Raman, infrared and x-ray diffraction study of phase stability in La 1−x Ba x MnO 3

doped manganites
Chaitali Roy and R. C. Budhani

Citation: Journal of Applied Physics 85, 3124 (1999); doi: 10.1063/1.369651

View online: http://dx.doi.org/10.1063/1.369651
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 JOURNAL OF APPLIED PHYSICS VOLUME 85, NUMBER 6 15 MARCH 1999

Raman, infrared and x-ray diffraction study of phase stability

in La12 x Bax MnO3 doped manganites
Chaitali Roy and R. C. Budhania)
Department of Physics, Indian Institute of Technology Kanpur, Kanpur-208016, India
~Received 11 May 1998; accepted for publication 8 December 1998!
Formation of different crystallographic phases and their characteristic Raman and infrared spectra
are studied in the manganite system La12x Bax MnO3 for x in the range of 0<x<1, and with
variations in oxygen stoichiometry. Synthesis of the end member LaMnO3 in pure argon
environment leads to the formation of Jahn–Teller distorted, antiferromagnetic orthomanganite.
While the observed Raman modes in this compound are primarily due to internal vibrations of
MnO6 octahedra, the infrared ~IR! spectra show an absorption edge in addition to the IR active
phonons. The oxygen rich LaMnO3 is rhombohedral and has fewer zero-wave-vector phonon
modes. In the barium substituted compositions with 0,x<0.25, a single phase rhombohedral
compound of decreasing rhombicity is formed. A further increase in x leads to the ideal cubic
perovskite structure for which a factor group analysis yields no Raman active and three IR active
phonons of F1u symmetry. The compound with x50.35, shows faint Raman modes of hexagonal
BaMnO3 ~P6 3 mc noncentrosymmetric group! whose presence is not seen in x-ray diffraction data.
For x.0.35, all three techniques used here show the formation of a two-phase mixture of
La0.65Ba0.35MnO3 and hexagonal BaMnO3. An attempt has been made to correlate the progressive
increase in symmetry of the crystal structure, shift of IR absorption edge to lower energies, and
disappearance of phonon modes with x and d with the reported electrical and magnetic behavior of
this hole-doped manganite. © 1999 American Institute of Physics. @S0021-8979~99!01006-3#

I. INTRODUCTION transport measurements show that the system evolves from

The mixed valent oxides of the type R12x Ax MnO3
where R is a rare earth element and A the divalent Ca, Sr, or
Ba have been a subject of scientific investigations for many
decades.1,2 The recent interest in these compounds emanates
from the observation of a large negative magneto-
resistance,3,4 charge and spin ordering effects as a function of
Mn31 /Mn41 ratio5,6 and similarity of many issues with the
problem of high T c superconductivity in the cuprates.7 The
most extensively studied derivatives of the above general
class of oxides are the compounds with formula
La12x Ax MnO3. The end members of this series, namely
LaMnO31 d and AMnO32 d where d represents the propensity
of the Mn ions to be in 31 or 41 valence states, present two
interesting classes of oxides. At room temperature, stoichio-
metric LaMnO3 is orthorhombic due to a mismatch between
La–O and Mn–O bond lengths, and due to a cooperative
Jahn–Teller distortion associated with Mn31 ions. The sys-
tem orders antiferromagnetically at T N ;135 K below which
some degree of canting of Mn31 spins leads to a parasitic
ferromagnetism. The changes in the crystallographic struc-
ture and, magnetic and electrical properties of this system as
d increases from zero have been studied by many
workers.8–10 Powder diffraction measurements of Topfer and
Goodenough8 for example, show an orthorhombic phase for
0< d <0.06 and a rhombohedral phase for 0.1< d <0.18. For
0.06< d <0.1 a two-phase mixture of orthorhombic and
rhombohedral phases has been predicted. The magnetic and
a!
Electronic mail: RCB@IITK.ERNET.IN
an antiferromagnetic and insulating state to a metallic ferro-
magnet through a spin glass phase on increasing d.
The magnetic and crystallographic structure of the other
end member, namely AMnO32 d , is quite complex. Here the
ideal cubic perovskite structure consisting of all corner shar-
ing MnO6 octahedra becomes unstable as the size of the A
cation becomes larger than the critical radius given by the
Goldschmidt formula.11 While the compound CaMnO32 d is
cubic for d as high as 0.5, the cubic phase is unstable for
SrMnO3 and BaMnO3. Instead, the structure consists of a
stacking of closed packed SrO3 ~or BaO3! layers with Mn
ions occupying interlayer octahedral sites. Based on the
number of layers, stacking sequence, and ordering of transi-
tion metal ions, numerous unique polytypes of these com-
pounds can be theoretically generated.12
The structure and magnetic phase diagram of
La12x Cax MnO3 system has been studied in detail.13 Structur-
ally, there is a complete solubility between CaMnO3 and
LaMnO3. In its magnetically ordered state, the solid solution
becomes metallic for 0.18<x,0.5. For x in the range of
0.5–1.0 it is insulating. The stability of the perovskite struc-
ture as a function of Sr or Ba concentration, on the other
hand, is not well established. However, there are a large
number of recent studies on electrical conduction and mag-
netic ordering in La12x Srx MnO314,15 system for x<0.4
where a single phase is formed. In the case of Ba-based
compound such detailed studies are lacking.
Most of the information available on the structure and
phase stability of La12x Ax MnO3 alloys has been deduced

0021-8979/99/85(6)/3124/8/$15.00 3124 © 1999 American Institute of Physics

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 J. Appl. Phys., Vol. 85, No. 6, 15 March 1999 C. Roy and R. C. Budhani 3125

through macroscopic tools such as x-ray and neutron diffrac-

tion or inferred from susceptibility measurements. A lot
more could be learned about the physics of these materials
through light scattering and absorption experiments. Inelastic
scattering of light by vibrational, magnetic, and electronic
excitations in these system, for example, can provide a pow-
erful means to track the structural and magnetic phase trans-
formation as a function of temperature and composition.
Similarly, light transmission/absorption studies allow under-
standing of the electronic and vibrational excitations. While
Raman scattering has been used extensively to study vibra-
tional and magnetic excitations in various alkali halide based
perovskites,16,17 and ternary oxides of iron and
chromium,18,19 the field of manganites is relatively unex-
plored. In this article, we present a systematic study of the
Raman and infrared ~IR! active phonon modes of various
crystallographic phases in the systems LaMnO31 d ,
BaMnO32 d , and La12x Bax MnO3. A comparison of the ex-
perimental data with a group theoretical analysis of the al-
lowed zero-wave-vector phonon modes for the respective
structures has been made to identify the presence of various
phases and to establish phase boundaries. The use of micro-
Raman technique has been made to detect small amounts of
secondary phase which falls below the detection limit of
x-ray diffraction. The Raman and IR measurements have
been augmented through room temperature x-ray powder dif-
fraction studies.
FIG. 1. X-ray powder diffraction patterns of LaMnO31 d samples prepared
under different annealing conditions; ~a! rhombohedral LaMnO31 d prepared
II. EXPERIMENTAL DETAILS in pure O2, ~b! orthorhombic LaMnO3 prepared under argon, ~c, d, and e!
LaMnO31 d prepared on annealing ortho-LaMnO3 in O2 at 600, 1000, and
Polycrystalline samples of La12x Bax MnO3 were synthe- 1100 °C, respectively.
sised following the standard ceramic processing routes. The
starting material, La2O3 ~99.9%!, BaCO3 ~99.9%!, and
Mn2O3 ~99.9%! from Aldrich chemicals USA taken in sto- conjuction with a video image of the sample topography,
ichiometric proportions were thoroughly mixed in a motor- allowed studies of the variations in the spectral content from
ized agate mortar. The powder was then calcined at 1000 °C, grain-to-grain. For infrared transmission measurements in
reground and calcined again three times following the same the spectral range of 400–2500 cm21, we have used a
steps. The calcined powder was then pelletized in the form of Fourier-Transform IR Nicolet spectrometer. The samples for
3 and 6 mm diameter discs. These discs were annealed in air IR transmission measurements were prepared by thoroughly
at 1200 °C and in some cases at 1350 °C for 5 h, in oxygen at mixing the finely ground samples with dry KBr. The mixture
1100 °C for 8 h and finally cooled to room temperature in was then palletized in the form of 0.5 mm thick discs.
flowing oxygen at a rate of 2 °C/min. In order to minimize d
in samples of LaMnO31 d , a separate set of samples was
III. RESULTS
synthesised by carrying out the calcination and annealing
steps described previously in flowing argon gas ~99.99%! We first present results of x-ray powder diffraction mea-
environment. These samples were then oxygenated at several surements on the end members LaMnO31 d and BaMnO32 d ,
temperatures. Scanning electron micrographs of the fractured and their alloys La12x Bax MnO3. Figure 1 shows the u –2u
surfaces of the pellets revealed a grain size in the range of scan for LaMnO31 d samples prepared in oxygen ~curve a!
1–2 mm. The crystallographic structure of the samples was and argon ~curve b! environments. All diffraction lines in
measured at room temperature through u –2u x-ray powder Fig. 1~b! can be indexed on the basis of an orthorhombic cell
diffraction with CuKa excitation. corresponding to GdFeO3 type structure ~space group Pbnm!.
Raman spectra were taken in a Spex 1877E Triplemate This observation is consistent with the earlier reports of
spectrometer by using the 514.5 and 488 nm lines from an preparation of orthorhombic LaMnO31 d . While we could
Ar1 laser. The detection system consisted of a liquid nitro- not make a quantitative measurement of oxygen concentra-
gen cooled charged coupled device array. Plasma lines from tion in our samples, the observation of orthorhombic struc-
the laser were removed by passing the beam through a small ture with lattice parameter a55.53 (Å), b55.74 (Å), and c
grating monochromator. The samples were placed in the mi- 57.70 (Å), suggest an upper bound of 0.04 for the d. The
crostage of the spectrometer where the incident light could x-ray pattern of the sample prepared in pure oxygen ~curve a!
be focused down to a spot of diameter ;2–3 mm. This, in can be indexed in terms of a rhombohedrally distorted per-
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 3126 J. Appl. Phys., Vol. 85, No. 6, 15 March 1999 C. Roy and R. C. Budhani

ovskite cell. A comparison of this result with the earlier

reports8–10 also suggests a value of 0.1–0.14 for the d.
We have used a controlled oxygen annealing technique
with the objective to vary the structures of LaMnO3 samples
between the two limiting phases listed above. An interesting
aspect of the annealing experiments is the possibility of mak-
ing a two-phase mixture of the orthorhombic and rhombohe-
dral phases. Towards this end, the samples originally synthe-
sized in argon atmosphere were heat treated in oxygen for 8
h at several temperatures. In Fig. 1 ~curves c, d, and e! we
show the x-ray diffraction patterns of the samples annealed
at 600, 1000, and 1100 °C, respectively. As evident from a
comparison of pattern b and c in Fig. 1, the oxidation of the
material at 600 °C leaves the orthorhombic structure intact.
But for the sample oxidized at 1100 °C, the orthorhombic
distortion from the ideal perovskite phase disappears and the
material tends to become cubic as evident from the diffrac-
tion pattern of Fig. 1~e!. The fact that the rhombohedral
angle a is close to 60° in this case becomes clear from a
comparison of the splitting between 200 and 222 reflections
in pattern e and a of Fig. 1. X-ray diffraction measurements
on samples oxidized at 600 and 1000 °C reveal that this
transformation from orthorhombic to cubic is gradual and
proceed via the rhombohedral phase. The existence of a two-
phase mixture is also established through the Raman mea-
surements, which are discussed in the subsequent sections.
The changes in the powder diffraction pattern of the
1200 °C sintered La12x Bax MnO3 samples as the concentra-
tion of Ba is increased are displayed in Fig. 2. For x,0.25, FIG. 2. X-ray powder diffraction ~u –2u! of the series La12x Bax MnO3 for
the powder diffraction pattern can be indexed as due to a different values of x. The phase separation at x50.4 is indicated by the
rhombohedral structure. At x50.25 however, the structure appearance of diffraction peaks ~marked by arrows! of the hexagonal
BaMnO3.
becomes cubic. The ideal cubic perovskite structure of
La12x Bax MnO3 exist in the composition range of 0.25<x
,0.4. The x-ray diffraction pattern of the sample with x
50.4 reveals the presence of a second phase in the back-
ground matrix of the cubic structure. The additional lines in of the Raman modes for this compound. Our factor group
the diffraction pattern are due to the presence of hexagonal analysis of the rhombohedral LaMnO31 d and
BaMnO320 ~space group P6 3 mc! in the sample which phase La12x Bax MnO3 results in five Raman active phonon modes
separates for x>0.4. The x-ray diffraction pattern of a of irreducible representations A 1g 14E g , whereas for the
La0.6Ba0.4MnO3 sample synthesized at 1350 °C also showed orthorhombic LaMnO3 it yields 24 Raman active phonons of
the presence of hexagonal BaMnO3 with nearly the same irreducible representations 7A g 15B 1g 17B 2g 15B 3g . The
concentration as in the sample sintered at 1200 °C. This ob- increase in the phonon modes from 5 to 24 on going from
servation suggests that the phase separation is an intrinsic rhombohedral to orthorhombic structure is due to the follow-
property of the La12x Bax MnO3 system.
ing three effects: ~i! Lowering of crystal symmetry which
The presence of various crystallographic phases in the
splits the doubly degenerate E g modes into nondegenerate
system La12x Bax MnO3 gives rise to characteristic variations
B 2g 1B 3g , ~ii! displacement of oxygen atoms into the lower
in the spectral content of the Raman scattered light as a func-
symmetry site of the La-plane which introduces six new Ra-
tion of x. However, before we discuss the Raman spectra, a
group theoretical analysis of the allowed zone-center vibra- man active vibrations, and ~iii! doubling of the unit cell
tions for various crystallographic structures seen in the which folds the zone-boundary modes of the rhombohedral
present case is in order. A factor group analysis of the zone- structure into zone-center modes of the orthorhombic struc-
center vibrational modes has been done using the correlation ture due to which nine new Raman active modes are created.
table method. Results of this analysis are presented in Table The cubic phase of La12x Bax MnO3 corresponds to space
I~a! & I~b! for orthorhombic and rhombohedral LaMnO31 d group Pm3m which has no Raman active modes. There are
~respectively!, and in Table I~c! for the hexagonal BaMnO3. however three IR active modes of Fiu symmetry. For the end
Preliminary results of this analysis have been reported member BaMnO3, which has a hexagonal 2L structure ~non-
elsewhere.21 The data presented here for the orthorhombic centrosymmetric space group P6 3 mc!, the allowed Raman,
phase of LaMnO3 are in agreement with a recent work of IR and acoustic phonon modes are 3A 1 14E 1 15E 2 , 3A 1
Iliev et al.,22 who have carried out a polarization dependence 14E 1 , and A 1 1E 1 , respectively.
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 J. Appl. Phys., Vol. 85, No. 6, 15 March 1999 C. Roy and R. C. Budhani 3127

TABLE I. ~a!. Factor group analysis and selection rules for the zone-center
vibrational modes of the orthorhombic LaMnO3 ~Pbmn!, z54.

Number of
equivalent positions Site Irreducible representations of
Atom ~Wyckoff notation! symmetry modes

La 4 ~c! Cs 2A g 1B 1g 12B 2g 1B 3g 1A u 1
2B 1u 1B 2u 12B 3u
Mn 4 ~b! Ci 3A u 13B 1u 13B 2u 13B 3u
O1 4 ~c! Cs 2A g 1B 1g 12B 2g 1B 3g 1A u 1
2B 1u 1B 2u 12B 3u
O2 8 ~d! C1 3A g 13B 1g 13B 2g 13B 3g 1
3A u 13B 1u 13B 2u 13B 3u

GRaman57A g 15B 1g 17B 2g 15B 3g Raman selection rules:

G IR59B 1u 17B 2u 19B 3u A g : a xx , a yy , and a zz
FIG. 3. Raman spectra of the rhombohedral LaMnO31 d ~curve a! and ortho-
G acoustic5B 1u 1B 2u 1B 3u B 1g : a xy
rhombic LaMnO3 ~curve b!.
G silent58A u B 2g : a xz
B 3g : a yz
cm21 and some weak spectral features at lower wave num-
TABLE I~b!. Factor group analysis and selection rules for the zone-center bers. This spectrum is identical to the one reported by Iliev
vibrational modes of the rhombohedral LaMnO31d (R3̄c), z52. et al.22 for polycrystalline samples of orthorhombic
LaMnO31 d . Based on their polarization dependent measure-
Number ments and lattice dynamics calculations, these authors at-
tribute the peak at 612 cm21 to B 2g modes which involve in
of equivalent
positions
~Wyckoff Site Irreducible representations phase stretched motion of O1 atoms in the xz plane. The
Atom notation! symmetry of modes broad peak centred at 490 cm21, on the other hand, is due to
phonon modes of A g and B 2g symmetry. Iliev et al.,22 have
La 2 ~b! C3i A 1u 1A 2u 12E u
Mn 2 ~a! D3 A 2g 1A 2u 1E g 1E u
also reported a stricking change in the Raman spectrum of
O 6 ~e! C2 A 1g 12A 2g 13E g 1A 1u 12A 2u 13E u the orthorhombic LaMnO3 with the increasing laser fluence.
The modification of spectra with the increasing incident en-
GRaman5A 1g 14E g Raman selection rules:
ergy has been attributed to oxidation of the sample and sub-
G IR53A 2u 15E u A 1g : a xx1 a yy , a zz sequent conversion to the rhombohedral phase. We have col-
G acoustic5A 2u 1E u E g : ~ a xx2 a yy , a xy! , ~ a xz , a yz! lected a series of spectra from the same spot of area ;7
G silent53A 2g 12A 1u ~mm!2 and the same exposure of time of 100 s at various
power densities. These data are shown in Fig. 4. In the ab-
TABLE I~c!. Factor group analysis and selection rules for the zone-center
vibrational modes of the hexagonal 2L BaMnO3 ( P6 3 mc), z52.

Number of
equivalent positions Site Irreducible representations of
Atom ~Wyckoff notation! symmetry modes

Ba 2 ~b! C3 v A 1 1B 1 1E 1 1E 2
Mn 2 ~a! C3 v A 1 1B 1 1E 1 1E 2
O 6 ~c! Cs 2A 1 12B 1 13E 1 13E 2 1A 2 1B 2

GRaman53A 1 14E 1 15E 2 Raman selection rules:

G IR53A 1 14E 1 A 1 : a xx1 a y y , a zz
G acoustic5A 1 1E 1 E 1 : ~ a xz , a yz!
G silent5A 2 14B 1 1B 2 E 2 : ~ a xx2 a yy , a xy!

In Fig. 3, we show the room-temperature unpolarized

Raman spectra of the orthorhombic and oxygen rich rhom-
bohedral phases of LaMnO31 d prepared in argon and oxygen
atmospheres respectively. The Raman spectrum of the rhom-
bohedral phase ~curve a! is characterized by two broad in-
tensity distributions centred at 492 and 620 cm21. The factor
group analysis for the allowed Raman modes of the rhombo- FIG. 4. Raman spectra of the orthorhombic phase prepared in argon envi-
ronment collected at different fluences of the laser beam from the same spot
hedral structure yields one A 1g and four E g symmetry vibra-
on the sample. Solid lines in the figure are Gaussian fits to the spectra used
tions. The Raman spectrum of the orthorhombic phase ~curve for extracting peak position and FWHM. Inset shows the power dependence
b! is characterized by two prominent lines at 612 and 490 of the peak intensity and FWHM of the Raman line at 612 cm21.
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 3128 J. Appl. Phys., Vol. 85, No. 6, 15 March 1999
FIG. 5. Raman spectra, a, b, and c of the samples prepared after annealing
ortho-LaMnO3 in O2 at 600, 1000, and 1100 °C, respectively.
sence of any laser induced structural changes, one would
expect the intensity of the peak at 612 cm21 to increase
linearly with the laser fluence. Inset of the Fig. 4 shows the
dependence of the peak height and full width at half maxi-
mum ~FWHM! on the intensity. A sublinear dependence of
the peak height and an increase in peakwidth on laser power
are manifestations of a change in the structure. The precise
magnitude of such changes however, would depend on many
extraneous factors such as porosity of samples, rate of heat
removal from the sample, and humidity in the environment.
In Fig. 5, we show the effect of oxidation on the Raman
spectra of orthorhombic LaMnO31 d . Spectrum a shows that
the prominent Raman peak at 612 cm21 observed in the
sample prepared in argon environment is reduced consider-
ably on annealing the sample at a temperature as low as
600 °C. Further annealing of the samples at 1000 and
1100 °C result in a Raman profile ~curves b and c! identical
to that of the rhombohedral phase ~Fig. 3!. These observa-
tions are consistent with x-ray diffraction measurements
shown in Fig. 1.
In Fig. 6, we show the room temperature Raman spectra
of La12x Bax MnO3 samples. It should be recalled that for x in
the range of 0; to ;0.2, x-ray diffraction measurements
show a rhombohedral phase albeit with a decreasing distor-
tion from the ideal cubic perovskite structure on increasing
the x. The Raman spectra of these samples are identical to
that of the rhombohedral LaMnO31 d but for a gradual shift
of the hump at 620 cm21 to lower wave numbers on increas-
ing the x. For x in the range of 0.25–0.35, the structure is
cubic ~space group Pm3m! for which there are no Raman
active modes. The Raman spectrum of the samples with x
50.25 and 0.3 show a very broad hump centred at 465 cm21.
Since in this range of composition the system
La12x Bax MnO3 is a metallic ferromagnet,3 the observed in-
tensity could arise from the free carrier contribution to Ra-
man scattering. While the x-ray data for the sample with x
50.35 show a single phase ~cubic! material, three faint peaks
centred at 415, 556, and 658 cm21 appear in the Raman
spectrum of this sample. The intensity of these peaks shows
a variation when the laser spot of size ;3 mm is focused at
different location on the sample. Further, the intensity grows
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C. Roy and R. C. Budhani
FIG. 6. Room temperature Raman spectra of La12x Bax MnO3 as a function
of x. The figure also shows the spectrum of hexagonal BaMnO3. The ap-
pearance of Raman lines at 415, 556, and 658 cm21 in the spectrum for
La0.65Ba0.35MnO3 indicate a phase separation.
in the case of the sample with x50.4 for which x-ray dif-
fraction results show the presence of a two phase mixture of
the cubic phase of La12x Bax MnO3 and the 2L hexagonal
phase of BaMnO3. In Fig. 6, we also show the room tem-
perature Raman spectrum of the hexagonal BaMnO3 for
comparison. The allowed Raman active modes of this struc-
ture ~space group P6 3 mc! are 3A 1 , 4E 1 , and 5E 2 . A com-
parison of our data with reported Raman measurements on
the ferroelectric phase of the compound YMnO323 ~space
group P6 3 mc, 6 formula units per unit cell! indicates that
the strongest line appearing at 659 and 415 cm21 in the spec-
trum may be due to the A 1 and E 1 symmetry vibrations
respectively. From this observation, it is clear that the Raman
line appearing over the background intensity of the cubic
phase in sample with x50.35 are due the BaMnO3 phase
which has precipitated out. The amount of this phase in
samples with x50.35 is below the detection limit of x-ray
diffraction.
The changes in the crystallographic and electronic struc-
ture of La12x Bax MnO3 with increasing barium concentration
are also reflected in the infrared transmission spectra of the
samples. In Fig. 7, we show the IR spectra of LaMnO3,
LaMnO31 d , and La12x Bax MnO3 for some specific values of
x in the spectral range of 2500–400 cm21. These spectra are
characterized by a set of discrete absorption bands in the
frequency range of 400–700 cm21 and a continuous absorp-
tion of increasing intensity as we go to higher energies.
While the low frequency absorption bands are due to lattice
vibrations of the perovskite structure, the continuous absorp-
tion whose onset ~edge! shifts to lower wave numbers with
the increasing barium concentration suggest a gap in the
electronic density of state of the material. The spectrum of
orthorhombic LaMnO3 ~curve a! has two prominent vibra-
tional bands centred at 405 and 603 cm21. These two spec-
tral features are characteristic of many ABO3 perovskite
oxides24 including doped manganites.25,26 In addition to
 J. Appl. Phys., Vol. 85, No. 6, 15 March 1999
FIG. 7. Infrared transmission spectra of La12x Bax MnO3 for some represen-
tation values of x; ~a! x50, d '0, ~b! x50, d .0, ~c! x50.1, ~d! x50.2, and
~e! x50.25. Inset shows the IR transmission spectra of hexagonal ~2L!
BaMnO3 and two mixed-phase samples with x50.5 and 0.9.
these, some weak features ~indicated by arrows! are also
present in the spectrum. These observations are in agreement
with reported IR measurements on LaMnO3. 24 From the fre-
quency mass relationship for a rigid oscillator, one would
expect these high frequency vibrations to be due to the inter-
nal modes of BO6 octahedra. Amongst all internal modes, the
streching motion of the B–O bond is expected to have the
highest frequency followed by the distortional vibration of
the O–B–O bond angle. Based on this argument, we at-
tribute the bands at 603 and 405 cm21 to B–O and O–B–O
vibrations, respectively. In the case of the rhombohedral
phase of LaMnO31 d , while the peak at ;603 cm21 remains,
the second feature of the orthorhombic LaMnO3 centered at
405 cm21 has a considerably reduced intensity. This peak is
absent in LaMnO3 doped with various amounts of barium. It
is also noticeable in the figure that the absorption edge due to
the electronic excitations gradually shifts to lower wave
numbers as more and more La atoms are replaced by Ba
atoms. This behavior, which is indicative of the disappear-
ance of the gap, is closely linked with the insulator-to-metal
transition in the system. The most interesting feature of the
IR spectra presented in Fig. 7 is the diminishing intensity of
the Mn–O stretch mode with the increasing concentration of
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C. Roy and R. C. Budhani 3129
barium in the structure. This behavior is also linked with the
onset of a metallic state in the system and will be discussed
at a later stage. In the inset of Fig. 7, we show the infrared
spectra of pure BaMnO3 and the samples with x50.5 and
0.9. The IR spectrum of hexagonal BaMnO3 is characterized
by strong phonon modes between 400–800 cm21 and a large
electronic absorption in the higher energy range. These char-
acteristics phonon modes are also present in the spectra of
samples with x50.5 and x50.9 indicating a two phase mix-
ture as already seen in x-ray and Raman data.
IV. DISCUSSION
The structure of LaMnO31 d and La12x Bax MnO3 for x
<0.35 goes to a state of higher symmetry as the Jahn–Teller
distortion is removed with the increasing Mn41 concentra-
tion. This is clearly evident from the decreasing number of
phonon modes seen in IR and Raman spectra and the change
of the crystal structure from orthorhombic to rhombohedral
and from rhombohedral to cubic as seen through x-ray dif-
fraction data. These changes are accomplished through a lo-
cal adjustment of bond angles and bond lengths without in-
volving large scale diffusion of cations in the material. Such
a large scale motion of atoms, however, occurs for x>0.35
where we see the formation of two distinct crystallographic
phases. The phase separation is triggered by the fact that the
long range cubic perovskite order is unable to accommodate
the larger divalent ion (Ba21) at a large number of La31
sites. The solubility of AMnO3 ~A5Ca, Sr, or Ba! and
LaMnO3 was perhaps studied for the first time by Jonker and
van Santen.2 These early results show that up to 50%
BaMnO3 can be accommodated in the cubic perovskite struc-
ture. Subsequent studies of this system are mostly limited to
the composition La2/3Ba1/3MnO3. 3
It has been amply demonstrated in the literature that the
structural state and physical properties of perovskite related
oxides are susceptable to changes in the oxygen nonstoichi-
ometry, the range of which has been extended in many cases
by adopting high pressure techniques and electrochemical
methods. The oxygen nonstoichiometry in lanthanum man-
ganite, however, can be realized by synthesizing the material
in oxygen rich or oxygen deficient environments at ambient
pressure following the standard solid-state route. While the
oxygen nonstoichiometry, in general written as d where d is
a positive fraction, it actually represents cation vacancies in
the structure rather than an excess of oxygen.8,10 For our
sample of LaMnO31 d prepared in pure argon environment,
the oxygen nonstoichiometry is effectively zero. This is evi-
dent from the observed orthorhombic structure whose lattice
parameters are identical to that of the phase reported by Tof-
ler and Goodenough8 and also by Hauback et al.9 Our mag-
netization measurements on this samples also reveal a T N of
;140 K and a weak parasitic ferromagnetism below the an-
tiferromagnetic ordering temperature. With this information,
we can say that the Raman spectrum of Fig. 3~b! is truely of
the orthorhombic phase of LaMnO3.
While the Raman active phonon, magnon, and electronic
modes of LaMnO3 have not been studied in detail, a consid-
erable amount of information is available on orthoferrites
 3130 J. Appl. Phys., Vol. 85, No. 6, 15 March 1999
and chromites of many rare earth elements. It is generally
seen that the Raman frequencies of these compounds in the
lower wave number region ~,450 cm21! depend on the type
of the rare earth element, whereas for n .450 cm21, the in-
ternal vibrations of the oxygen octahedra incasing the tran-
sition metal ion dominate the spectrum. The most intense
internal vibration at 612 cm21 in the present case is due to
inphase streching motion of oxygen atoms in the ab plane.
The second intense peak at 490 cm21 is of A g symmetry
involving out of phase bending motion of oxygen atoms in
the octahedra. Since these modes are forbidden for the rhom-
bohedral and cubic phases structure, their position and inten-
sity must reflect the extent of orthorhombic distortion of the
structure.
The continuous absorption with an onset at ;500–600
cm21 and of increasing intensity as we go to higher wave
numbers seen in the transmission spectrum of orthorhombic
LaMnO3, perhaps involves interband electronic transitions.
Electronic structure calculations27 for LaMnO3 suggest that
the lowest energy band-to-band excitation in this system
would involve transitions between the Jahn–Teller split e 1g ↑
and e 2g ↑ bands. The e 1g ↑ band overlaps with O 2p band due
to strong hybridization, while e 2g ↑ band forms the lowest
lying empty conduction band. Optical reflectivity measure-
ments of Jung et al.28 indicate that the centre of gravity ~CG!
of the e 1g ↑ and e 2g ↑ bands are separated by ;1.9 eV. The
extrapolated value of the absorption edge in the present case
is ;0.06–0.07 eV. The lower energy of the edge as com-
pared to the band-to-band separation of 1.9 eV is understand-
able in view of the fact that absorption edge is a measure of
the separation between band edges rather than the band CGs.
In the present case, the separation is also susceptible to small
variations in oxygen concentration in the sample. It is also
important to point out that the observation of a gap is con-
sistent with the reported semiconducting behavior of
LaMnO3. The shift of the absorption edge to lower wave
numbers as the oxygen concentration is increased or as lan-
thanum is replaced by barium suggest a lowering of the en-
ergy gap and an eventual insulator-to-metal transition in the
system. While a correct determination of the edge becomes
difficult due to overlap of electronic and phonon parts, the
trend is quite clear in the figure. This type of behavior of the
absorption edge is observed in many doped perovskite sys-
tems such as La12x Bax CuO4, 29 and LaNi12x Crx O3. 30 For
La12x Bax MnO3, while a systematic study of the insulator-to-
metal transition as a function of x is lacking, from a com-
parison with Sr and Ca doped systems13 this transition
should occur in the vicinity of x>0.18. Another remarkable
effect of the increased hole concentration in the system is on
the behavior of the phonon modes. While some of the modes
become forbidden because of the raising of the crystal sym-
metry, the modes which remain show a considerably lower
intensity on increasing the x. A strickingly similar behavior
of the phonon modes has also been seen in hole doped
La2CuO429,31 and in some doped nickolates30 and the low T c
oxide superconductor BaPb12x Bix O3. 32
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C. Roy and R. C. Budhani
V. SUMMARY
We have reported x-ray diffraction, Raman scattering,
and IR transmission measurements on various crystallo-
graphic phases of the system La12x Bax MnO3 for 0<x<1.
For the undoped compound LaMnO31 d , our Raman and IR
results confirm the reported susceptibility of the structure of
this compound to variations in d. An increase in d can be
realized either by heating the orthorhombic phase ( d '0) at
temperatures as low as 600 °C or via laser annealing. The
higher symmetry of the crystallographic structure achieved
through oxidation is indicated by a decrease in the number of
IR and Raman active phonons. The effect of Ba substitution
is similar to that of an increase in d. The behavior of IR
absorption edge and phonon modes is indicative of an
insulator-to-metal transition in this system. Our micro-
Raman measurements fix the maximum solubility of Ba in
cubic perovskite structure at x<0.35. For higher values of x,
a two-phase mixture of hexagonal BaMnO3 and cubic
La0.65Ba0.35MnO3 is formed.
ACKNOWLEDGMENTS
This research has been supported in part by the council
of Scientific and Industrial Research, Government of India
through project No. 80 ~0007!/94/EMR-II. We thank Prof. H.
D. Bist and Dr. A. Pradhan for their interest and support
during the course of these studies. The authors also thank M.
S. Navati for infrared transmission measurements.
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