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Symmetry of the charge-ordered

phases in Pr0.5Ca0.5MnO3
a

P.R. Sagdeo & N.P. Lalla

Discipline of Physics & Discipline of Surface Science Engineering,

Indian Institute of Technology Indore, Indore, 452017, India.
b

UGC-DAE Consortium for Scientific Research, University Campus,

Khandwa Road, Indore, 452001, India.
Published online: 03 Oct 2013.

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To cite this article: P.R. Sagdeo & N.P. Lalla (2014) Symmetry of the charge-ordered phases in
Pr0.5Ca0.5MnO3, Philosophical Magazine, 94:2, 117-124, DOI: 10.1080/14786435.2013.845312
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Philosophical Magazine, 2014

Vol. 94, No. 2, 117124, http://dx.doi.org/10.1080/14786435.2013.845312

Symmetry of the charge-ordered phases in Pr0.5Ca0.5MnO3

P.R. Sagdeoa* and N.P. Lallab
a

Discipline of Physics & Discipline of Surface Science Engineering, Indian Institute of

Technology Indore, Indore 452017, India; bUGC-DAE Consortium for Scientic Research,
University Campus, Khandwa Road, Indore 452001, India

Downloaded by [University of Strathclyde] at 07:36 07 October 2014

(Received 7 February 2013; accepted 10 September 2013)

The crystallographic symmetry of the charge-ordered Pr0.5Ca0.5MnO3 manganite
is studied at 98 K using convergent beam electron diffraction technique.
These studies have revealed appearance of two different type of charge-ordered
phases in different domains of the same grain. These correspond to be monoclinic and triclinic phases. These studies reveal that the symmetry of the
charge-ordered phase is highly sensitive to the local strain conditions.
Keywords: crystal symmetry; electron diffraction; phase separation
PACS number(s): 75.47.LX, 61.50.KS, 61.50.AH

Introduction
The phase competition in colossal magnetoresistive manganites is one of the hottest
topics in condensed matter physics. The manganites exhibit a variety of electronic,
magnetic and structural phase transitions and phase coexistence over a wide temperature
and composition ranges [1,2]. The occurrence of phase coexistence is attributed to the
charge, orbital and spins degrees of freedoms. Since, all manganites invariably show
JahnTeller distortion due to Mn3+ ions, the lattice degrees of freedom also necessarily
becomes another important attribute to the phase coexistence, i.e. lattice strain may also
result either in stabilizing or destabilizing various phases. Some recent reports do
highlight the important role of strain on electronic and structural phase coexistence in
manganites [36]. In mixed valence manganites such as La1 xCaxMn3+1 xMn4+xO3, the
Mn3+ and Mn4+ ions are randomly distributed throughout the lattice above certain temperatures. For certain composition range and below a critical temperature (TCO), the
Mn3+ and Mn4+ redistribute coherently throughout the lattice and give rise to a chargeordered state. Even though vast literature is available [710] on these topics, but clear
understanding of the structure of charge-ordered states of manganites is still lacking.
Previously, synchrotron X-ray and neutron diffraction has been used to explore the
structure of the charge-ordered phase in La1 xCaxMnO3. These studies independently
show the presence of P21/m [11] and Pnma [12] space groups for these charge-ordered
manganites. Whereas, some studies such as electron microscopy, sound velocity and
optical spectroscopic measurements on similar charge order manganites, do suspect the
*Corresponding author. Email: prs@iiti.ac.in
2013 Taylor & Francis

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P.R. Sagdeo and N.P. Lalla

presence of triclinic structure for these charge-ordered states [1315]. Moreover, our
earlier studies on Pr0.5Ca0.5MnO3 [5] clearly reveal the presence of new type of chargeordered phase having charge modulations along (1/4,1/2,1/4) of the basic Pnma phase;
thus it appears that the crystal structure/symmetry of the charge-ordered phase is not
unique. Most of the earlier studies have been done using conventional X-ray and neutron scattering, which are not able to probe the local changes in structure/space group,
thus give information about the global structure. On the other hand electron scattering,
whose amplitude is several orders of magnitude higher, can probe very small volumes.
In this paper, we describe and discuss the studies done by us to investigate the symmetry of charge order state of one of the manganites, Pr0.5Ca0.5MnO3 to explore the possible role of localized strain. We have carried out the symmetry analysis following the
convergent beam electron diffraction (CBED) technique. The CBED technique has a
unique capability for crystallographic symmetry determination [16]. We have carried
out SAD and CBED studies on the charge-ordered Pr0.5Ca0.5MnO3 at 98 K.
Experimental details
Pr0.5Ca0.5MnO3 was prepared using solid-state reaction using 99.9% pure CaCO3,
Pr6O11 and MnO2 as the starting ingredients. The details of sample preparation employing solid-state reaction, bulk structural characterization using powder X-ray diffraction
(XRD) of the as-prepared samples and temperature-dependent electron diffraction studies carried out using TECNAI-G2-20 (FEI) TEM are described elsewhere [17,18]. TEM
was operated in selected area diffraction (SAD) and convergent beam diffraction
(CBED) modes. Zero-order Laue zone (ZOLZ) CBED patterns were recorded using a
50 m condenser aperture.
Results and discussions
Sample characterization by XRD
Figure 1 shows the room temperature XRD data of the as-prepared sample. The data
were rened using FULLPROF-2k Rietveld renement program with the space group
Pnma [19]. The absence of even a weakest unaccounted peak in the rened powder
XRD prole conrms the phase purity of the sample. To conrm the concentration of
Pr and Ca in the as-prepared sample, EDAX analysis was carried out. The measured
composition was found to be Pr0.49Ca0.51MnO3, which is close to the synthesized composition within the typical error of EDAX analysis.
Electron diffraction studies
In order to study the low-temperature symmetry of the charge-ordered phase of
Pr0.5Ca0.5MnO3, the sample was cooled down to 98 K. The electron diffraction studies
were carried out employing SAD and CBED techniques. Figure 2 shows a typical electron micrograph of a Pr0.5Ca0.5MnO3 grain. This has been taken along [0 1 0] zone. The
complete black contrast of the grain is due to the fact that the whole grain is properly
oriented in this low index zone of [0 1 0]. In this grain, we see domain like features.
These are basically twin domains of Pnma phase, appearing due to solid-solid phase

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Intensity (a.u.)

Experimental data
Rietveld fitting to the data

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33.0

30

40

33.2

50

33.4

60

70

80

90

100

Figure 1. Rietveld rened room-temperature powder XRD data of the synthesized

Pr0.5Ca0.5MnO3 sample using Pnma space group. The absence of any unaccounted peak in the
rened pattern conrms single phase of the sample.

Figure 2. A typical electron micrograph of a Pr0.5Ca0.5MnO3 grain showing various domains

within the grain. The twin domains R1 and R2 are marked for clarity.

 phase during cooling of the sample after sintransformation of the parent cubic (Pm3m)
tering. In such twin domains a and c axes of the one domain will be mutually perpendicular to that of the neighbouring twin domain. That is what has actually been
observed in the present case.
The [0 1 0] zone SAD patterns collected at room temperature from regions R1 and
R2 are shown in Figure 3(a) and (b) respectively. The mutually perpendicular a axes
can be seen in the two SADs. The presence of well-dened superlattice spots in these

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Figure 3. [0 1 0] zone SAD patterns (a) from domain R1 and (b) from domain R2, showing the
presence of diffuse incommensurate superlattice spots along a. From SAD, it is clear that a
(R1) and a (R2) of two domains are perpendicular to each other.

SAD patterns at room temperature indicates the occurrence of charge and orbital
ordering (COO) in Pr0.5Ca0.5MnO3 manganite right at room temperature itself. This is
consistent with those reported earlier for La1 xCaxMnO3 [9,10,20]. A typical SAD

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pattern from a well-ordered COO state in Pr0.5Ca0.5MnO3 at 98 K is shown in Figure 4.

The occurrence of intense and sharp superlattice spots due to charge and orbital ordering can be seen along a-axis. Figure 5(a) and (b) depicts the CBED patterns from
regions R1 and R2, respectively. A careful inspection of the two CBED patterns reveals
that the pattern in Figure 5(a) neither has a two-fold rotation axis along [0 1 0] zone nor
a mirror symmetry along a-axis. But, it has a mirror parallel to the c-axis. The
absence of mirror along a-axis and presence of mirror along c-axis are clear from the
comparison of the orientations of broad black line like features in (2 0 0) and (2 0 0)
discs, indicated by arrows, as well as the intensities of (4 0 4) and (4 0 4) discs and the
(
4 0 4) and (
40
4) discs, as indicated by arrows. Please note that the indices given are
based on the charged-ordered lattice having doubled a-parameter. But the pattern in
Figures 5(b) neither has two-fold rotation about [0 1 0] nor mirror symmetry along a or
c. The features responsible for breaking mirror symmetry in the CBED of Figure 5(b)
are indicated by arrows. The asymmetric intensity distribution in the discs responsible
for the breaking of mirror symmetry along the c-axis is indicated by black arrows and
the features responsible for breaking mirror symmetry along a-axis are indicated by
white arrows. The absence of two-fold rotation axis about [0 1 0] in CBED of Figure 5
(b) is evident from the orientations of black broad line like features in (2 0 0) and
(
2 0 0) discs and (8 0 0) and (
8 0 0) discs, as indicated by white arrows. Although the
black broad lines are rather diffuse but difference in their orientations are clear. It can
be noted that the orientations of these broad black lines do not comply with a two-fold
rotation. To make this point clear, we present in Figure 5(c), a qualitative sketch of the
[1 0 0] row of disks of Figure 5(b), two-fold symmetry is completely absent in it. Keeping in view the similarity between the charge-ordering (CO) modulations observed in

Figure 4. A typical SAD collected from charge-ordered phase of Pr0.5Ca0.5MnO3 at 98 K.

Charge-ordered superlattice reections, as indicated by arrows, are now commensurately ordered
along a.

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(a)

(b)

Figure 5. CBED collected from (a) twin domain R1 and (b) twin domain R2. Presence of mirror
along c in (a) is indicated by the dotted line. CBED in (b) neither pose two-fold nor any mirror
symmetry along a or c. (c) Schematic sketch of [1 0 0] row of discs in (b).

the present observations and that of Loudon et al. [10], it becomes essential here to
discuss the observed intensity features of the CBED discs in its light. Loudon et al.
report that the CO is basically a charge density wave (CDW) type modulation which is
usually incommensurate with modulation vector not exactly along the a-axis. It has
some b and c components also. In our case also, the CO is incommensurate but the

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CO modulation vector is exactly along a-axis, see SADs in Figure 3(a) and (b), where
CO reections are aperiodically spaced. But, as the sample was cooled down to 98 K,
the incommensurate phase transformed to a commensurate one. Therefore, the space
group analysis being presented here is true only in the limit of commensurate modulation. It should be noted that the decision of the absence of two-fold in the CBED given
in Figure 5(b) is made based on the (2 0 0) and (8 0 0) reections, which are kinematically allowed fundamental reections and therefore their positions will not be affected
by the incommensurate CDW modulation. Moreover, at 98 K, all the CO superlattice
reections are quite away from the fundamental ones and the CBED discs made by
them are not touching with that of the fundamental reection discs. Thus, the intensity
distribution in the fundamental discs is not being directly affected by the slightly split
CO reections and therefore the symmetry of the intensity distribution in the fundamental discs is a true representation of the symmetry of the crystal structure. Thus, the
whole pattern (WP) symmetry of the CBED pattern, in Figure 5(a) will be m, the diffraction group will also be m and therefore point group will also be m. Thus, the
structure of the low-temperature CO phase in region R1 is monoclinic. Whereas, due to
absence of two-fold and mirror symmetries, the WP symmetry of the CBED pattern
shown in Figure 5(b) will simply be 1 i.e. the diffraction group is also 1. Since
[0 1 0] zone is supposed to be the most symmetric axis, the presence of only 1 in the
diffraction group clearly indicates that the point group symmetry of the low-temperature CO phase in region R2 is triclinic only. The occurrence of different symmetries in
the adjacent COO domains of the same grain, monoclinic (in R1) and triclinic (in R2)
at 98 K, clearly indicates the indeniteness in the phenomenon of charge ordering in
Pr0.5Ca0.5MnO3. In the absence of any compositional inhomogenity, the observed indefiniteness in the symmetry of charge ordering in these domains appears to be due to the
presence of strain in these samples. The tremendous effect of strain on the charge
ordering [20] and the presence of local variation in the charge-ordering modulation
vector, due to the presence of strain [21], are experimentally well-observed facts. The
important point here is to note that the symmetry of the CO phase is very sensitive to
the local strain conditions.
Conclusions
Based on the above described analysis of the results of CBED carried on chargeordered phase of Pr0.5Ca0.5MnO3 at 98 K, it is concluded that the symmetry of the
charge-orbital-ordered phase is not unique. The present observations clearly reveal that
it differs even in the adjacent domains of the same grain. Its symmetry may not always
be P21/m (i.e. monoclinic), but it may vary depending on the local strain condition of
the domain. We could see both monoclinic and triclinic symmetries in the same grain of
charge-ordered Pr0.5Ca0.5MnO3.
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