Polarization reversal and capacitance-voltage characteristic of epitaxial Pb ( Zr , Ti ) O 3

layers
L. Pintilie, M. Lisca, and M. Alexe

Citation: Applied Physics Letters 86, 192902 (2005); doi: 10.1063/1.1926403

View online: http://dx.doi.org/10.1063/1.1926403
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 APPLIED PHYSICS LETTERS 86, 192902 共2005兲

Polarization reversal and capacitance-voltage characteristic

of epitaxial Pb„Zr, Ti…O3 layers
L. Pintiliea兲 and M. Lisca
Max Planck Institute for Microstructure Physics, Weinberg 2, 06120 Halle, Germany and NIMP,
P.O. Box MG-7, Bucharest-Magurele, 077125, Romania
M. Alexe
Max Planck Institute of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany
共Received 18 January 2005; accepted 29 March 2005; published online 2 May 2005兲
Capacitance-voltage 共C–V兲 measurements were performed on epitaxial layers of Pb共Zr0.2Ti0.8兲O3
共PZT兲 with top and bottom SrRuO3 共SRO兲 electrodes. It is shown that the sharp capacitance
peak/discontinuity which is present in the C–V characteristics at different frequencies is directly
associated with the polarization reversal. The ferroelectric film is assumed as a large band-gap
semiconductor with Schottky contacts at the metal-ferroelectric interfaces. The capacitance
discontinuity at the reversal 共coercive兲 voltage is associated with a discontinuity in the built-in
potential at the PZT/SRO interfaces. The C–V characteristics for voltage ranges outside the coercive
values can be used to extract the free carrier concentrations as in the case of Schottky
metal-semiconductor contacts. The carrier concentration was found to be 共2–4兲 ⫻ 1018 cm−3,
independent of measuring frequency and temperature up to 1 MHz and 170 °C, respectively,
suggesting completely ionized shallow impurities. © 2005 American Institute of Physics.
关DOI: 10.1063/1.1926403兴

Ferroelectric thin films are of high interest mostly due to
their potential applications in microelectronics, especially in
the field of nonvolatile memories.1 The electrical character-
ization of thin ferroelectric films is widely based on three
type of measurements: dielectric hysteresis loop 共D-E or
P-E兲, current-voltage 共I–V兲 characteristic, and capacitance-
voltage 共C–V兲 characteristic.2 Despite the widespread use of
the above measurements, there are no generally accepted
models to allow a unitary and coherent description of the
results.
The C–V characteristic has a butterfly-loop shape in the
case of metal-ferroelectric-metal structures. The voltage de-
pendence of the capacitance is usually explained either in
terms of the pure field dependence of the dielectric constant
or by the voltage dependence of the depletion layers that
build up at the contact between the electrode and the ferro-
electric film. In the first case the ferroelectric film is consid-
ered an ideal insulator, whereas in the second case the ferro-
electric film is regarded as a semiconductor with a voltage-
dependent dielectric constant.3–6 It was also asserted that the
C–V measurement can be used to extract the reversible po-
larization, based on the fact that the dc bias sets the polar-
ization value, while the small ac voltage produces reversible
movements of the domain walls.7 The origin of the capaci-
tance peaks in the C–V characteristics was not clearly ex-
plained, considering that such peaks can occur also in non-
ferroelectric structures with Schottky contacts or involving
p-n junctions.8 The possible link between the maxima in ca-
pacitance and the polarization reversal has not been investi-
gated in detail. A major drawback of previous C–V studies
was the quality of the investigated films, most of them being
polycrystalline. Additional effects due to grain boundaries,
a兲
Author to whom all correspondence should be addressed; electronic mail:
pintilie@mpi-halle.mpg.de
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electrically active impurities, or structural defects, etc., were
neglected. Meaningful studies of the link between the C–V
characteristic and polarization reversal will require high
quality single crystalline thin films.
The present article discusses C–V characteristics of a
high-quality epitaxial Pb共Zr, Ti兲O3 共PZT兲 film with oxide
electrodes. The single-crystal-like ferroelectric film allowed
us to separate the switching effects from the pure electronic
behavior of the electrode-film interface, as well as an estima-
tion of the free carrier concentration.
Epitaxial PZT films with a Zr/Ti ratio of 20/ 80 were
grown at 600 °C on epitaxial SrRuO3 共SRO兲 layers acting as
bottom electrode. The growth was performed by pulsed laser
deposition on 共100兲-oriented SrTiO3:Nb 共0.5 % wt兲 single
crystals. The bottom SRO electrode was grown at 750 °C.
The top SRO electrode was deposited at room temperature
through a shadow mask with an area of 0.275 mm2 and then
annealed at 575 °C. Details on growth procedure and struc-
tural properties are given elsewhere.9 The selected PZT com-
position minimizes the structural misfit with the electrode
material. That minimizes the influence of extended structural
defects, i.e., misfit dislocations, on the electrical properties of
the ferroelectric film. The growth process was carefully op-
timized using transmission electron microscopy, x-ray dif-
fraction, and atomic force microscopy 共AFM兲. AFM and pi-
ezoelectric AFM showed an average roughness of about 0.4
nm, the absence of grain boundaries, and a very low density
of a domains.
The hysteresis loop was measured at 1 kHz using a
TF2000 analyzer in dynamic mode. A typical hysteresis loop
is presented in Fig. 1. A remnant polarization of about
40 ␮C / cm2 and a coercive field of about 150 kV/cm are
typical values for the optimized epitaxial PZT layers. The
shape of the hysteresis loop is very close to the ideal loop,
i.e., almost rectangular, although the reversal is not symmet-
86, 192902-1 © 2005 American Institute of Physics
 192902-2 Pintilie, Lisca, and Alexe
FIG. 1. Hysteresis loop acquired on an epitaxial SRO/PZT 共20/ 80兲/SRO
layer structure at 1 kHz.
ric with voltage polarity, suggesting possible not equivalent
electrode-ferroelectric interfaces.
The present work focuses on analysis of the C–V char-
acteristics which were experimentally acquired using an
HP4194A impedance/gain analyzer. The electric field associ-
ated with the ac signal was always kept well below the co-
ercive field. The thickness of PZT films was about 200 nm
and the ac signal was 50 mV. Typical C–V characteristics
obtained at different frequencies are presented in Fig. 2. The
shape is the same no matter the voltage is swept up-down, or
vice versa. The “butterfly” shape is obtained for all frequen-
cies. Marked capacitance peaks for both positive and nega-
tive voltages can be observed at low frequencies, i.e., up to
10 kHz. These peaks transform into capacitance discontinui-
ties at higher frequencies.
The following experiment was performed in order to de-
termine if the peaks/discontinuities in the capacitance are
related to the polarization reversal. The polarization was
switched down by applying a negative voltage of ⫺6 V for
about 1 min. Then the C–V characteristics were measured by
sweeping the voltage up and down between zero and ⫹6 V.
The obtained results are presented in Fig. 3. The capacitance
peak occurs only by sweeping up the voltage, and is absent
by sweeping the dc voltage down to zero. Subsequent sweep-
ing up and down the dc voltage in the same range do not
reveal any peak. Similar results were obtained after prepol-
ing the film with ⫹6 V and performing the C–V measure-
ment by sweeping the voltage down and up between zero
FIG. 2. C–V characteristics acquired at different frequencies. The ac prob-
ing signal was 50 mV. The number of steps for sweeping up or down the dc
voltage was 400, thus the step was of 35 mV. The total time for a measure- when the polarization is absent, while at the other interface
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ment was of 35 s. The corresponding frequency is about 0.028 Hz.
128.59.222.12 On: Fri, 28 Nov 2014 18:08:28
Appl. Phys. Lett. 86, 192902 共2005兲
FIG. 3. C–V characteristics at 1 kHz measured after poling the film with
⫺6 V for one minute.
and ⫺6 V. These results indicate that the capacitance peaks
and the butterfly shape are directly related to the irreversible
switching of the ferroelectric polarization. Capacitance peaks
can also originate from trapping/detrapping effects near the
Schottky contacts but such phenomena are reversible, thus
the butterfly shape should not be present in this case. A quali-
tative indication suggesting the connection between the po-
larization switching processes and the C–V characteristics is
that the switching asymmetry observed in the hysteresis loop
can be found also in the C–V curves in Fig. 2 where the
slopes toward the switching peaks are clearly different for
the two branches. This helps to correlate the slim hysteresis
loop, usually exhibited by polycrystalline ferroelectric films,
with the broad switching peaks observed in their C–V char-
acteristics.
The link of the capacitance peak with the polarization
reversal has important consequences. First, the C–V charac-
teristics do not show only reversible processes, as it was
previously claimed, but includes also the irreversible pro-
cesses due to the polarization switching by sweeping the dc
voltage. A second important aspect is that the voltages cor-
responding to capacitance peaks are in fact the coercive volt-
ages. It means that the average coercive field evaluated from
the C–V measurements 共Fig. 2兲 is about 80 kV/cm, which is
about half of the value determined from the hysteresis loop
of Fig. 1. The P-E loop is acquired at a certain frequency,
i.e., 1 kHz, while the C–V curve is a quasistatic measure-
ment, i.e., the dc bias voltage is swept with few millivolts/
second 共equivalent to millihertz in frequency兲. This fact sug-
gests that there is a significant difference in the quasistatic
and dynamic switching processes.
A reasonable explanation is that a different irreversible
process, closely related to the polarization reversal, is re-
sponsible for the capacitance discontinuity in the C–V char-
acteristics. This explanation is based on the assumption that
the ferroelectric film is a large band-gap semiconductor and
the SRO-PZT interfaces act as a Schottky contacts. The
structure is described by a back–to–back connection of two
Schottky diodes. The PZT film is considered p type2,10 with a
band diagram similar to that proposed by Scott.2 The built-in
potential, which is a measure of the band bending near the
electrode interfaces,11 is controlled by the polarization charge
value and sign.12 At one interface the polarization charge
decreases the built-in potential compared with the situation
the built-in potential is increased by the polarization charge.
 192902-3 Pintilie, Lisca, and Alexe
FIG. 4. Carrier concentration calculated with Eq. 共1兲 from the C–V mea-
surements at 1 kHz 共dots兲 and 1 MHz 共solid line兲. The boxes indicate the
voltage ranges in which Eq. 共1兲 might be applied.
The capacitance of a Schottky contact depends on the
built-in potential.11 Therefore, when the polarization
switches a sudden change of the built-in potential occurs by
changing the sign of the polarization charges at the two in-
terfaces. This sudden and irreversible change in the built-in
potential, due to polarization reversal, leads to the capaci-
tance discontinuity observed in the C–V characteristic. Once
the polarization reversed and saturated, the built-in potential
remains the same up to the coercive voltage of opposite sign.
This explains why the capacitance peak in Fig. 3 occurs only
when the voltage is swept up, and polarization is reversed,
and is absent when the voltage is swept down, and no rever-
sal is present.
It can be assumed that outside the voltage range where
the polarization reversal takes place, the system behaves as a
normal Schottky contact and the associated theory can be
applied. Thus, the C–V characteristics can be used to extract
the free carrier concentration in the same way as in the case
of semiconductor Schottky contact using the relation13
2
共1兲
c共T兲 = ,
qA ␧0␧st关d共1/C2兲/dV兲
2 2
where c共T兲 is the free carrier concentration 共electrons or
holes兲 at the given temperature T, q is the electron charge, ␧0
is the free space permittivity, ␧st is the static dielectric con-
stant as determined from capacitance measurements at zero
applied field. This is a general equation, which is used to
extract the spatial distribution of the free carrier concentra-
tion, known also as the “doping profile.”13 The capacitance
dependence on the applied dc voltage is not important in this
case, as the free carrier concentration is not evaluated from
the slope of a particular representation such as 1 / C2 ⬃ V or
similar.2,14 The voltage dependence of the free carrier con-
centration for the extreme frequencies of 1 kHz and 1 MHz
is presented in Fig. 4. As expected, there is a hysteresis loop.
The sharp change in the sign is not due to the change in the
carrier type. This is due to sign changing in the d共1 / C2兲 / dV
derivative when the reversal takes place 共see Fig. 2兲. The
rectangles in Fig. 4 mark the voltage ranges where Eq. 共1兲
can be accurately used to evaluate the free carrier concentra-
tion of the film. It appears that for positive up voltage on the
reference top electrode the concentration is constant with
voltage, indicating a uniform distribution of the free carriers
within the film 共as the depletion region moves with the ap-
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128.59.222.12 On: Fri, 28 Nov 2014 18:08:28
Appl. Phys. Lett. 86, 192902 共2005兲
plied bias兲. If the PZT film is p type, then positive polarity
on the top electrode means reverse bias. It appears from Fig.
4 that the concentration near the top interface is uniform,
while at the other interface, it is not as uniform. The nonuni-
formity cause can be a gradient of the doping impurity or can
be related to the carriers trapping on deep centers.
The carrier concentration determined from Eq. 共1兲 is in
the 共2–4兲 ⫻ 1018 cm−3 range. This value is of the same order
as other reports.15,16 It worth noting that the above value is a
free carrier concentration, while the previous reports refer to
fixed or trapped charges. The concentration is frequency and
temperature independent up to 1 MHz and 170 °C, respec-
tively, suggesting a complete ionization of the doping impu-
rity and a negligible contribution from deep traps, at least for
the time scale of the dc voltage change during the C–V
measurement.17
In conclusion we have shown that the sharp capacitance
peaks occuring in the C–V characteristics measured on epi-
taxial PZT films, assumed to be wide band-gap semiconduc-
tors with Schottky contacts, are related to the polarization
reversal. The voltage dependence of the dielectric constant
might be important for values between the coercive voltages
when the reversal takes place. Outside the coercive voltages
the polarization is fully saturated and the dielectric constant
is nearly voltage independent. Therefore, the C–V character-
istic can be used to extract the concentration of free carriers.
For epitaxial PZT共20/ 80兲 films a concentration of 共2–4兲
⫻ 1018 cm−3, independent of the measuring frequency and
temperature was found. This suggests a fully ionized doping
impurity and negligible contributions from deep traps. Fur-
ther studies are needed to clarify the nature of the doping
impurities, and to investigate the possible link between deep
traps and polarization reversal.
The work was partly supported by the Volkswagen
Stiftung under Contract No. 1/77738.
K. Uchino, Ferroelectric Devices 共Marcel Dekker, New York, 2000兲.
1
J. F. Scott, Ferroelectric Memories, in Advanced Microelectronics Series,
edited by K. Itoh and T. Sakurai 共Springer-Verlag, Berlin, 2000兲.
3
A. Outzourhit, A. Naziripour, J. U. Trefny, T. Kito, B. Yarar, R. Yandrof-
ski, J. D. Cuchiaro, and A. M. Hermann, Integr. Ferroelectr. 8, 227 共1995兲.
J. F. Scott, Ferroelectrics 232, 25 共1999兲.
4
5
C. Basceri, S. K. Streiffer, A. I. Kingon, and R. Waser, J. Appl. Phys. 82,
2497 共1997兲.
6
C. H. Lin, P. A. Friddle, C. H. Ma, A. Daga, and H. Chen, J. Appl. Phys.
90, 1509 共2001兲.
7
D. Bolten, U. Boettger, and R. Waser, J. Appl. Phys. 93, 1735 共2003兲.
8
J. F. M. Cillessen, M. W. J. Prins, and R. M. Wolf, J. Appl. Phys. 81, 2777
共1997兲.
9
L. Pintilie, M. Lisca, and M. Alexe, Proc. of the 27th International Semi-
conductor Conference, October 4–6, 2004, Sinaia, Romania, IEEE Cata-
log No. 04TH8748 共MiniPrint, Bucharest, 2004兲, Vol. 2, p. 415.
10
M. Dawber and J. F. Scott, J. Phys.: Condens. Matter 16, L515 共2004兲.
11
S. M. Sze, Physics of Semiconductor Devices, 2nd ed. 共Wiley, New York,
1981兲.
12
L. Pintilie and M. Alexe, J. Appl. Phys. 共accepted for pubication兲.
13
D. K. Schroeder, Semiconductor Material and Device Characterization
共Wiley-Interscience, New York, 1998兲.
14
S. K. Dey, P. Alluri, J. J. Lee, and R. Zuleeg, Integr. Ferroelectr. 7, 341
共1995兲.
15
S. K. Dey and R. Zuleeg, Ferroelectrics 109, 1643 共1990兲.
16
T. Mihara, H. Watanabe, H. Yoshimori, C. A. Paz de Araujo, B. Melnick,
and L. D. McMillan, Integr. Ferroelectr. 1, 269 共1992兲.
17
A. K. Jonscher, Dielectric Relaxation in Solids 共Chelsea Dielectrics,
London 1983兲.