Charge ordering in thin films: A

new form initiated by strain effects of

substrate
Cite as: Journal of Applied Physics 88, 3545 (2000); https://doi.org/10.1063/1.1286468
Submitted: 25 January 2000 . Accepted: 01 May 2000 . Published Online: 30 August 2000

A. M. Haghiri-Gosnet, M. Hervieu, Ch. Simon, B. Mercey, and B. Raveau

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© 2000 American Institute of Physics.

JOURNAL OF APPLIED PHYSICS VOLUME 88, NUMBER 6 15 SEPTEMBER 2000

Charge ordering in Pr0.5Ca0.5MnO3 thin films: A new form initiated

by strain effects of LaAlO3 substrate
A. M. Haghiri-Gosnet,a) M. Hervieu, Ch. Simon, B. Mercey,
and B. Raveau
Laboratoire CRISMAT-ISMRA, CNRS UMR 6508, 6 Boulevard du Maréchal Juin,
14050 Caen Cedex, France
共Received 25 January 2000; accepted for publication 1 May 2000兲
The growth of 关101兴 epitaxial films of Pr0.5Ca0.5MnO3 on LaAlO3 substrates has been achieved. The
structure, nanostructure, and magnetotransport properties are reported and compared to those of the
bulk material. The electron diffraction study evidences, at RT, a monoclinic cell with a⬇c
⬇5.4 Å, b⬇7.6 Å, and ␤⬇91°. The monoclinic distortion is assumed to be due to strain effects. At
92 K, a system of extra reflections is observed which implies an incommensurate modulated
structure. The component q of the modulation vector along a * ranges between 0.35 and 0.40. The
lattice images show that the modulation is established throughout the whole film. The q value
observed in the film is significantly lower than the one of the bulk material. This effect is correlated
to strain effects of the substrate, limiting the cell distortion induced by charge ordering. An unusual
insulating-ferromagnetic phase is observed with a critical temperature of 240 K, close to the T CO .
© 2000 American Institute of Physics. 关S0021-8979共00兲08415-2兴

I. INTRODUCTION transition. It is of importance to test the effect of the cell

The properties of thin films of magnetic oxides are very
sensitive to the nature of the substrate, due to the strains,
which can be imposed by the latter.1–4 In this respect, the
colossal magnetoresistance 共CMR兲 manganites, for which
application-driven studies have been carried out on thin
films5 these last years, are of great interest. The CMR prop-
erties of those films can indeed be strongly influenced by a
small distortion of the structure induced by the substrate.
This may explain the large discrepancies sometimes ob-
served between the magnetotransport properties of bulk ma-
terials and thin films having the same composition.
The role of charge ordering 共CO兲, and its competition
with ferromagnetism 共FM兲 in the CMR properties of manga-
nites, although well established, is so far not completely un-
derstood. In the case of thin films, the influence of strains
due to the substrate upon CO has not been investigated to
date, in spite of the important role of this phenomenon in the
CMR. The half doped manganite Pr0.5Ca0.5MnO3 , whose
structure and especially charge ordering properties have been
extensively studied in bulk materials,6–9 can be used as a
model material for a thin film study of the charge ordering
substrate interaction. The advantage of this oxide is also that
the calcium and praseodymium distribution should not influ-
ence the structure since these two cations have the same size.
We report herein on the growth, structure, and magne-
totransport properties of epitaxial films of Pr0.5Ca0.5MnO3
共PCMO兲 on LaAlO3 substrates. Since the temperature varia-
tion of the substrate is small and linear, whereas bulk PCMO
exhibits a strong and rather abrupt distortion at the CO phase
transition, the epitaxy should induce a modification of this
a兲
Author to whom correspondence should be addressed; electronic mail:
anne-marie.haghiri@ismra.fr
parameters constrain 共at least, two of them兲 for a given com-
pound, i.e., keeping unchanged the cation size and mismatch.
One of the signatures of the CO is the modulated superstruc-
ture, which takes the phase below T CO in the Ln1-x Cax MnO3
compounds. Electron microscopy is a perfectly suited tech-
nique to characterize such structural phenomena. We focus
our attention on the structural and nanostructural features of
the film at room temperature, in one hand, and on the modu-
lation vector below T CO in the other. The effect of the strain
induced by the substrate is also analyzed from the magne-
totransport properties.
II. THIN FILM DEPOSITION
Dense targets of Pr0.5Ca0.5MnO3 共PCMO兲 were synthe-
sized via the standard ceramic synthesis methods. CaCO3 ,
MnO2 , and Pr6O11 were mixed in the appropriate ratios and
intimately ground using a semiplanetary ball mill. The pow-
der was annealed at 900 °C for 24 h and then at 1100 °C for
24 h, with intermediate grindings. The pellet was isostati-
cally cold pressed 共900 kg cm⫺2兲 and sintered at 1220 °C for
72 h. To avoid crack formation during heating and cooling
stages, slow temperature variation rates were used. The as
synthesized target is 5 mm thick and has a diameter of 2 cm.
X-ray diffraction has been used to check the single-phase
nature of the target.
The pulsed laser deposition 共PLD兲 apparatus is described
elsewhere.10,11 Briefly, a Lambda Physics excimer laser:
␭⫽248 nm with a pulse rate of 3 Hz was used. The laser
beam was focused to obtain a power density of 2 J/cm2. The
substrate target distance is about 5 cm. Films were deposited
on single-crystal substrates of 关001兴 LaAlO3 , which was
held during deposition at constant temperature ranging from
540 to 620 °C in a dynamic vacuum of 0.3 mbar. Before

0021-8979/2000/88(6)/3545/7/$17.00 3545 © 2000 American Institute of Physics

3546 J. Appl. Phys., Vol. 88, No. 6, 15 September 2000
FIG. 1. X-ray diffraction of a Pr0.5Ca0.5MnO3 film grown on a LaAlO3
substrate. S denotes the reflections from LaAlO3 .
deposition, the optical quality substrates were ultrasonically
cleaned in acetone, then in alcohol, and were glued to the
heater block using silver paste. The temperature, which is
referred to as the deposition temperature, was measured via a
K-type thermocouple, mechanically attached to the heater
block close to the substrate. At the end of the deposition
process, the chamber was filled with 500 mbar of oxygen and
the heater block was cooled to room temperature at 20 °C/
min.
For the above conditions, 1000–1500 Å thick
Pr0.5Ca0.5MnO3 films were deposited on LaAlO3 . The x ray
diffraction and electron microscopy characterization showed
that the films are well crystallized and single phased.
Four point resistance measurements were carried out as a
function of magnetic field and temperature. Contacts were
made to the films using thermal evaporation of silver through
a mask; gold wires were then ultrasonically bounded to the
contacts. Temperature dependent four point resistance mea-
surements were performed using a Quantum Design PPMS
system, for temperatures ranging from 4 to 400 K in a mag-
netic field applied along the direction of growth and varying
between 0 and 7 T. Magnetization of the film was measured
with a Quantum Design dc semiconducting quantum inter-
ference device for temperatures ranging from 4 to 400 K 共H
in plane兲.
III. X-RAY AND ELECTRON DIFFRACTION:
CHARACTERIZATION AT ROOM TEMPERATURE
The x-ray patterns registered at room temperature with a
Seifert x-ray diffraction 共XRD兲 300 diffractometer, using
Cu K ␣ 1 radiation shows that the best crystallized films are
obtained at 600 °C. A typical XRD pattern is shown in Fig.
1. Besides the two peaks labeled S, corresponding to the 001
and 002 reflections of the substrate, two other peaks are ob-
served, which fit with perovskite-like reflections. They allow
us to calculate the thin film interreticular distances along the
direction perpendicular to the substrate plane. For films de-
posited at 600 °C, this distance is refined to 3.85 Å and does
not vary with the temperature deposition in the range 540–
600 °C. This value, significantly larger than those measured
Haghiri-Gosnet et al.
for the bulk 共d 101⫽3.803 Å and d 020⫽3.82 Å兲, suggests that
a compression has been induced by the substrate in the film
plane, leading to an expansion along the perpendicular direc-
tion, in agreement with previous studies on manganites.1–4
The actual orientation of the film cannot be determined un-
equivocally from the x-ray pattern, as already shown for
other manganites crystallizing in the Pnma space group.12
The close relationships between lattice parameters of the
bulk material combined with the condition 0k0:k⫽2n, al-
lows two possible orientations of the film with respect to the
substrate plane to be proposed. Either the film is 关101兴 ori-
ented and the two observed reflections are 101 and 202 re-
flections or the film is 关010兴 oriented and the reflections are
020 and 040. The small difference between lattice param-
eters of the film with respect to those of the bulk does not
allow us to decide between the two possibilities, but the elec-
tron diffraction 共ED兲 study allows the real orientation to be
determined without any ambiguity.
For the electron microscopy 共EM兲 study, the samples
were prepared according to two different methods to get
complementary information. In the first one, the whole film
was smoothly taken out from the thick part of the substrate
and crushed without any ion milling. Characterizing many of
the as-obtained fragments gives a good idea of the crystalli-
zation, composition, domain size, and other microstructural
information along the different crystallographic orientations
of the material. In the second one, a cross section was pre-
pared by ion milling. This technique provides essential infor-
mation on the film/substrate interface and on the nature of
the film along the deposition axis; however, only the milled
area is characterized, contrary to the first method.
The ED study, carried out with a JEOL 200CX electron
microscope and energy-dispersive x-ray 共EDX兲 analyses
show that the film composition is homogeneous. Its actual
cationic composition Pr0.5⫹⑀Ca0.5⫺⑀Mn is identical to that of
the target in the limit of the accuracy 共⑀⫽0.02 is the maxi-
mum observed deviation兲. The reconstruction of the recipro-
cal space, carried out by tilting around the crystallographic
axes, confirms that the cell parameters are a⬇a p 冑2, b
⬇2a p , and c⬇a p 冑2. The intense reflections obey the
hk0:h⫽2n and 0kl:k⫹1⫽2n conditions of reflections,
which are consistent with those observed in the bulk mate-
rial. The 关101兴 and 关010兴 ED patterns are given in Figs. 2共a兲
and 2共b兲, respectively.
In order to determine the film orientation with respect to
the substrate, large areas of the film ⫹ substrate fragments
were examined. They show that the film is mainly 关101兴
oriented 关Fig. 3共a兲兴 but 关010兴-oriented domains are locally
present. The surface proportion of 关010兴 oriented domains is
roughly estimated to be 10%. Note that such a 关101兴 orien-
tation is in agreement with our previous results obtained for
other manganite films crystallizing with the Pnma space
group.12 The high-resolution electron microscopy 共see Sec.
I V兲 showed that the width of these 关010兴-oriented domains is
highly variable, from a few to several hundred nanometers.
The ED patterns recorded with the electron beam per-
pendicular to the substrate normal 共cross section兲 confirm
that the film is mainly 关101兴 oriented. Figure 2共c兲 presents
such a pattern where the substrate and film reciprocal planes
J. Appl. Phys., Vol. 88, No. 6, 15 September 2000
FIG. 2. 共a兲 关101兴 and 共b兲 关010兴 ED patterns of the PCMO thin film deposited
on LaAlO3 . 共c兲 Superposition of the film and substrate ED patterns of a
cross section sample.
are superimposed. The reflections in the rows parallel to the
substrate are very sharp, indicating a perfect matching be-
tween the film and the substrate along that direction, which is
关101̄兴 of the film and as of the substrate. Along the direction
perpendicular to the substrate plane, one observes a weak
splitting of the high order spots; this indicates that the cs
parameter of the substrate 共3.79 Å兲 is slightly smaller than
the interreticular distance d101 of the as deposited film, in
Haghiri-Gosnet et al. 3547
FIG. 3. Schematical representations of the majoritarily orientation of the
PCMO film on the substrate.
agreement with the 3.85 Å distance determined by XRD.
Thus, one observes the 关101兴 direction of the Pnma cell
(d 101⫽3.85 Å) perpendicularly to the substrate plane in
agreement with XRD. Taking into account the different ori-
entations of the film substrate and the cross section, the in
plane directions are 关101̄兴 and 关010兴, in agreement with the
observed parameters which are close to those of the substrate
共3.79 Å兲. The geometrical relationships between these differ-
ent parameters 关Fig. 3共b兲兴 determine that the cell is mono-
clinic. This distortion is clearly observed in the 关010兴 ED
patterns 关Fig. 2共b兲兴, which show that a⬇c⬇5.4 Å and
␤⬇91°. The theoretical parameters of a monoclinic cell, cal-
culated considering the relations d 101⫽3.85 Å, d 101¯
⫽3.79 Å, and 关101兴⬜关101̄兴 are: a⬇5.403 Å, b⬇7.58 Å, c
⬇5.403°, ␤⬇90°9, which perfectly fit with the experimental
ones.
Note that these calculations are carried out for a cubic
LaAlO3 , although the actual cell is slightly distorted 共rhom-
bohedral: a⫽5.357 Å and ␣⫽60°6兲. In fact, in the course of
our investigation, we did observe that the LaAlO3 single
crystals exhibit twinning domains, generated by this distor-
tion. The width of these twinning domains is on the order of
a few tens of nanometers. They do not influence the film
orientation, so that they have been neglected in the calcula-
tions, considering only the average as and bs parameters.
The first important results of this ED characterization is
the fact that the substrate transfers a strain to the epitaxial
film. The Pnma structure type is retained but the
Pr0.5Ca0.5MnO3 film cell is monoclinic.13
IV. HIGH RESOLUTION ELECTRON MICROSCOPY
„HREM… AT ROOM TEMPERATURE
The HREM study was carried out with a TOPCON elec-
tron microscope operating at 200 kV (C s ⫽0.4 mm) and
equipped with an EDX analyzer. The 关010兴 and 关101兴 images
of this thin film are very close to those recorded for the bulk
manganites, indicating that the average structure of the ma-
3548 J. Appl. Phys., Vol. 88, No. 6, 15 September 2000
FIG. 4. 关101兴 HREM image of defective areas. The defective layers appear
as the rows of the brightest dots. The white arrows show example of defects
in the form of short segments. ‘‘0212’’ and ‘‘0223’’ indicate the local for-
mation of n⫽2 and n⫽3 members of the Ruddelsden–Popper series, re-
spectively.
terial is similar to that of the bulk materials. An example of
a 关101兴 HREM image is given in Fig. 4. In fact, the main
nanostructural difference between the film and bulk material
is the formation of extended defects. This enlarged image
clearly shows that they consist of additional 关 AO兴 ⬁ layers
共see white and black arrows in Fig. 4兲. They involve the
formation of two adjacent 关 AO兴 ⬁ layers, ⬇2.3 Å spaced
along b and in which the A and O atoms are in staggered
positions, i.e., the local formation of one 关 (Ca,Pr兲O兴 ⬁ rock
salt 共RS兲-type layer. The intergrowth of RS layers and per-
ovskite layers is a well-known structural mechanism, which
is the basis for the Ruddelsden–Popper series:
An⫹1 Mn O3n⫹1 . 14 It is also observed in bulk15–17 and film18
manganites. In our film, the tiny Mn deficiency evidenced by
the EDX analyses in the defective areas with regard to the
perfect matrix suggests that these RS layers are mainly built
up from Pr3⫹ and Ca2⫹ cations as illustrated by the huge
number of manganites characterized by such intergrowth
structures.
Several remarks can be made about the formation, dis-
tribution, and frequency of these defects.
共a兲 The perovskite/RS intergrowths could, theoretically,
be formed along any one of the three equivalent ap axes of
the perovskite subcell. In fact, due to the 关101兴 orientation of
the film and cell distortion, the defective layers are mainly
perpendicular to the b axis. Only short perpendicular defec-
tive segments are observed along 关101̄兴 forming small rect-
angular islands of perovskite, bordered by perpendicular de-
fective RS layers 共see small white arrow in Fig. 4兲.
Haghiri-Gosnet et al.
FIG. 5. 关010兴 ED pattern and corresponding dark field image recorded at
92 K.
共b兲 Two of these defects are often associated, separated
by two or three perovskite layers, and are often only locally
stabilized 共see arrows and labels 0223 and 0212 in Fig. 4兲.
共c兲 Most of the defective boundaries do not extend over
the whole film along the direction perpendicular to the sub-
strate, but run only over a few nanometers long and are ac-
commodated by the film without any drastic strain. This
means that the structural mechanism of formation of addi-
tional 关AO兴 layers is also engaged in the third direction,
equivalent to the ap direction of the perovskite subcell.
However, most of the crystals display very large areas
with a perfect structure, the defective areas such as those
shown in Fig. 4 being in fact uncomment events.
V. ELECTRON MICROSCOPY AT LOW TEMPERATURE
The ED study versus temperature and the bright/dark
field imaging were carried out with a JEOL 2010 EM fitted
with a double tilt cooling sample holder 共⫾40°兲 for 92 K
⭐T⭐300 K. The sample was cooled down to 92 K in the
microscope, under a magnetic field estimated at 1.5 T. All
the ED patterns were recorded at this temperature, with a
constant current density, which is maintained during warm-
ing of the sample. The ED patterns of the 92 K form system-
atically exhibit additional reflections in incommensurate po-
sitions as observed in the inset of Fig. 5. Similar satellites
have been observed for the bulk composition.9,19 They are
the signature of the charge ordering between the Mn3⫹ and
Mn4⫹ species and of the orbital ordering. However, the
modulation vector q which is parallel to a * is significantly
J. Appl. Phys., Vol. 88, No. 6, 15 September 2000
FIG. 6. 共a兲 The magnetization of the film vs temperature measured with an
applied field of 1.45 T applied parallel to the film. The magnetization of the
substrate was here subtracted. 共b兲 Evolution of the q vector vs T in the
Pr0.5Ca0.5MnO3 bulk sample 共open symbols兲 共Ref. 9兲. The black symbol
corresponds to the q value measured in the film. 共c兲 Evolution of the cell
parameters of the bulk sample from neutron diffraction data from Ref. 8.
smaller than the one observed for the bulk material: it ranges
from 0.35 to 0.40, instead of 0.48 for the ceramic.
The dark field lattice images recorded at 92 K display a
system of gray and bright fringes 共Fig. 5兲 which provide
some interesting information. One indeed observes two in-
terfringe distances, which correspond to two periodicities
along a, namely 2 a p 冑2⬇10.8 Å and 3 a p 冑2⬇16.2 Å. The
fringe spacings are randomly distributed; this is consistent
with the incommensurate character of the modulation and the
q value 共intermediate between 0.5 and 0.33兲. The modulation
is established throughout are observed fragments of the film.
While warming the sample from 92 K up to room tem-
perature 共RT兲, one observes that the intensity of the satellites
decreases. Finally the satellites vanish at 220 K, which can
be considered as corresponding to the T CO temperature. At
the same temperature, the magnetic susceptibility exhibits a
peak which is known to be characteristic of the charge or-
dering 共Fig. 6兲.
Haghiri-Gosnet et al. 3549
TABLE I. PCMO: parameters and inter-reticular distances 共in Å兲.
Bulk Film 共calculated兲
a⫽5.4052 (2) d 101⫽d 101¯ ⬇3.82 a⫽5.403 d 101⫽3.79
RT b⫽7.6064 (2) d 020⬇3.803 b⫽7.58 d 020⫽3.79
c⫽5.3949 (1) c⫽5.403 d 101¯ ⫽3.85
␤⫽91°
10 K a⫽5.4348 (2) d 101⫽d 101¯ ⬇3.843
b⫽7.4819 (2) d 020⬇3.741
c⫽5.4335 (2)
This is more important information and different hypoth-
eses can proposed to explain the significant differences be-
tween the bulk and film modulations. They are likely corre-
lated to either the oxidation state of manganese or strain
effects. Let us analyze the two effects.
Keeping in mind that the cation composition is
Pr0.5Ca0.5Mn, as in the bulk, the smaller q value of the modu-
lation vector could be due to the presence of excess of
Mn4⫹ . Concerning the excess Mn4⫹ , it has been shown that
if one considers the Ln1⫺x Cax MnO3 series, q decreases as x
increases and is approximately equal to 1⫺x, 19 so that if we
keep the ‘‘O3 ’’ stoichiometry, q⫽0.35 would correspond to
the formula Pr0.35Ca0.65MnO3 . Such a hypothesis is in con-
tradiction with the EDX analyses and consequently can be
ruled out. Another possibility would be the existence of cat-
ionic defects, symmetric on both A and Mn sites as for
LaMnO3 , 20,21 leading to the formula
(Pr0.5Ca0.5兲1⫺␦Mn1⫺␦O3 , with ␦⬇0.025. Although it cannot
be definitely ruled out, such a nonstoichiometry has not been
observed for bulk PrMnO3 and is still less probable when a
large amount of calcium is introduced into the structure.
Moreover the bulk phase Pr0.5Ca0.5MnO3 was not found to
be as sensitive to oxygen since an oxygen pressure of 100
bar only reduced the q value to 0.44. Also taking into ac-
count the fact that the film deposition is made at rather low
oxygen pressure, the hypothesis of an overoxidation appears
to be less probable.
Let us now consider the distorted monoclinic cell of the
film, the average in plane parameter of the substrate (ā
⫽3.79 Å) and those of the bulk. At room temperature, as we
discuss above, the strain effect is so intense that it involves a
monoclinic distortion of the film, although the deviation
from ā⫽3.79 Å is 0.03 Å maximum 共see Table I兲. By cool-
ing the bulk sample, one observes 共Fig. 6兲 an abrupt increase
of the d 101 (⫽d 101¯ ) and a coupled abrupt decrease of the b
parameter of the bulk. On the contrary, the substrate param-
eter decrease is small and smooth. From RT observations,
one should also note that the substrate prevents the evolution
of the film parameter vs T. Such a ‘‘lock-in’’ will oppose the
structural transition to the charge ordering, which cannot be
achieved, i.e., the full development of the CO which would
induce the expected limit value q⬃0.5 (0.48) cannot be
reached.
If we superpose the q vs T curve with that of the param-
eters 共especially d 101 and b兲 in the bulk 共Fig. 6兲, we can
observe that for a ‘‘lock-in’’ value of 3.79 Å 共and the per-
pendicular direction slightly inferior to 3.85兲, the corre-
sponding q value is close to 0.38 for a T close to 220 K. This
3550 J. Appl. Phys., Vol. 88, No. 6, 15 September 2000
FIG. 7. The resistivity of the film measured at 0 and 7 T with the field
applied perpendicular to the film.
value of 0.38 fits the experimental one in the film. These
results clearly evidence the close relationship between the
in-plane cell parameters and the electronic instability, which
is at the origin of the charge ordering.22
VI. MAGNETOTRANSPORT PROPERTIES OF THE
FILM
The resistivity of the compound is presented in Fig. 7
with and without 7 T applied perpendicular to the film. In
both cases, the behavior is semiconducting. This is similar to
the behavior of the bulk sample in which a magnetic field of
28 T is necessary to collapse the charge ordering phase.23
Since the low temperature structure is very different
from that of the bulk sample of similar composition, the
magnetic properties should also be very different. In particu-
lar, the q value of the modulation vector 共0.38 instead of 0.5兲
is not compatible with the charge exchange 共CE兲 antiferro-
magnetism which imposed q⫽0.5. The magnetization mea-
surements 共Fig. 8兲 indeed present a clear FM component
FIG. 8. The ferromagnetic magnetization as a function of the temperature
under a field of 0.3 T applied parallel to the film. These values are obtained
from the hysteresis cycles measured at each temperature. An example of this
hysteresis cycle is shown in the inset for 220 K. At each temperature, the
paramagnetic component originated from the substrate and from the film
was subtracted.
Haghiri-Gosnet et al.
with a Curie temperature of 240 K. This strongly contrasts
with the case of the bulk compound which exhibits 共by neu-
tron scattering兲 a CE type antiferromagnetic 共AF兲 up to
170 K.
The number of ordered moments is difficult to determine
accurately in thin films because of the presence of a strong
additional paramagnetic background, which was subtracted
to obtain this figure. This also explains the relative uncer-
tainty of the absolute values of this curve. This ferromag-
netic component can be evaluated to about 1 ␮ B /Mn. In the
absence of any possibility of detecting an AF phase in thin
films 共the signal will be too small in both magnetization and
neutron scattering兲, the interpretation of these results should
be rather speculative.
There are several possibilities, such as:
共i兲 An electronic phase separation with the coexistence
of a metallic ferromagnetic phase 共observed in the magneti-
zation measurements兲 and a nonmetallic modulated phase
共observed in electron microscopy兲 exists, in which the me-
tallic phase does not percolate 共to explain the resistivity re-
sults兲.
共ii兲 The ferromagnetic phase is in fact a phase that is
modulated and canted in which the antiferromagnetic com-
ponent is not observed. This type of structural and magnetic
ordering was not observed in any bulk manganites.
VII. CONCLUSION
The PLD deposition of Pr0.5Ca0.5MnO3 films on LaAlO3
substrates allowed us to obtain a strained Pr0.5Ca0.5MnO3
structure in which the CO distortion cannot fully develop. As
a consequence, the modulation vector q cannot reach 0.5 and
the CE–AF cannot be obtained. Instead of that, an
insulating-ferromagnetic phase was found with a critical
temperature of 240 K.
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