Magnetic structure and magnetic properties

of Nd1−xNaxMnO3 compounds
Cite as: J. Appl. Phys. 110, 093906 (2011); https://doi.org/10.1063/1.3656714
Submitted: 22 May 2011 • Accepted: 22 September 2011 • Published Online: 03 November 2011

B. Samantaray, S. Ravi, A. Das, et al.

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 JOURNAL OF APPLIED PHYSICS 110, 093906 (2011)

Magnetic structure and magnetic properties of Nd12xNaxMnO3 compounds

B. Samantaray,1 S. Ravi,1,a) A. Das,2 and S. K. Srivastava3
1
Department of Physics, Indian Institute of Technology Guwahati, Guwahati 781039, India
2
Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
3
Institute Néel, CNRS and Université Joseph Fourier, BP 166, F-38042 Grenoble Cedex 9, France
(Received 22 May 2011; accepted 22 September 2011; published online 3 November 2011)
The crystal structure, magnetic structure, and magnetic properties of Nd1-xNaxMnO3 (x ¼ 0, 0.15, and
0.20) compounds were studied using magnetization and neutron powder diffraction techniques. The
magnetic ordering is found to undergo a transition from A-type antiferromagnetic (AFM) structure
for x ¼ 0 to pseudo charge-exchange (CE)-type AFM phase for x ¼ 0.20 through the spin canted
ferromagnetic (FM) phase for x ¼ 0.15. Two magnetic transitions at 75 K and 15 K were observed for
x ¼ 0 sample and are ascribed to AFM ordering of Mn ions and ferrimagnetic ordering of Nd ions,
respectively. In the case of x ¼ 0.15, a canted FM ordering at around 80 K and a pseudo CE-type AFM
magnetic structure at 5 K were observed. The x ¼ 0.20 sample exhibits a charge-ordering transition at
180 K followed by a spin-glass like transition at around 40 K. The magnetic structure of x ¼ 0.20
sample below 125 K is found to be pseudo CE-type AFM structure. The propagation vectors associated
with Mn3þ and Mn4þ sublattices are (0 0 1=2) and (1=2 0 1=2), respectively. The maximum refined
magnetic moments of Mn3þ and Mn4þ ions in x ¼ 0.20 sample are found to be 3.20 lB and 3.00 lB,
C 2011 American Institute of Physics. [doi:10.1063/1.3656714]
respectively. V

I. INTRODUCTION magnetoresistance, coexistence of ferromagnetic metallic

(FMM) and AFM charge/orbital ordered (COO) insulating
NdMnO3 based colossal magneto-resistance materials
phases, electronic phase separation, etc.13 These complex
fall in the category of a medium size eg electron bandwidth,
properties are very sensitive to average size of the A-site cat-
where one can tune the bandwidth, by appropriate Nd site
ion hrAi, external applied field, pressure, chemical substitu-
substitution. So, it is relatively easy to tune the system from
tions at the Mn site, and the geometrical and chemical
double exchange (DE) ferromagnetic (FM) phase to the
environment at the surface of the system.10,14 The charge
charge ordered phase. Unlike LaMnO3 series, these com-
ordering (CO) in doped perovskite is characterized by an
pounds exhibit complex behavior due to the presence of two
ordering of Mn3þ and Mn4þ ions within the MnO2 plane,
magnetic sublattices namely Mn and Nd. The perovskite
which causes the localization of eg electrons and hence the
structure of NdMnO3 with Pnma space group is ortho-
AFM spin ordering. According to the Goodenough model,15
rhombically distorted due to the tilting of MnO6 octahedra.1
this charge ordering is followed by orbital ordering, where
In this distorted MnO6 octahedra, the degeneracy of eg orbi-
the dz2 orbitals of Mn3þ ions order ferromagnetically in
tals of Mn ions is destroyed due to the cooperative Jahn-
zigzag chains within a-c plane. The CO is usually observed
Teller distortion. A-type antiferromagnetic (AFM) structure
in half-doped manganites like La0.5Ca0.5MnO3,16
has been observed in the parent NdMnO3 compound.2–4 In
Nd0.5Ca0.5MnO3,17 and Nd0.5Sr0.5MnO318 and in narrow
NdMnO3, the Mn sub-lattice atoms undergo AFM ordering
band-width systems like Pr0.75Na0.25MnO319 and
with Neel temperature TN  78 K and the Nd sub-lattice 20,21
Nd0.8Na0.2MnO3. La0.5Ca0.5MnO3 with an average ionic
atoms undergo magnetic ordering at T  13 K.2 The negative
radius hrAi of 1.198 Å undergoes successive transitions in to
magnetization observed in NdMnO3þd was explained in
FMM (TC  230 K), AFM insulative (TN  170 K), and
terms of magnetic phase separation by Bartolome et al.5,6
charge and orbital ordered states (TN) with decrease in tem-
using neutron powder diffraction (NPD) and x-ray magnetic
perature. Transformation from CE-type to A-type AFM
circular dichroism techniques and Troyanchuk et al.7 have
structure, with increase in Sr concentration was reported by
proposed a two phase model to explain such magnetization
Dhiman et al.22 in La0.5Ca0.5xSrxMnO3 compound. In Ca
behavior. The decrease in ionic radius of R ion in RMnO3
doped Nd-Mn-O series, FM transition with TC around 110 K
compounds is found to lower the TN values from 150 K for
along with the signature of CO and AFM has been observed
R ¼ La to 40 K for R ¼ Eu.8 Similar systematic decrease in
without any metal-insulator transition.23,24 The magnetic
TN value has been reported by increasing the Y concentration
properties of Nd1xCaxMnO3 compounds were explained in
in Nd1xYxMnO3.9
terms of two phase model by considering the exchange cou-
In Nd-Mn-O series, several authors have studied the
pling between AFM and FM phases.7 In Nd0.5Ca0.5MnO3,
magnetic properties by doping the divalent alkaline-earth
CE-type AFM structure was reported from neutron powder
elements, such as Ca, Ba, and Sr in place of Nd.10–12 The
diffraction studies.17 In Nd0.7Sr0.3MnO3 series, FM and
doped manganites exhibit rich phenomena such as colossal
metal-insulator (M-I) transitions have been observed with TC
in the range of 230 K to 250 K due to its relatively large
a)
Electronic mail: sravi@iitg.ernet.in. A site ionic size (hrAi ¼ 1.212).25–27 On the other hand,

0021-8979/2011/110(9)/093906/9/$30.00 110, 093906-1 C 2011 American Institute of Physics

V
093906-2 Samantaray et al. J. Appl. Phys. 110, 093906 (2011)

Nd0.5Sr0.5MnO3 is reported to exhibit, CO at around 150 K

as per the detailed neutron diffraction, magnetization and
electrical resistivity studies.12,18,28–30
The monovalent doping in place of Nd has some advant-
age over its divalent counterpart, because each doped mono-
valent atom oxidizes two Mn ions from Mn3þ to Mn4þ state.
Recently, we have reported that Nd0.8Na0.2MnO3 compound
exhibits a CO transition at 180 K, followed by FM transition
at around 50 K and reentrant spin-glass (RSG) like transition
below 40 K as per the magnetization measurements.21 Jirák
et al.31 have reported that Pr1-xNaxMnO3 compounds exhibit
decrease in Jahn-Teller distortion and undergo transition
from A-type AFM structure (for x ¼ 0) to pseudo CE-type
structure (for x ¼ 0.20), through a spin canted arrangement
(x  0.05) and double exchange FM (x ¼ 0.10 and 0.15) with
increase in Na concentration. Even though, the magnetic
properties of Na doped Nd-Mn-O series were studied, their
magnetic structure has not been reported. In this paper, we
report the analysis of neutron powder diffraction patterns
recorded on Nd1xNaxMnO3 (x ¼ 0, 0.15, and 0.20) at differ-
ent temperatures down to 5 K.

II. EXPERIMENTAL DETAILS

Nd1xNaxMnO3 (x ¼ 0, 0.15, and 0.20) compounds
were prepared by solid state reaction method as reported in
(Ref. 21). X-Ray diffraction patterns (XRDs) were recorded
by using Bruker D8 Advance XRD machine with CuKa radi-
ation to check the single phase nature of the compounds. The
oxidation state of Mn was determined by a chemical titration
method, in which the samples were dissolved in dilute sulfu-
ric and phosphoric acids with an addition of excess amount
of Fe(NH)2(SO4)2 and were titrated against self indicating
KMnO4 solution.
NPD patterns were recorded at selected temperatures
between 5 K and 300 K by using multi-position sensitive de-
tector based powder diffractometer (k ¼ 1.249 Å) at Dhruva
reactor, BARC, Mumbai. The patterns were refined by the
Rietveld refinement technique using FullProf program.32 The
magnetization measurements were carried out by using
quantum design SQUID magnetometer.
III. RESULTS AND DISCUSSION
A. Magnetic properties
Fig. 1 shows the temperature variation of zero field
cooled magnetization for x ¼ 0, 0.15, and 0.20 samples at
200 Oe. The parent compound, x ¼ 0 exhibits a peak at
around 75 K and it can be attributed to the AFM ordering of
Mn ions. At 15 K, a second transition indicated by a sharp
fall in magnetization is observed. Such a behavior can be
interpreted in terms of ferrimagnetic coupling between two
magnetic sublattices, namely Mn and Nd ions. The x ¼ 0.15
sample exhibits PM to FM transition with TC  104 K fol-
lowed by low temperature spin glass like transition at 40 K.
Unlike x ¼ 0.15 sample, the x ¼ 0.20 sample exhibits a CO
transition at 180 K. The increase in magnetization below
125 K followed by a sharp peak at around 40 K can be
FIG. 1. (Color online) Temperature variation of magnetization under zero
field cooled (ZFC) condition for x ¼ 0, 0.15, and 0.20 samples for an applied
field of 200 Oe.
ascribed to the presence of weak FM and RSG behavior,
respectively.
To further study the magnetic properties, we have car-
ried out field variation of magnetization measurements at
5 K for a maximum field of 610 T. All the measurements
were performed after cooling the sample from 300 K in the
absence of magnetic field. The M-H loops recorded at 5 K
for x ¼ 0, 0.15, and 0.20 samples are shown in Fig. 2. First,
quadrant of M-H loops are shown for better clarity. The par-
ent compound exhibits a high coercive field of 1 T. No satu-
ration of magnetization was observed even for the field of
10 T as shown in Fig. 2(a) and it indicates the AFM nature of
ordering as corroborated by neutron diffraction results dis-
cussed later. However, the observed remnant magnetization
of 1.5 lB/f.u suggests the coexistence of FM and AFM order-
ing. It is difficult to estimate the FM contribution of “Nd”
moment at 5 K quantitatively from this measurement alone.
The saturation magnetization (MS) was determined by fitting
the initial magnetization data to M(H) ¼ MS [1  a/H 
b/H2] þ vdH; where vd is the high field differential suscepti-
bility and a and b are constants. The estimated MS value is
found to be 2.62 6 0.05 lB/f.u. The initial magnetization
curve of x ¼ 0.15 sample is found to be outside the magnet-
ization loop and no saturation of magnetization is observed
as shown in Fig. 2(b). The MS value determined from the
above technique is found to be 2.18 lB/f.u. and is
093906-3 Samantaray et al. J. Appl. Phys. 110, 093906 (2011)

Here, the field induced FM transition is an irreversible pro-

cess, with a distinct initial curve seen outside the loop. This
spin flip behavior is usually observed in metamagnetic tran-
sitions.17,33 The rather large MS value of 4.3 lB/f.u. observed
at 5 K for x ¼ 0.20 sample can be attributed to the contribu-
tion from spin canted Nd ions.

B. Crystal structure
All the samples in Nd1xNaxMnO3 (x ¼ 0, 0.15, and
0.20) series are found to crystallize with an orthorhombic
structure in Pnma space group. The Rietveld refinement of
the NPD pattern recorded at 300 K was carried out by vary-
ing cell parameters, position of the Nd/Na and O atoms, oc-
cupancy, and thermal parameters. Fig. 3(a) shows the NPD
pattern of the parent compound (x ¼ 0) at 300 K along with
the Rietveld refinement. All the Bragg reflections could be
indexed and compared with the distorted orthorhombic per-
ovskite GdFeO3 compound. The refined structural parame-
ters at 300 K determined from this analysis are summarized
in Table I. The typical values of lattice parameters are
found to be a ¼ 5.7200(13) Å, b ¼ 7.5729(22) Å, and
c ¼ 5.4075(12) Å for x ¼ 0 sample. They are in good agree-
ment with those reported by Muñoz et al.2 Decrease in unit
cell volume with increase in doping concentration is
observed and it can be understood in terms of generation of
Mn4þ ions at the expense of Mn3þ ions. The ionic size mis-
match is quantitatively
P determined in terms of variance, r2
2 2 2
expressed as r ¼ xi ri  h rAi , where xi is the fractional
occupancy of the A site ion, ri is the corresponding ionic ra-
dius, and hrAi is the average size of A-site cation. The r2 val-
ues of x ¼ 0.15 and 0.20 samples are found to be comparable
to that of the charge ordered La0.5Ca0.4Sr0.1MnO3 com-
pound.22 This larger value of size disorder could plausibly
be responsible for the coexistence of FM and AFM phases.34
The Mn-O bond lengths in MnO6 octahedra presents one
long Mn-O bond length (>2.0 Å) and two shorter (<2.0 Å)
bond lengths, which are the characteristics of Jahn-Teller
distortion. dJT is a measure of Jahn-Teller distortion and is
quantitatively determined by using the relation,35

FIG. 2. (Color online) Magnetization versus magnetic field for (a) x ¼ 0, (b)
x ¼ 0.15, and (c) 0.20 samples at 5 K. The insets show initial magnetization
curve along with fitted data.

considerably smaller than the theoretical value of 3.7 lB. At

5 K, which is lower than the transition temperatures corre-
sponding to CO, FM, AFM, and RSG states in x ¼ 0.20 sam-
ple, the recorded M-H loop exhibits distinct behavior as
shown in Fig. 2(c). The initial magnetization is found to
increase slowly and linearly, up to a threshold field of 4.5 T;
beyond which, a first order transition into the FM state with
a sharp jump in M value from 1 lB/f.u to 4.1 lB/f.u is
observed. It is attributed to the field induced quenching of FIG. 3. (Color online) Neutron powder diffraction patterns of x ¼ 0 along
CO and spin glass behavior and, stabilization of FM phase. with Rietveld refinements at (a) 300 K and (b) 5 K.
093906-4 Samantaray et al. J. Appl. Phys. 110, 093906 (2011)

TABLE I. Structural parameters obtained from the Rietveld refinement of the NPD patterns for Nd1xNaxMnO3 (x ¼ 0, 0.15, and 0.20) compounds at 300 K.

Refined parameters x¼0 x ¼ 0.15 x ¼ 0.20

2
v 2.12 2.35 2.86
Rp 4.24 3.90 4.79
Rwp 5.25 5.41 6.48
RBragg 17.24 10.8 16.1
Rf 15.25 8.03 10.6
a (Å) 5.7200(13) 5.4537(9) 5.4297(14)
b (Å) 7.5729(22) 7.6805(14) 7.6674(19)
c (Å) 5.4075(12) 5.4315(9) 5.4225(19)
Volume (Å3) 234.24(10) 227.51(07) 225.76(10)
Mn-O1(Å) 1.9454 1.9526 1.9398
Mn-O21(Å) 2.1505 2.0030 1.9795
Mn-O22 (Å) 1.9230 1.9459 1.9565
Nd-O1(Å) 2.4405 2.5060 2.4889
Nd-O21(Å) 2.5778 2.6762 2.6427
Nd-O22 (Å) 2.3761 2.3790 2.3427
Mn-O1-Mn (deg) 153.3 159 162.2
Mn-O2-Mn (deg) 151.1 154.1 154.2
hrAi (Å) 1.163 1.175 1.18
r2  103 (Å)2 0 0.921 1.156
d JT (Å) 0.1023 0.0405 0.0167
(Nd, Na) (x, y, z) {0.0632(15), 1=4, 0.9818(17)} {0.0305(7), 1=4, 1.0060(15)} {0.0261(9), 1=4} 0.9976(23)}
(Mn) (x, y, z) {0, 0, 1=2} {0, 0, 1=2} {0, 0, 1=2}
O1 (x, y, z) {0.4863(15), 1=4, 0.0815(13)} {0.4864(11), 1=4, 0.0638(15)} {0.4906(16), 1=4, 0.0544 (17}
O2 (x, y, z) {0.3128(15) 0.04174(13) 0.7127(17)} {0.2942(7), 0.0407(7), 0.7130(8)} {0.2901(12), 0.0419(9), 0.7128(14)}
Occupancy {Nd0.92MnO2.93} {Nd0.85Na0.15MnO3.02} {Nd0.82Na0.20MnO3.06}
Mn Valency 3.06 3.33 3.46

" #
p 1 X 2
dJT ¼ ðMn  OÞi  < Mn  O >
3 i
The parent compound shows strong Jahn-Teller distortion of
the octahedra. The distortion decreases with increase in Na
concentration. The Mn-O-Mn bond angle increases with
increase in Na concentration and leads to enhancement of
magnetic transition temperature. The stoichiometry ratio of
the compounds as per the refinement of occupancy values
for x ¼ 0, 0.15, and 0.20 samples are tabulated in Table I.
The x ¼ 0 sample exhibits vacancy at oxygen and Nd sites.
The average Mn valency values obtained from the chemical
titration are listed in Table I. We have also estimated the
valency of Mn ions from the occupancy values determined
from NPD analysis and are found to be comparable to those
obtained from chemical titration results. The systematic
increase in Mn valence with Na substitution indicates the
formation of Mn3þ/Mn4þ mixture with increase in Mn4þ
concentration.
NPD patterns were recorded at various temperatures
down to 5 K for all compounds. The refined parameters
determined from NPD analysis at 5 K are given in Table II.
The temperature variations of lattice parameters for x ¼ 0
sample are shown in Fig. 4(a). The lattice parameters are
found to decrease with decrease in temperature and at around
50 K, a clear change in slope is observed; where a steeper
decrease in a and b parameters are seen. Similar trend was
observed in the temperature variation of unit cell volume.
The x ¼ 0.15 sample exhibits the regular thermal expansion
of cell parameters. The lattice parameters for x ¼ 0.20 sam-
ple exhibit an anomalous behavior at around 180 K as shown
in Fig. 4(b). A distinct increase in a & c parameters and
decrease in b parameters are seen below 180 K. This behav-
ior is usually observed in systems having CE-type AFM
ordering or pseudo CE-type AFM ordering, which is associ-
ated with the dz2 orbital ordering in the a-c plane. This indi-
cates the presence of orbital ordering in this compound
below T  200 K. The average Mn-O bond length values are
found to be almost temperature independent as shown in
Fig. 4(c). The Mn-O1-Mn bond angle is found to decrease
considerably below TCO; while the Mn-O2-Mn bond angle
increases in the same temperature region as shown in
Fig. 4(d).
C. Magnetic structure
1. x 5 0 (A-type AFM phase)
The low temperature NPD patterns could be refined by
including suitable magnetic phases together with the nuclear
phase for different compounds. As the temperature is
decreased below 75 K, the parent compound shows an
increase in intensity of fundamental {(101) (020)}, (111),
(121), and (201) reflections. The temperature variations of
integrated intensity of some of these reflections have mag-
netic contribution as shown in Fig. 5. In addition to these
fundamental reflections, one prominent super-lattice reflec-
tion (010) is also observed. These observations are similar to
those reported by Muñoz et al.2 in NdMnO3 sample. The
093906-5 Samantaray et al. J. Appl. Phys. 110, 093906 (2011)

TABLE II. Structural and magnetic parameters obtained from the Rietveld refinement of the NPD patterns for Nd1xNaxMnO3 (x ¼ 0, 0.15, and 0.20) com-
pounds at 5 K.

Refined parameters x¼0 x ¼ 0.15 x ¼ 0.20

v2 1.45 3.3 2.91

Rp 2.85 4.33 4.75
Rwp 3.62 5.78 6.57
RBragg 10.9 10.7 9.31
Rf 7.85 7.03 6.88
a (Å) 5.7068(6) 5.4498(8) 5.4259(10)
b (Å) 7.5472(10) 7.6608(14) 7.6547(11)
c (Å) 5.4004(6) 5.4166(9) 5.4259(9)
Volume (Å3) 232.60(5) 226.15(6) 225.35(06)
Mn-O1(Å) 1.9420 1.9459 1.9470
Mn-O21(Å) 2.1850 2.0119 1.9602
Mn-O22 (Å) 1.9075 1.9354 1.9578
Nd-O1(Å) 2.4101 2.4344 2.4893
Nd-O21(Å) 2.6113 2.6674 2.6704
Nd-O22 (Å) 2.3510 2.3551 2.3712
Mn-O1-Mn (deg) 152.6 159.6 158.7
Mn-O2-Mn (deg) 150.1 153.4 156.6
Mn (lB/f.u) AFM Mx(2.59(03)), My(1.57(1)) 1.03(8) 3.10(3)
Mn (lB/f.u) FM — Mx(1.78(5)), My(1.95 (5)) —
Nd (lB/f.u) FM 1.39(1) — —
(Nd, Na) (x, y, z) {0.0603(8), 1=4, 0.9864(10)} {0.0329(6), 1=4, 1.0009(16)} {0.0254(7), 1=4} 0.9943(21)}
(Mn) (x, y, z) {0, 0, 1=2} {0, 0, 1=2} {0, 0, 1=2}
O1 (x, y, z) {0.4790(11), 1=4, 0.0821(10)} {0.4849(10), 1=4, 0.0617(12)} {0.4971(6), 1=4, 0.0660(12}
O2 (x, y, z) {0.3140(7), 0.0453(6), 0.7134(8)} {0.2977(7), 0.0405(6), 0.7119(8)} {0.2852(9), 0.0380(8), 0.7150(11)}

size of the chemical and the magnetic unit cells are found to
be same. The magnetic cell was refined by using P-1 space
group. We have refined the NPD pattern at 5 K, using a
model very similar to that reported by Muñoz et al.2 The
NPD pattern along with Rietveld refinement at 5 K is shown
in Fig. 3. The moments of both Mn and Nd sites were
refined. Different choices of magnetic moment orientations
were used in the refinement to get the best fit. We have found
that the moments of Mn ions are slightly canted away from
the a-c plane. Therefore, two components of the moment
were taken for the refinement, i.e., x-component along a-axis
and y-component along b-axis. The x-component moments
are coupled ferromagnetically within the plane and antiferro-
magnetically between the planes along the b-axis. The y-
component moments are coupled ferromagnetically both
within the plane and between the planes. The Nd moment is
found to be coupled ferrimagnetically to the y-component of
the Mn moment. Our results are in small disagreement with
the analysis of Muñoz et al.2 They found that the coupling
between Mn and Nd spins was ferromagnetic; whereas, our
analysis shows that it is ferrimagnetic. The magnitudes of
Mn and Nd moments at 5 K are 3 lB and 1.3 lB, respectively.
The refined magnetic moment components at 5 K are tabu-
lated in Table II. The magnetic structure is shown in Fig. 6.
The magnetic moment values are comparable to those
observed by Muñoz et al.2 The magnitude of Mn moment is
found to be lower than that of expected moment for Mn3þ
ions. This could be either due to the incomplete ordering of
Mn atoms at 5 K or due the presence of considerable concen-
tration of Mn4þ ions due to the oxygen off-stoichiometry.
The above magnetic moment value is comparable to that of
saturation magnetization obtained from M vs. H loop
measurement.
2. x 5 0.15 (Spin canted FM phase)
Fig. 7 shows the NPD patterns along with Rietveld
refinement for x ¼ 0.15 at three different temperatures.
Unlike x ¼ 0 sample, no superlattice reflection corresponding
to A-type AFM behavior is observed. The increase in inten-
sity of (101) and (121) peaks with decrease in temperature
below 80 K indicates the FM nature of the sample. The low
temperature patterns below 80 K could be refined by taking
into account the FM phase, in addition to the nuclear phase.
The patterns at low temperature were refined by varying the
magnetic moments of Mn ions only. Different choices of
magnetic moment orientation were used in the refinement to
get the best fit. The best possible refinement was obtained by
varying the moments Mx and My simultaneously. At 5 K,
three super lattice reflections are observed at 2h ¼ 6.58 ,
9.28 , and 14.68 with weak intensity and could be indexed
as (0 0 1=2), (1=2 0 1=2), and (1 0 1=2), respectively. The NPD
pattern at 5 K was modeled in terms of coexistence of FM
and AFM phases. The AFM structure is found to be pseudo
CE-type and is analyzed in the P21/m space group. The
pseudo CE-type structure signifies that the x ¼ 0.15 sample
enters into the charge ordered phase. We have discussed
more about CO phase and pseudo CE-type structure in x ¼ 0.20
sample. Temperature variations of refined x-component of
magnetic moment (Mx), y-component of moment (My), and
the net magnetic moment (M) corresponding to the FM phase
are shown in Fig. 8. The refined components of magnetic
093906-6 Samantaray et al. J. Appl. Phys. 110, 093906 (2011)

FIG. 4. (Color online) Temperature variations of (a) lattice parameters for x ¼ 0 sample, (b) lattice parameters for x ¼ 0.20 sample, (c) Mn-O bond lengths for
x ¼ 0.20 sample, and (d) Mn-O-Mn bond angles for x ¼ 0.20 sample.

FIG. 6. (Color online) Magnetic structure of x ¼ 0 sample. Magnetic

FIG. 5. (Color online) Temperature variations of refined magnetic moment moments of Nd and Mn spins are shown as arrows in blue (small arrow) and
and integrated intensity of different reflections for x ¼ 0 sample. purple colors (bigger arrow) respectively.
093906-7 Samantaray et al.
FIG. 7. (Color online) Neutron powder diffraction patterns of x ¼ 0.15 sam-
ple along with Rietveld refinements at (a) 300 K, (b) 25 K, and (c) 5 K.
moment per Mn ion corresponding to the FM structure at 5 K
are found to be Mx ¼ 1.78(05) lB and My ¼ 1.95(05) lB.
The magnetic moments corresponding to Mn3þ and Mn4þ
ions in pseudo CE-type AFM structure are found to be
1.11(07) lB and 0.94(09) lB, respectively.
3. x 5 0.20 (Charge ordered phase)
Fig. 9 shows the evolution of low angle portion of the
NPD patterns for x ¼ 0.20 sample in the temperature range
5–300 K. The NPD data in the temperature range 200–300 K
could be refined by using only the nuclear structure in Pnma
space group. Below T ¼ 125 K, the integrated intensity of
some of the forbidden Bragg reflections (0 0 1=2), (1=2 0 1=2),
and (1 0 1=2) at 2h ¼ 6.57 , 9.30 , and 14.73 , respectively,
increases with decrease in temperature. With further
decrease in temperature below 50 K, additional super lattice
reflections (0 0 3/2), (1/2 2 1/2), (1/2 0 3/2), (0 2 3/2),
and (1/2 2 3/2) at 2h ¼ 19.8 , 20.93 , 23.85 , 27.37 , and
28.18 , respectively, are observed. The above super lattice
reflections show that k is even integer, which is associated
with pseudo CE-type AFM ordering.36 The common feature
FIG. 8. (Color online) Temperature variations of refined magnetic moments
of x ¼ 0.15 sample.
J. Appl. Phys. 110, 093906 (2011)
FIG. 9. (Color online) Evolution of low angle reflections of neutron diffrac-
tion patterns in the temperature range 5–300 K for x ¼ 0.20 sample and the
inset shows the temperature dependence of refined magnetic moments corre-
sponding to Mn3þ and Mn4þ ions in pseudo CE-type structure.
between pseudo CE-type and CE-type ordering is AFM
arrangement with in the plane. However, the inter planar
arrangement along b-axis is FM in pseudo CE-type magnetic
structure and AFM in CE-type magnetic structure. In the
present case, the absence of k ¼ odd reflections rules out
AFM coupling between adjacent a-c planes. So, these super-
lattice reflections are indexed on a 2 a  b  2 c cell, having
a pseudo CE-type structure. We have not observed any
increase in intensity of fundamental reflections such as (1 0 1),
(1 2 1), and (1 0 2) and it indicates the absence of coexis-
tence of AFM and FM ordering. The low temperature NPD
data could be refined by introducing pseudo CE-type AFM
structure in the P21/m space group and is shown in Fig. 10
for 5 K. In this structure, two different Mn sublattices, i.e.,
Mn3þ and Mn4þ occupy two distinct sites. The propagation
vectors associated with Mn3þ and Mn4þ ions are (0 0 1=2) and
(1=2 0 1=2), respectively. The arrangement of Mn ions in this
superstructure is the direct evidence of the CO state. The tem-
perature variations of moments of two Mn sites in pseudo CE-
type structure are shown in the inset of Fig. 9. The maximum
refined moments for Mn3þ and Mn4þ sublattices are found to
be 3.20(05) lB and 3.00(02) lB, respectively. The net refined
magnetic moment value at 5 K is tabulated in Table II.
IV. DISCUSSION
A systematic change in crystal structure and magnetic
structure is observed for different concentrations of Na in
Nd1xNaxMnO3 system. The crystal structure of NdMnO3 is
found to be similar to LaMnO3. The lattice parameters fol-
low the relation b=H2  c  a and correspond to the ortho-
rhombic distorted crystal structure. The elongation and
contraction of Mn-O bond lengths indicate the buckling of
MnO6 octahedra due to cooperative Jahn-Teller distortion.
093906-8 Samantaray et al.
FIG. 10. (Color online) Neutron powder diffraction patterns along with
Rietveld refinements for x ¼ 0.20 sample at 5 K and 300 K.
The magnetic structure of NdMnO3 compound is quite simi-
lar to the A-type AFM structure observed in LaMnO3. In
A-type AFM structure, the Mn spins are ordered ferromag-
netically along a-c plane and the coupling between the
planes along b-direction is AFM. We have observed that
the moments of Mn ions are slightly canted away from the
a-c plane. At low temperatures (<15 K), magnetic sublattice
corresponding to Nd ion is also found to be ordered and
coupled ferrimagnetically with magnetic sublattice corre-
sponding to Mn ion. However, Muñoz et al.2 have observed
FM coupling between Nd and Mn ions. The magnetic struc-
ture of Na doped NdMnO3 system is completely different
from that of parent compound. The x ¼ 0.15 sample shows
FM with spin canted structure below 80 K. However at 5 K,
the system enters into the CO state and could be confirmed
from the three weak super lattice reflections observed at
lower angles of NPD data. These super lattice peaks could
be refined by including pseudo CE-type AFM structure. So
at low temperature, coexistence of spin canted FM and CO-
AFM is observed in the hole rich compound. Thus, the exis-
tence of phase separation (PS) scenario could be understood
in this sample. The evolution of this magnetic PS can be due
to either electronic or structural PS.7 The Nd0.8Na0.2MnO3
compound shows CO state with pseudo CE-type AFM
structure below 125 K. It is very interesting to have
CO phenomena in systems having compositions away
from the half doped region. Basically, the half doped man-
ganites like La0.5Ca0.5MnO3,37 Pr0.5Ca0.5MnO3,38 and
Nd0.5Ca0.5MnO3,17 exhibit CE-type AFM ordering. Accord-
ing to the Kajimoto et al.,18 the energy difference between
the A-type AFM ordering and CE-type AFM ordering is
very small. They have observed CE-type AFM ordering in
Nd0.5Sr0.5MnO3 compound and a coexistence of CE-type
and A-type ordering for higher concentration of Sr.18 The
magnetic structure of CO manganites with doping concentra-
tion away from the half doped composition exhibits pseudo
CE-type AFM ordering. In Pr0.7Ca0.3MnO3 compound, Cox
et al.39 observed pseudo CE-type structure in the CO region.
J. Appl. Phys. 110, 093906 (2011)
In monovalent doped Pr1xNaxMnO3 series, the system
undergoes transition from A-type AFM ordering (for x ¼ 0)
to the pseudo CE-type AFM ordering (for x ¼ 0.2) through a
spin canted arrangement (for x ¼ 0.025 and 0.05).31 Pseudo
CE-type structure has been also reported in CO
Bi0.75Sr0.25MnO3 compound.40 A direct evidence of CO tran-
sition around 170 K was observed in Nd0.75Na0.25MnO3 from
electron diffraction.41
V. CONCLUSIONS
We have studied the crystal and magnetic structures and
magnetic properties of Na doped NdMnO3 (x ¼ 0, 0.15, and
0.20) compounds from neutron powder diffraction and mag-
netization measurements. At room temperature, all com-
pounds are found to be in single phase form and crystallized
in Pnma space group. The patterns at low temperature could
be refined by considering both nuclear and magnetic reflec-
tions based on different magnetic structures. The fall in lat-
tice parameters with a clear change in slope with decrease in
temperature was observed at around Neel temperature for the
x ¼ 0 sample. However in x ¼ 0.20 sample, the shrinkage of
b parameter below 180 K and the moderate expansion of a
and c parameters reveal pseudo CE-type AFM ordering. The
magnetic structure of x ¼ 0 sample below 75 K could be
explained in terms of A-type AFM with canting of Mn
moments away from the a-c plane. The ordering of Nd
moments and their ferrimagnetic coupling with Mn moments
were observed at around 15 K. The x ¼ 0.15 sample shows
spin canted ferromagnetism. However, three superlattice
reflections of weak intensities were observed at 5 K and
could be refined to the pseudo CE-type structure. The coexis-
tence of canted FM and CO states could be confirmed from
the high field magnetization measurements. So, there is a
presence of magnetic phase separation in the lower doped
sample. Finally, the CO phase in x ¼ 0.20 sample below
125 K could be refined by including pseudo CE-type AFM
structure in the P21/m space group. The maximum refined
moments for Mn3 þ and Mn4þ sublattices are found to be
3.20 (05) lB and 3.00 (02) lB, respectively. The high field
M-H loop at 5 K shows the field induced irreversible meta-
magnetic transition above a threshold field (Hf) of 4.5 T.
ACKNOWLEDGMENTS
Authors acknowledge the financial support from UGC-
DAE-CSR, Mumbai towards a collaborative research scheme
and DST, New Delhi for the magnetometer.
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