric layer.
where

冉 冊 冕
␥共t兲 = 冕 共t兲
Vou共t兲 1
A
+
1
Rosc R f
dt −
共t兲
Vin共t兲
RfA
dt.
With expressions (8), (12), and (13), it is now possible to
compute Psd-E f loops from measured voltages Vin共t兲 and
Vou共t兲. Exactness of these relations have first been checked
for by applying them to Vin共t兲 and Vou共t兲 files computed in
the preceding section: correct Psd-E f loops have always been
recovered providing the same values of parameters are each
time used again. But, for a correct implementation of these
relations one must precisely estimate the parameters of the
PZT sample under test, i.e., ␧il, dil, Vbi, ␧ f , and R f . Concern-
ing R f , we have already shown, in previous articles, how to
proceed: it is enough to set R f at a minimum value giving a
Psd-E f loop with a minimum area, taking care that the calcu-
lated polarization loop presents closed saturated branches
with no twisted part.20,21 For the film studied in this work we
found R f = 50 M⍀, hence a resistivity of 109 ⍀ cm at F
= 200 Hz.
With regard to Vbi, the latter is a known parameter since
its value 共−6.5 V兲 has been determined after the symmetry of
D-E loops was restored by application of a dc voltage. Thus,
only three parameters remain to be determined (␧il, dil, and
␧ f ). However, the thickness of the interfacial layer is ex-
pected to be much smaller than that of the ferroelectric layer.
Therefore, if one assumes dil Ⰶ d, one may express E f and Psd
as follows,
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A. Determination of ␧f
共13兲 It was demonstrated above that, due to the built-in po-
tential, the external D-E loops shift toward the negative side
of E axis. Simultaneously, the positive maximum value of E f
in the ferroelectric layer increases, whereas the negative one
diminishes. As a result, Psd-E f polarization loops are more
saturated for positive E f . Now, the corresponding change of
electric displacement ⌬D may be expressed from expression
(7) (assuming dil Ⰶ d, hence ␣ ⬵ 1),
␧o␧ f Vbi
⌬D = − , 共18兲
d
so that ⌬D is directly related to Vbi and ␧ f . This relation
means that, compared to a saturated and symmetrical D-E
loop, i.e., as measured on a ferroelectric capacitor with no
interfacial space charge (Nil, hence Vbi, null), a negative Vbi
value should yield a supplementary excursion along the posi-
tive saturated branch given by Eq. (18), whereas the excur-
sion along the negative one should diminish as much. This is
a different, but equivalent, approach to interpret the shift, in
agreement with qualitative analysis [see Fig. 5(b)]. This
arises from the terms calling out Vbi and accounting for the
shifts, which simultaneously occur in expressions of E f , D,
and Psd. All other terms provide symmetrical contribution
upon action of the input sine wave. In other words, the ⌬D
contribution has also been compensated for when the hyster-
esis loops were made symmetrical by application of a dc
 5720 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
FIG. 12. Switchable polarization in the ferroelectric layer (continuous line)
computed from hysteresis measurement carried out on the PZT sample [the
case where Vdc was set to −6.5 V, see curve in continuous line of Fig. 2(b)]
according to the model presented [expressions (14)–(17)]. For comparison,
the measured hysteresis loop is reported (in dashed line), using E共t兲
= 关Vsin共t兲 − Vou共t兲兴 / d to form E axis.
voltage, i.e., when the Vbi effect was cancelled. Therefore, it
is enough to compare the right-hand saturated parts of the
hysteresis loops measured with and without Vdc to estimate
⌬D [see Figs. 2(a) and 2(b)]. One finds ⌬D = 3 ␮C / cm2, and
from Eq. (18), ␧ f = 130.
B. Determination of Cil
During S-T hysteresis measurements, the maximum in-
put voltage was set at a value large enough to saturate both
left-hand and right-hand branches of the hysteresis loop, af-
ter the PZT capacitor was submitted to a dc voltage [see Fig.
2(b)]. Therefore, when using expressions (14)–(17) above,
the correct value of Cil is the one that leads to a saturated
Psd-E f loop as well, i.e., to a polarization loop with horizon-
tal tips. Indeed, additional computations shown that inaccu-
rate estimation of Cil led to rotation shifts similar to those
encountered when one corrects for the linear capacitance of a
ferroelectric capacitor using an external circuit
compensation.24,25 Overestimation of Cil yielded clockwise
shifts, whereas underestimation produced counterclockwise
shifts.20 Using Vin共t兲 and Vou共t兲 files recorded during hyster-
esis measurement [related to the curve plotted in continuous
line of Fig. 2(b)], the best fit was obtained when Cil = 5 nF.
The corresponding Psd-E f loop is presented on Fig. 12. The
parameters values used for the computation are summarized
in Table II.
One can observe that the effect of the built-in potential
has been correctly taken into account since now the shift is
suppressed and absolute values of both positive and negative
TABLE II. Summary of the parameters used to calculate Psd − E f loop due to the switching domains in the ferroelectric layer from S-T hysteresis measurement
performed on the PZT sample.
d A F Rosc
250 nm 5.29⫻ 10−8 m2 200 Hz 1 M⍀
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Le Rhun, Bouregba, and Poullain
TABLE III. Some possible values for dil, Nil, and ␧il parameters calculated
from Cil 共5 nF兲 and Vbi 共−6.5 V兲.
dil (nm) Nil 共m−3兲 ␧l
2 3.8⫻ 1027 20
5 1.5⫻ 1027 53
10 7.7⫻ 1026 107
12 6.3⫻ 1026 ␧ f = 130
coercive fields in ferroelectric layer are equal. Moreover, it
can be seen that the Psd-E f loop is straightened and appears
more vertical, because the tilt due to Cil effect has been prop-
erly compensated for. Accordingly both remnant and sponta-
neous polarizations are increased. This is visible when com-
paring the calculated Psd-E f loop with the apparent D-E loop
measured after applying Vdc = −6.5 V and using Vsin共t兲 to
form E axis (see the loop in dashed line on Fig. 12). As the
polarization loop presented a squarelike shape, then this sug-
gests that both Cil and ␧ f values found above are realistic.
This point must be outlined because Cil value will condition
further determination of the interfacial charge Qil, hence es-
timation of Nil, ␧il, and dil (see below).
C. Estimation of Nil, ␧il, and dil
The charge Qil stored by the interfacial layer is given by
␳ildilA
Qil = CilVbi = . 共19兲
2
From Cil and Vbi values found above, Qil ⬵ 33⫻ 10−9 C.
The product 共Nil · dil兲 is thus a known quantity. Now, one can
estimate Nil from arbitrary dil values, knowing that dil must
be much smaller than the film thickness. ␧il may in turn be
determined from the expression of Cil or Vbi. However, for a
given Cil value, it can be shown that dil cannot exceed a
maximum, otherwise ␧il would be larger than ␧ f . Accord-
ingly, one expects a minimum for Nil since the product
共Nil · dil兲 is kept constant. Indeed, if one assumes that the
interfacial layer is nonferroelectric (as treated all over this
paper), then the latter probably exhibits degraded dielectric
properties compared to the bulk ferroelectric layer. Hence
one can reasonably state ␧il 艋 ␧ f . In what follows we will use
this criterion to determine a range of possible values for Nil,
dil, and ␧il.
Table III presents some values found by this way. Maxi-
mum dil and ␧il are 12 nm and 130, respectively, whereas
minimum Nil is 6.3⫻ 1026 m−3. If one takes dil values close
to that proposed in the literature13,23 (typically 20 nm), then
one can reasonably assume dil ⬵ 8 – 12 nm in our case. Ac-
cordingly, Nil would be few 1026 m−3 and ␧il ⬵ 100. It should
be noted that values found for Nil, dil, ␧il are in good agree-
ment with those used during simulations performed in the
Cst Rf ␧f Cil Vbi
22 nF 50 M⍀ 130 5 nF −6.5 V
 J. Appl. Phys., Vol. 96, No. 10, 15 November 2004
preceding section. This suggests that they are probably real-
istic because the calculations have been performed separately
and without any a priori. Although appearing excessive, the
Nil value of few 1026 m−3 is still probably close to the genu-
ine charge concentration in the space charge layer. Compu-
tations carried out in Sec. IV indeed revealed that shifts were
visible only when Nil ⬎ 1026 m−3. Moreover, it should be re-
minded that the PZT sample was prepared without oxygen in
plasma gas and that the built-in potential observed on this
sample was unusually large 共Vbi = −6.5 V兲. On the other
hand, such a large Nil value represents still only few percent
of the total oxygen content in a stoechiometric PZT film.
Last, it should be noted that as dil Ⰶ d, the assumption made
before is verified.
VI. CONCLUSION
To summarize, hysteresis loop measured on an oxygen
deficient PZT thin film with a S-T circuit displayed strong
deformations: significant shift along electric field axis and
polarization suppression were observed. An original model,
taking into account the physical parameters involved during
the measurement, has been developed.
Our results demonstrate that a potential barrier Vbi, due
to a negatively charged layer at the interface between the top
electrode and the PZT layer, is responsible for the observed
deformations. The built-in potential in this layer indeed in-
fluences the electric field repartition in the ferroelectric layer
and prevents polarization reversal to occur in a symmetrical
manner, even though the driving voltage is perfectly sym-
metrical. In other words, the switching domains are not
pinned, rather the total switchable polarization is still avail-
able but the ferroelectric layer is no more symmetrically
driven. Making hysteresis loop symmetrical by applying a dc
voltage enables not only to reveal the presence of an interfa-
cial layer, but also to directly determine the built-in potential.
High value was found for the latter 共Vbi = −6.5 V兲, associated
with a large number of charge concentration (Nil of few
1026 m−3) in ultrathin interfacial layer 共dil ⬵ 10 nm兲.
However, the same effect may be demonstrated by as-
suming a space charge layer with opposite sign accumulated
at the other interface, i.e., a positive layer at the bottom in-
terface. Thus, we cannot conclude on whether a negative or a
positive space charge layer accumulates at top or bottom
interface, respectively, nor if both kind of layers are simul-
taneously involved at these interfaces. Further investigations
are required to clarify this point, obviously by considering
the lack of oxygen in the sample. For instance, as Vbi was
independent of the electric field strength, one may suppose
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Le Rhun, Bouregba, and Poullain 5721
that the space charge layer is formed by fixed charges accu-
mulated during the growth of the film and resulting from
oxygen vacancies in the film.
As the hysteresis shift observed in this work is similar to
those encountered in the course of aging of ferroelectric ca-
pacitors, our results strongly suggest that imprint is manifes-
tation of charge accumulation at the interfaces.
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