Effect of crystallographic orientation on ferroelectric properties of

PbZr0.2Ti0.8O3 thin films

R. Ramesh, T. Sands, and V. G. Keramidas

Citation: Applied Physics Letters 63, 731 (1993); doi: 10.1063/1.109943

View online: http://dx.doi.org/10.1063/1.109943
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 Effect of crystallogra iic orientation on ferroelectric properties
of PbZrOJiOS803 thin films
R. Ramesh, T. Sands, and V. G. Keramidas
Bellcore, Red Bank, New Jersey 07701
(Received 19 January 1993; accepted for publication 19 May 1993)
We report on the effect of cooling rate on the crystallographic orientation and ferroelectric
properties of PbZr,,,Ti,,O, (PZT) thin films grown on a lattice matched bottom electrode such
as c-axis oriented Y-Ba-Cu-0 (YBCO) . The cooling rate from deposition temperature influences
the crystallographic orientation of the ferroelectric c axis of the PZT film as well as the electrical
properties of the YBCO bottom electrode. As the volume fraction of the ferroelectric phase with
the c axis in the plane of the film becomes higher, the hysteresis loops become more rounded and
the polarization values become smaller. Highly c-axis oriented films, obtained by cooling from
the growth temperature at 20 “C/min, show an almost square hysteresis loop with the largest
polarization values.

With the advent of sophisticated thin-film deposition
technologies, the field of ferroelectrics has attained re-
newed enthusiasm and attention. Research and develop-
ment efforts in many laboratories are focused on integrat-
ing submicron thin ferroelectric films of, for example, lead
zirconate titanate (PZT), with the mature silicon based
memory technology to yield nonvolatile high speed, solid
state ferroelectric random access memories (FRAMs).
The status of this technology is reviewed in recent arti-
cles. 1-5
In order to assess the influence of film crystallinity on
the technologically relevant electrical properties, several
research groups have initiated programs to grow and char-
acterize epitaxial ferroelectric films (see Refs. 1 and 2). To
obtain such films, the bottom electrode should also be ep-
itaxial and single crystalline. More importantly, it is essen-
tial that the crystalline lattices of the ferroelectric material
and the bottom electrode have nearly identical dimensions
and similar crystal chemistry. Such a materials combina-
tion is available in the form of the family of cuprate super-
conductors and related perovskite metallic oxides. These
compounds, for example, Y-Ba-Cu-0, have lattice param-
eters and structural chemistry that are very similar to that
of the ferroelectric perovskites, specifically PZT.
Our basic approach in the fabrication of epitaxial
ferroelectric thin films is outlined in earlier reports.6
Briefly, it consists of using the cuprate superconductors
(which are metallic at room temperature) or other metal-
lic perovskites such as La-&-Co-O as bottom electrodes.‘-’
This gives us the opportunity to grow the ferroelectric film
with a specific crystallographic orientation and, under suit-
able conditions, induce epitaxy. Such heterostructures are
grown by in situ pulsed laser deposition, the details of
which are described elsewhere.6 The heterostructures are
grown on single-crystal perovskite substrates such as
LaAlOs, which provide the correct structural and chemi-
cal template for epitaxial growth. For example, the c-axis
oriented bottom YBa,Cu307 (YBCO) electrode in this ex-
periment was grown at a substrate heater temperature of
810 “C (the substrate surface temperature is typically
-50 “C lower than this temperature), while the c-axis ori-
ented ferroelectric PbZr0.2Ti0,,0s layer was grown at
700 “C. It is important to note that during the deposition,
the YBCO layer is in the nominally tetragonal structure
while the PZT layer grows in the cubic structure. Both the
layers undergo structural phases transformations as they
are cooled to room temperature. In the case of YBCO the
tetragonal-orthorhombic transition occurs in the tempera-
ture range of 400-600 “C!, while the cubic PZT layer be-
comes tetragonal at approximately 390 “C!, which is the
curie temperature. Below this temperature the film is ferro-
electric.
Both these transformations are accompanied by twin-
ning to accommodate the strain involved. In the case of
PZT, one mode of twinning involves the formation of 90”
twin boundaries, across which the c axis of the tetragonal
structure is rotated by 90”. For example, in a PZT film with
the c axis normal to the substrate surface, one observes
twins with the c axis in the plane of the film, i.e., u-axis
oriented normal to the surface. The control of the volume
fraction of such a-axis oriented material and its effect on
the ferroelectric properties is the focus of this letter.
There are many ways to control the volume fraction of
a-axis oriented material in the PZT Iilm. One of them is to
change the composition of the material (for example, by
lanthanum substitution at lead sites or the zirconium:tita-
nium ratio), when the bottom electrode is unchanged. The
deposition temperature of the PZT layer also has an influ-
ence on the relative fractions of the two orientations, as has
been demonstrated in an earlier publication. The in-plane
lattice parameters of the electrode material at deposition
temperature and, more importantly, during the phase
transformation process, also affect the c/a volume fraction.
The cooling rate from deposition temperature influences
the c/a fraction as does the thermal expansion mismatch
between the substrate and the film. The effect of the cooling
rate is especially important in the case where the electrode
is also a perovskite material such as YBCO (which is con-
ducting when fully oxidized), for which the amount of
oxygen incorporated will depend on the rate at which the
film is cooled down to room temperature. Finally, the
amount of a-axis oriented material also depends upon

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 IJY”“.”
r~~
13500.0
12000.0
(0OZ)PzT
1
(2OO)PzT
3000.0
i%cl
i’
1500.0
0.0 -“r”-“---, I , , 1 , ,
43 44 45 46
Angle, 26, degrees
FIG. 1. A small angular section of x-ray diffraction patterns for epitaxial
heterostructures deposited under identical conditions, but cooled to room
temperature at different rates. Note the systematic difference in the rela-
tive intensities of the (200),, and (002),z, Bragg peaks and the
(O06)vaco peak position and intensity.
whether there are any constraints on the film during the
transformation, i.e., whether there is an epitaxial top elec-
trode or not. This letter addresses the effect of cooling rate
from deposition temperature on the electrical properties of
PZT/YBCO heterostructures grown on single crystal
LaA103. Under these growth conditions, the PZT film on
top is free to relax during cooldown to room temperature,
without the constraint of the top electrode. The top elec-
trodes in this case are Pt/Au pads that are evaporated
through a shadow mask after the deposition process.
Rutherford backscattering spectrometry was used to
confirm that the compositions of the two layers were com-
mensurate with that of the targets, while x-ray diffraction
was used to study the crystallographic quality of the two
layers. Ferroelectric hysteresis loops were obtained using
both pulsed testing as well as resistance compensated.
Sawyer-Tower measurements, capable of measuring over a
continuous range of frequencies from 0.01 Hz to 1 MHz in
the voltage range of O-l 5 V. Fatigue and aging experiments
were carried out using the Radiant Technologies RT66A
pulsed testing apparatus.
Planar section transmission electron micrographs of all
the samples indicate that the ferroelectric film does not
have large angle grain boundaries in it. The effect of the
cooling rate on the structural evolution is illustrated in the
set of x-ray diffraction patterns in Fig. 1 which shows a
small angular section of the 19-20 scan from the samples
cooled at different rates. There are two important features
that draw attention. The first is the effect of the cooling
rate on the relative fractions of the (002)PZT and
(200)PZT peaks. When the sample is cooled at 5 “C/min,
there is a significant fraction of a-axis oriented material,
which decreases to a very small value when the cooling rate
is increased to 20-25 “C/min. Further increases in the cool-
ing rate do not affect the amount of a-axis oriented mate-
rial. The second point of interest is that as the cooling rate
is increased to above 20 “C/min, the intensity of the
(006)YBC0 peak drops dramatically. Concurrently, the
732 Appl. Phys. Lett., Vol. 63, No. 6, 9 August 1993
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f:,~5Wrn,“,,
I
(006)YSCO 0.3 pm
I I
0.1 pm
ii,i-, 20Wmin.
I
..!
Virtunl Ground Made I
1. \ “i-Savyer-T”wer Made
x-axis : Electric Field : t di” = ,!I0 kV / Ern
y-lx!3 : Polnrbnli‘,” : I *iv =.3x.5 pc I cnl~
I , I
-6o”clmin.
‘lOO°Clmin.
& I I J
47 FIG. 2. Ferroelectric hysteresis loops for the samples cooled at different
rates. Note the systematic change in the squareness of the hysteresis loop
and the magnitude of the polarization as a function of cooling rate. The
inset shows a schematic diagram of the heterostructure and the measure-
ment method.
c-axis lattice parameter of the YBCO layer also increases,
as evidenced by the shift of the (006)YBC0 peak to lower
28 values. The decrease in diffraction intensity of the
(006)YBCO peak with cooling rate correlates with incom-
plete incorporation of oxygen into the YBCO lattice. The
oxygen-deficient YBCO structure, as is well known, also
has a larger lattice parameter compared to the completely
oxygenated structure. lo The most important inference from
the x-ray diffraction patterns is that as the cooling rate is
increased, the YBCO layer becomes less conducting (since
it is not fully oxygenated).
These changes in structure have a direct influence on
the polarization properties of the capacitor, which is illus-
trated in the series of hysteresis loops in Fig. 2. This figure
also shows schematically the measurement method. As de-
scribed earlier, the top electrodes are Pt/Au dots that are
evaporated through a shadow mask. The right-hand side of
this figure shows hysteresis loops measured at 5 V using a
Sawyer-Tower setup. The loops are measured at 506 Hz
and are resistance compensated. The film cooled at 5 “C/
min shows a low polarization value, consistent with the
fact that a significant part of the c axis (the polarization
direction) is in the plane of the film. The highest value of
polarization is obtained for the film cooled at 20-25 “C/
min, which shows almost no u-axis oriented material.
From the x-ray diffraction patterns in Fig. 1 one would be
led to think that increasing the cooling rate would also
increase the polarization. However, there is actually a de-
crease in polarization for the samples cooled at higher
rates. We attribute this to the fact that as the cooling rate
is increased, the bottom YBCO electrode becomes less me-
tallic (i.e., more semiconducting). This conclusion is fur-
ther supported by comparing the fatigue and aging behav-
ior of the films cooled at 100 “C/min with films grown on
PrBCO as the bottom electrode instead of YBCO. It is well
known that when fully oxidized, PrBCO behaves like a
semiconductor with a room-temperature resistivity that is
approximately 50 times larger than that of optimally oxi-
dized YBCO.”
Figure 3 shows data on the aging behavior of the films
cooled at different rates in comparison with a PZT film
grown on c-axis oriented PrBCO that was grown at the
Rqmesh, Sands, and Keramidas 732
 % 100 fatigue performance. We point out that the fatigue proper-
Y ties of these capacitors are much inferior to those grown
Y 80 with symmetric oxide electrodes, since the top electrode in
n
s this case is Pt. However, these data along with the aging
'J
d 60 behavior, serves to illustrate that the electrode conductivity
'5 is an important parameter, in addition to the nature of the
a 40 electrode-film interface, in determining the ferroelectric
ELi -If- YBCO-25”C/min
3 -.- PrBCO performance. Since the conductivity of metallic perovskite
20
3 + YBCO-lOO”C/min oxides is sensitive to the degree of oxygenation, it is im-
t8 o i_.,.,.,.....,.,,..“--.-.., portant to optimize the oxygen content of the films during
t# lo” 100 IO’ 102 ld IO’ 105 106 the deposition and subsequent cooldown process. Conse-
Aging Time, seconds quently, the cooling rate from deposition temperature be-
comes an important variable in optimizing the ferroelectric
FIG. 3. A plot of remnant polarization (normalized with respect to that properties.
at the beginning of the experiment) as a function of aging time for a write In conclusion, a clear effect of the ferroelectric prop-
voltage of - 4 V and a read voltage of + 3 V. The capacitor cooled at
lOO’C!/min behaves very similarly to a capacitor with PrBCO bottom erties on the cooling rate from the deposition temperature
electrode, indicating the effect of electrode conductivity. has been demonstrated. The cooling rate from the deposi-
tion temperature is one of the variables that can be used to
same temperature as YBCO (i.e., 810 “C). This hetero- control the c/a fraction in the ferroelectric film. The opti-
structure was cooled at 20 “Urnin (i.e., similar to the best mum cooling rate for PZT films of this composition is in
film on YBCO). The aging experiment was carried out the range of about 20 “C/min. The effect of the cooling rate
with a write voltage of -4 .V followed by a read at + 3 V. on fatigue and aging is due to the change in the conduc-
The films cooled at 5 and 20 “C/niin show very similar tivity of the YBCO electrode with oxygen incorporation.
aging behavior, characterized by a small log-linear de- We acknowledge many stimulating discussions
crease in the remnant polarization with aging time. On the with and the technical assistance of W. K. Chan and
other hand, the film cooled at 100 “C/min shows a dra- B. Wilkens.
matic log-linear drop in the remnant polarization after
about 30 s of aging, with a slope that is much larger than
that of the slowly cooled samples. The most interesting
point is that the aging behavior is very similar to that of a
film grown on PrBCO, indicating that the aging behavior is ’See for example, Proceedings of Materials Research Society Fall Meeting
Symposium on Ferroelectric Thin Films II, edited by A. Kingon, E. R.
distinctly ini-luenced by the electrode conductivity. Myers, and B. Tuttle (Materials Research Society, Pittsburgh, P A
Finally, Fig. 4 compares the fatigue properties of films 1991); Proceedings of Third International Symposium on Integrated Fer-
cooled at different rates. Also shown are the c/a volume roelectrics, edited by C. A. Paz de Araujo, University of Colorado,
fractions and the remnant polarization for these samples. Colorado Springs, CO., April 1991; Proceedings of Fourth Interna-
The c/a volume fractions, were determined as the ratio of tional Symposium on Integrated Ferroelectrics, Monterey, CA, March
1992.
the x-ray peak intensities of the (002),, and ( 200)pzT *J. F. Scott and C. A. Paz de Araujo,- Science 246, 1400 (1989); M.
peaks. Fatigue data for a film grown on PrBCO and cooled Sayer and K. Sreenivas, Science 247, 1056 ( 1990); G. H. Haertling, J.
at 20 “C/min are also shown in this tigure for comparison. Vat. Sci. Technol. 9, 414 (1991).
Clearly, the film cooled at about 20 “C/min shows the best 3S. Sinharoy, H. Buhay, D. R. Lampe, and M. H. Francombe, J. Vat.
Sci. Technol. A 10, 1554 ( 1992).
‘J. T. Evans and R. D. Womack, IEEE J. Solid State Circuits 23, 1171
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s 100 108
(1 schnig, D. L. Hart, and J. M. Tarascon, Science 252, 944 ( 199 1); R.
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con, V. G. Keramidas, D. K. Fork, J. Lee, and A. Safari, Appl. Phys.
b2 -a- fatigue life 10’ 2. Lett. 61, 1537 (1992). -.
; 60 ’R. M. Wolf, in Proceedings of Materials Research Society Fall Meeting
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x PrBCO, fatigue life
Myers, and B. Tuttle (Materials Research Society, Pittsburgh, PA,
ii
lo6 u” 1991).
i
2. 4o
20 *J. T. Cheung, P. E. D. Morgan, and R. R. Neurgaonkar, in Proceedings
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Paz de Araujo, Monterey, CA, March, 1992, pp. 158-170.
lo5
‘R. Ramesh, H. Gilchrist, T. Sands, V. G. Keramidas, R. Haakenaasen,
1. 0 20 40 60 80 100 120
Cooling rate, “C/min and D. K. Fork (unpublished).
‘“G. V. Subba Rao and U. V. Varadaraju, in Chemistry of High Temper-
FIG. 4. A comparison of the crystallographic perfection (i.e., c/a ratio), ature Superconductors, edited by C. N. R. Rao (World Scientific, River
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grown on PrBCO bottom electrode and cooled at 20 ‘C/min. Yamada, Phys. Rev. B 38, 2910 (1988).

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