Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

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Journal of Magnetism and Magnetic Materials

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Research articles

Coupling between Ho and Mn/Cr moments and its influence on the T

structural and magnetic properties of HoMn1−xCrxO3 (0 < x ≤ 1)
compounds
⁎
Pulkit Prakasha, Ripandeep Singha, S.K. Mishraa, C.L. Prajapatb, A. Kumara, A. Dasa,c,
a
Solid State Physics Division, Bhabha Atomic Research Center, Mumbai 400085, India
b
Technical Physics Division, Bhabha Atomic Research Center, Mumbai 400085, India
c
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India

A B S T R A C T

The effect of doping non Jahn-Teller (JT) Cr3+ ion on the crystallographic structure and magnetic ordering has
been studied in a series of polycrystalline compounds HoMn1−xCrxO3 (0 < x ≤ 1). These compounds crystallize
in a mixture of hexagonal and orthorhombic phases for x < 0.125 whereas the orthorhombic phase is present
for all higher concentrations. It is observed that Cr doping leads to decrease in the mismatch of the bond length
in Mn-O6 octahedra indicating reduction in the static orbital ordering due to JT effect. In addition, doping with
Cr3+ introduces ferromagnetic Mn3+-O-Cr3+ interactions in an antiferromagnetic matrix consisting of Mn3+-O-
Mn3+ and Cr3+-O-Cr3+ interactions. A change in the magnetic structure from Г4 (AxFyGz) to Г2 (CxGyFz) is
observed in samples with x > 0.75, which is attributed to the anisotropic interactions between the Ho3+ and
Cr3+ spins. An incommensurate magnetic order corresponding to the wave vector (0.4, 0, 0) is observed in the
orthorhombic phase associated with the x = 0.05 sample. The hexagonal phase in the Mn-rich end exhibits a
reduced magnetic ordering temperature of 55 K and a spin reorientation at 15 K, in comparison to h-HoMnO3.
The temperature variation of dielectric data shows weak magnetodielectric coupling in these compounds.

1. Introduction reorientation with lowering of temperature [14], the moments in h-

The origin of the multiferroic behavior in rare earth manganites
(RMnO3) [1,2] and chromites (RCrO3) [3,4] (where R = Rare Earth
element) is a subject of intense current interest. The challenges in these
studies partly originate from the interplay of varied crystallographic
structures they adopt and the presence of competing magnetic inter-
actions viz., Mn/Cr–Mn/Cr, R-Mn/Cr, R-R, in these compounds. The
RMnO3 compounds (R = La-Dy) grown under ambient pressure, crys-
tallize in an orthorhombically distorted perovskite structure (space
group Pnma) while those with R = Ho-Lu and Y, crystallize in a hex-
agonal unit cell with space group P63cm (S.G no. 185). On the other
hand the entire series of RCrO3 compounds (R = La–Yb) crystallize in
the orthorhombic structure. The magnetism in both RMnO3 [5–8] and
RCrO3 [9–12] series of compounds are found to be influenced by the R-
Mn and R-Cr interactions, respectively.
Powder neutron diffraction studies on hexagonal HoMnO3 show
that the Mn spins order in a triangular structure with moments parallel
to the (1 0 0) axes, corresponding to the irreducible representation Г2 at
78.5 K [13]. In contrast to hexagonal YMnO3 which shows no spin
HoMnO3 below TSR ∼ 44.6 K rotate in the basal plane to become per-
pendicular to the (1 0 0) axis and the magnetic structure is explained by
Г1 IR. The origin of the spin reorientation in the hexagonal phase is
given by the trigonal anisotropy [15] present between the Ho and Mn
spins. In addition to the influence on the magnetism of hexagonal
structures, the presence of magnetic rare earth ions in between the Mn-
O5 bipyramids, reduces the frustration parameter from ∼5.55 as ex-
hibited by h-YMnO3 [16] to nearly 0.6 in h-HoMnO3. The effect of the
rare earth moment on the magnetic structures in h-RMnO3 has been
investigated previously in YbMnO3 [17] and HoMnO3 [6,18] and found
to alter the magnetic structures in these compounds and thereby other
properties.
The substitution at Mn-site in HoMnO3 creates disorder directly in
Mn-O network, leading to a strong impact on its magnetic, structural
and transport properties. Substitution with only 20% Fe leads to sta-
bilization of the orthorhombic phase and results in decline of ferroe-
lectricity associated with h-HoMnO3 [19]. On the other hand with only
10% Co doping the orthorhombic phase is stabilized. XPS studies con-
firm that Co at Mn site stabilizes in +2 state and +3 state, thus forcing

⁎
Corresponding author at: Solid State Physics Division, Bhabha Atomic Research Center, Mumbai 400085, India.
E-mail address: adas@barc.gov.in (A. Das).

https://doi.org/10.1016/j.jmmm.2018.05.080
Received 26 February 2018; Received in revised form 25 May 2018; Accepted 25 May 2018
Available online 26 May 2018
0304-8853/ © 2018 Published by Elsevier B.V.
P. Prakash et al.
Fig. 1. Crystal Structure of HoMn1−xCrxO3 in (a) Hexagonal phase (space group P63cm) and (b) Orthorhombic Phase (space group Pnma).
Mn to form in the +3 and +4 states. This leads to competing FM
Mn3+-O-Mn4+ double exchange interactions in Co doped compounds.
Ferromagentism observed in these compounds in addition to anti-
ferromagnetic behavior is attributed to the double exchange interac-
tions [20]. In hexagonal YMnO3, doping Mn with 10% non Jahn-Teller
Cr3+ ion is found to increase the antiferromagnetic transition tem-
perature from 73 to 89 K while decreasing the effective magnetic mo-
ment [21,22]. Further, it has been shown that Cr substitution in both h-
YMnO3 and o-YMnO3 significantly enhances the ferromagnetic com-
ponent, although the antiferromagnetic (AFM) phase remains dominant
[16,23]. In the case of o-YMnO3, 10% Cr substitution is found to in-
crease the intrinsic polarization of the compound.
In the series RCrO3 (R = La-Yb), Cr moments exhibit G-type AFM
configuration with canted moments which give rise to weak ferro-
magnetic (FM) and A-type antiferromagnetic (AFM) components also.
The canting behavior is attributed to the antisymmetric Dzyaloshinskii-
Moriya (DM) interactions present in these systems [24]. The transition
temperature of these compounds varies from 282 K, for LaCrO3 [25], to
112 K, for LuCrO3 [26] (depending upon the size of the rare-earth ion).
The ferroelectric temperatures and associated mechanisms of these
compounds are still under debate [9,27–29]. In HoCrO3, from magne-
tization studies it is inferred that the Cr spins order at 140 K whereas
the Ho spins order at 7.5 K. However, neutron diffraction experiments
indicate an induced Ho ordering occurring at ∼30 K. This has been
attributed to the strong Ho-Cr coupling in HoCrO3 [12,30]. The role of
the moment on the rare earth site and its coupling with the transition
metal site however, remains unclear in these studies.
Magnetic properties of manganites are found to vary the most on
doping with Cr ions, where even small additions has been found to
change the magnetic ground state [31]. Doping with a eg0 hole in the
Mn-O network via the Cr3+ ion (3d3) leads to the inclusion of eg1-O-eg0
interactions in the system which by Goodenough-Kanamori (GK) rules
are weakly ferromagnetic. Additionally Cr3+, in the absence of eg
electrons is a JT inactive ion whereas Mn3+ is an active one. Further
Cr3+ has smaller ionic radii than Mn3+ which creates chemical pres-
sure in the HoMnO3 system. Cr substitution in h-HoMnO3 is therefore
expected to influence both distortion and magnetism in these com-
pounds and also bring out the role of Ho-Mn and Ho-Cr interactions. In
this manuscript we have studied the effect of these in the evolution of
magnetic structures in the series of compounds HoMn1−xCrxO3
(0 < x ≤ 1).
2. Experimental details
Polycrystalline samples of HoMn1−xCrxO3 (0 < x ≤ 1) were pre-
pared by conventional solid state reaction route. The starting materials
Ho2O3, Mn2O3 and Cr2O3 were mixed in stoichiometric ratio and
71
Journal of Magnetism and Magnetic Materials 465 (2018) 70–80
calcined in air at 1200 °C for 60 h with several intermediate grindings.
The phase purity of these samples was confirmed by x-ray powder
diffraction recorded on a Rigaku diffractometer, using Cu Kα radiation
in the angular range 10° ≤ 2θ ≤ 90° at room temperature.
Magnetization measurements were carried out on a Superconducting
quantum interference design magnetometer (SQUID). The zero field
and the field cooled measurements were carried out in a magnetic field
of 0.1 T. For dielectric measurements, disk shaped pellets of approxi-
mately 16 mm diameter and 1–2 mm thickness were prepared using a
uniaxial isostatic press. Silver paste was applied on the polished sur-
faces of the disk to form electrodes. Low temperature dielectric mea-
surements were carried out using a Novocontrol alpha impedance
analyzer. For cooling the sample down to 5 K, a closed cycle refrigerator
with He-gas exchange attachment was used. Temperature dependent
capacitance data was measured in the frequency range 1 Hz–1 MHz
with a hearting rate of 0.8 K/min in the range from 5 to 300 K. Neutron
diffraction and neutron depolarization measurements were carried out
at the Dhruva reactor, Bhabha Atomic Research Centre, Mumbai. The
neutron diffraction patterns were recorded on the PD2 powder neutron
diffractometer (λ = 1.2443 Å) at temperatures between 6 K and 300 K
in the angular range 5° ≤ 2θ ≤ 140o. The Rietveld refinement of the
patterns were carried out using FULLPROF program [32]. The depo-
larization measurements (λ = 1.205 Å) were carried out on the po-
larized neutron spectrometer (PNS) in Dhruva reactor with Cu2MnAl
(1 1 1) as polarizer and Co0.92Fe0.08 (2 0 0) as analyzer. FC neutron
depolarization measurements were carried out by first cooling the
sample from room temperature down to 4 K in presence of 50-Oe field
and then carrying out the measurements in warming cycle under the
same field. The incident neutron beam polarization was 98.6% and a
DC flipper was used to flip the polarization.
3. Results and discussion
The compounds in the series HoMn1−xCrxO3 (0 < x ≤ 1) crystal-
lize in mixed orthorhombic (Pnma) and hexagonal phase (P63cm) for
x < 0.125 and orthorhombic phase (Pnma) for higher doping. The
crystal structures of the hexagonal and orthorhombic phases are shown
in Fig. 1. In the hexagonal structure (space group P63cm) Mn3+ ions
occupy the 6c position with the co-ordinates (x,0,z) and are surrounded
by 5 oxygen ions forming trigonal bipyramids whereas the Ho ions are
seven fold co-ordinated and occupy the positions 2a, 4b with the co-
ordinates (0,0,z) and (1/3, 2/3, z) respectively. In this symmetry Mn3+
ions form a two dimensional network of MnO5 bipyramids separated by
layers of Ho3+ ions. On the other hand in perovskites with the or-
thorhombic structure (space group Pnma) Mn3+ ions occupy the 4b
position with the co-ordinates (0, 0, ½) and are surrounded by 6 oxygen
ions forming a Mn-O6 octahedra whereas the rare earth ions are nine
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

1.0 temperature, structural transition is not observed in any of the samples.

(a) x = 0.875 Fig. 2(a) and (b) show the Rietveld refined plots of x-ray and neutron
diffraction data for a few representative samples in the series. The re-
0.5 sults of the refinement of the orthorhombic phase at 300 K and 7 K are
summarized in Tables 1 And 2 respectively.
For x < 0.125, Bragg reflections corresponding to the hexagonal
0.0
Intensity (arb units)

Pnma phase, characteristic of h-HoMnO3 compound together with reflections

corresponding to orthorhombic phase, appear in the x-ray diffraction
1.0 data and thus the refinement for these compositions were carried,
x = 0.50 taking into account, a mix of hexagonal and orthorhombic phases. A
0.5 small substitution of Cr at the Mn-site (< 2 at. %) in HoMnO3 is found
to strongly favor the crystallization of the orthorhombic phase. A rapid
suppression of hexagonal phase is observed on increasing x. Similar
0.0 behavior had also been reported earlier where structural transition in
Pnma
HoMnO3 is observed with doping on the Ho and Mn sites [19,20]. The
1.0 samples above x ≥ 0.125 crystallize in a single orthorhombic phase
x = 0.05 (space group Pnma) with glazer tilt system a−b+a−. The cell para-
meters and the volume of the end compound HoCrO3 were found to be
0.5
in good agreement with that reported earlier [33,34]. A gradual de-
crease in the volume of the compounds is observed with increase in Cr
0.0 P63cm concentration which is attributed to the lower ionic radii of Cr3+
Pnma (0.615 Å) ion as compared to the Mn3+ (0.645 Å) ion.
The variation of cell parameters and volume as a function of Cr
10 20 30 40 50 60 70 80 content (x) in the orthorhombic phase is shown in Fig. 3. In the Pnma
symmetry the in plane lattice parameters are a and c, whereas b-axis
(deg) projects out of plane. The inequality in the expansion of the a and c axes
arises from the in phase tilting of the Mn-O6 octahedra along the b-axis
which causes the long Mn-O bonds to align closely with the a-axis than
(b) x = 0.875
with the c-axis. This behavior is observed in compounds having co-
30
operative Jahn-Teller distortions in the presence of GdFeO3 type tilting.
The structure is found to change from O′ (b/√2 < c ≤ a) to O (c < b/
15 √2 ≤ a) orthorhombic at x ∼ 0.25, indicative of cooperative Jahn-
Pnma
Teller distortion caused by large concentration of Mn ions, 80%, in this
Intensity (arb units)

range [35] and its reduction on doping with non-JT Cr3+ ion for
0
x > 0.25.
x= 0.50 The variation of bond distances in the orthorhombic phase is shown
50 in Fig. 4. The distance from the apical oxygen (Mn-O1) remains nearly
the same with x (Table 1). In the Mn rich end, because of the Jahn-
Teller effect, the three bond distances are unequal and can be classified
as long (l), medium (m) and short (s) for Mn-O21, Mn-O1 and Mn-O22
respectively. Along the (0 1 0) axis the Mn bond distances are equal but
0 Pnma
in the (0 1 0) plane they are alternately long and short. The electron
ordering producing this Jahn-Teller effect gives completely empty eg
100 x = 0.05 orbitals directed along the s bonds, half filled orbitals directed along the
l bonds, and less than half filled orbitals along the m bonds. This leads
50 to anisotropic exchange interaction for the Mn rich compounds [35].
The average tilt angle < φ > around the pseudocubic [1 1 1] axis has
P63cm been calculated from the two superexchange angles between the Mn
0
Pnma spins (θ1 = Mn-O(1)-Mn and θ2 = Mn-O(2)-Mn), using the geometrical
expression derived by O’Keefe and Hyde [36]. The systematic decrease
20 40 60 80 100 in the tilt angle with increase in Cr content shows the steric effect that is
introduced due to the inclusion of Cr ions. Similarly to evaluate the
(deg) octahedral distortion Δ of co-ordination polyhedron Mn/Cr-O6 with an
Fig. 2. (a) X-ray diffraction pattern and (b) Neutron diffraction pattern of average bond distance 〈Mn-O〉, we have used the expression
(dn− < d >) 2
HoMn1−xCrxO3 (x = 0.05, 0.5, 0.875) at 300 K. Open circles are observed data
points. The solid line represents the Rietveld refined fit. In both the figures, blue
()1 N
Δ = N ∑n = 1 { <d> }
[37]. The structural parameters obtained
from refinement of neutron diffraction data at 300 K and 7 K are sum-
and the green markers show the nuclear Bragg peak positions for the orthor-
marized in Tables 1 And 2 respectively. The Mn/Cr-O-Mn/Cr angles
hombic and the hexagonal phase respectively.
were observed to change from ∼144° at the Mn rich end to ∼147° at
the Cr rich end. It has been reported earlier that as the bond angle Mn-
fold co-ordinated and occupy the position 4c with the co-ordinates (x, O-Mn in o-RMnO3 changes from 146° to 144° the magnetic structure
¼, z). The structural characterizations of all the samples were carried changes from A-AFM to incommensurate AFM to E-type AFM [38].
out using x-ray and neutron diffraction techniques. No impurity phase Therefore, at the Mn rich end an incommensurate structure associated
was observed. The Rietveld refinement of the data was carried out by with the orthorhombic phase of HoMnO3, which we observe can be
varying the scale, cell parameters, background, position of atoms, caused due to the change in the bond angle. However, a complete
thermal parameters, occupancy and magnetic moment. On lowering of transition to an E-type AFM order is not observed in our samples.

72
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

Table 1
Lattice parameters, Mn-O bond lengths, Mn-O-Mn bond angles and octahedral distortion (Δ) as obtained from Rietveld refinement of the Neutron Diffraction data of
HoMn1−xCrxO3 compounds at 300 K. The atomic sites are Ho 4c(x,1/4,z); Mn/Cr 4b(0,0,0.5); O1 4c(x,1/4,z); O2(x,y,z) in the Pnma space group. The symbol O1
denotes the oxygen atom along the b-axis (apical) and O21 and O22 are the oxygen atoms in the ab plane (equatorial). The symbols Δ and φ denote octahedral
distortion and average tilt angle, respectively.
x 0.125 0.25 0.5 0.875 1

a (Å) 5.761 (5) 5.717 (5) 5.630 (4) 5.526 (4) 5.510 (3)
b (Å) 7.398 (7) 7.441 (9) 7.469 (6) 7.531 (5) 7.533 (4)
c (Å) 5.254 (5) 5.259 (6) 5.247 (4) 5.248 (4) 5.243 (2)
V (Å−3) 223.92 (4) 223.76 (5) 220.62 (3) 218.43 (3) 217.65 (2)

Ho
x 0.0786 (6) 0.0767 (6) 0.0738 (4) 0.0675 (4) 0.0650 (3)
z −0.0164 (7) −0.0188 (8) −0.0139 (5) −0.0158 (5) −0.0152 (4)
Biso (Å2) 0.61 (7) 0.54 (6) 0.12 (4) 0.39 (3) 0.23 (4)

Mn/Cr
Mn occupancy 0.4375 0.375 0.50 0.0625 0.00
Cr occupancy 0.0625 0.125 0.50 0.4375 0.50
Biso (Å2) 0.72 (3) 0.64 (6) 0.53 (8) 0.61 (4) 0.58 (6)

O1
x 0.4621 (9) 0.464 (1) 0.4632 (7) 0.4655 (7) 0.4653 (5)
z 0.1069 (9) 0.105 (1) 0.1028 (7) 0.1062 (5) 0.1004 (5)
Biso (Å2) 1.21 (7) 0.91 (6) 0.62 (4) 0.60 (2) 0.37 (4)

O2
x 0.3287 (7) 0.3231 (7) 0.3167 (6) 0.3051 (9) 0.3032 (4)
y 0.0525 (5) 0.0533 (3) 0.0547 (4) 0.0522 (5) 0.0534 (2)
z −0.2992 (8) −0.2984 (9) −0.3061 (6) −0.3062 (6) −0.3061 (4)
Biso (Å2) 1.21 (7) 0.91 (7) 0.62 (4) 0.60 (2) 0.37 (4)
Mn-O1(Å) 1.945 (1) 1.951 (2) 1.954 (3) 1.972 (3) 1.965 (8)
Mn-O21(Å) 2.202 (4) 2.167 (5) 2.093 (3) 2.013 (3) 1.997 (8)
Mn-O22(Å) 1.896 (4) 1.909 (5) 1.952 (3) 1.976 (3) 1.978 (2)
Mn-O1-Mn (deg) 143.91 (7) 144.93 (8) 145.61 (5) 145.31 (5) 146.88 (3)
Mn-O2-Mn (deg) 143.9 (2) 144.7 (2) 144.0 (1) 145.8 (1) 146.18 (9)
〈Mn-O〉 (Å) 2.014 (2) 2.009 (3) 1.999 (2) 1.987 (2) 1.980 (5)
Δ (Mn-O) × 10−4 44.385 (1) 31.654(2) 10.894(1) 0.863(2) 0.440(3)
< φ > (deg) 22.0(3) 21.4(3) 21.5(3) 21.1(3) 20.4(3)

χ2 5.75 6.65 4.22 1.67 2.53

RBragg (%) 4.05 10.8 8.87 3.73 8.35

3.1. Magnetization values of Curie-Weiss temperature indicating the presence of anti-

The temperature dependence of magnetization (M) measured in low
fields for all the samples are shown in Fig. 5. For x < 0.125, the
samples exhibit a Curie-Weiss like behavior at temperatures much
above TN (above ∼160 K), similar to that observed in the case of
hexagonal YMnO3 [16] and other frustrated compounds [17]. In this
case the paramagnetic contribution of Ho ions plausibly masks the in-
dication of antiferromagnetic transition in the sample, which is other-
wise observed in the neutron diffraction data. The x = 0.125 and 0.25
samples were found to follow the C-W behavior down to 5 K indicating
the paramagnetic nature of these samples. However, very weak hys-
teresis loops are observed in high magnetic fields suggesting weak
ferromagnetic nature of these samples. For x > 0.5, in the Cr-rich end,
a sharp increase in the M(T) behavior is observed at T = 140 K, in-
dicative of ferromagnetic like transition. A similar behavior is observed
in the parent compound HoCrO3 [39] and has been attributed to the
canted AFM ordering of Cr3+ spins due to Dzyaloshinskii-Morya (DM)
interactions. The transition at 140 K although still present for the
x = 0.5 and 0.375 samples is not so sharp because of weakening of
Cr3+-O-Cr3+ interaction, due to doping with Mn, which leads to
weakening of the DM interaction, responsible for the canting of the Cr
spins. Further from neutron diffraction studies (shown later) we find
that the Ho moments do not exhibit any long magnetic range order for
samples with x < 0.75, which rules out Ho ferromagnetic contribution
to the samples. The inverse of susceptibility for all the samples were
fitted to Curie-Weiss law χ = C/(T − θ), where C is the Curie constant
and θ is the Curie-Weiss temperature. The paramagnetic susceptibility
is found to follow the Curie-Weiss law in the range ∼140–300 K for
samples with x ≥ 0.375.All the samples were found to have negative
ferromagnetic interactions in these samples. From the curie constant
values the paramagnetic moment (µeff) was calculated using the rela-
2
tion C = Nμeff μB2 /3kB . The values of μeff
cal exp
, μeff and θCW obtained from the
fits are listed in Table 2. The value of θCW becomes less negative in the
interval 0.02 < x < 0.25, as ferromagnetic interactions Mn3+-O-Cr3+
appears in the system, and for x > 0.25 the value of θCW becomes more
negative because of the strengthening of the AFM Cr3+-O-Cr3+ inter-
actions. The expected effective moment values were calculated by as-
cal
suming Ho, Mn and Cr in the trivalent state. The value of, μeff is cal-
cal 2 2 2
culated as μeff = xμeff (Cr 3 +) + (1−x) μeff (Mn3 +) + μeff (Ho3 +) where
µeff for Mn3+, Cr3+ and Ho3+ are 4.89µB, 3.87µB, and 10.61µB re-
spectively. The experimentally obtained values of μeff exp
are in agreement
with those calculated, as shown in Table 2, indicating the trivalent
nature of the Ho and Mn/Cr ions.
The variation of magnetization with magnetic field at 5 K for se-
lected compositions is shown in Fig. 6. The magnetization curves did
not exhibit any hysteresis at room temperature and were found to be
linear (not shown here). But at low temperatures M(H) curves were
seen to display a narrow hysteresis loop with a large slope at high
magnetic fields, suggesting the co-existence of ferromagnetic and anti-
ferromagnetic interactions. Both coercivity and retentivity of the fer-
romagnetic loops were found to increase with increasing x. To under-
stand the FM ordering tendency with increase in Cr doping, one con-
siders the strong competition between the AFM (neighboring Mn3+-
Mn3+ pairs and Cr3+-Cr3+ pairs) and FM (neighboring Mn3+-Cr3+
pairs) interactions that are expected in this series of compounds
[14,40]. Although the FM (neighboring Mn3+-Cr3+ pairs) interactions
may not be strong for small values of x, the net FM component becomes

73
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

Table 2
Lattice parameters, Mn-O bond lengths, Mn-O-Mn bond angles, octahedral distortion (Δ) and the magnetic structure of Mn/Cr and Ho moments as obtained from
Rietveld refinement of the Neutron Diffraction data of HoMn1−xCrxO3 compounds at 7 K. The atomic sites are Ho 4c(x,1/4,z); Mn/Cr 4b(0,0,0.5); O1 4c(x,1/4,z);
O2(x,y,z) in the Pnma space group. The symbol O1 denotes the oxygen atom along the b-axis (apical) and O21 and O22 are the oxygen atoms in the ab plane
(equatorial).
x 0.125 0.25 0.5 0.875 1

a (Å) 5.754 (5) 5.709 (5) 5.626 (3) 5.522 (4) 5.506 (3)
b (Å) 7.382 (7) 7.425 (9) 7.451 (5) 7.518 (5) 7.521 (4)
c (Å) 5.246 (5) 5.252 (6) 5.239 (3) 5.239 (4) 5.237 (2)
V (Å−3) 222.83 (4) 222.63 (4) 219.61 (2) 217.51 (3) 216.85 (2)

Ho
x 0.0814 (5) 0.0776 (5) 0.0757 (3) 0.0686 (4) 0.0663 (3)
z −0.0177(7) −0.0147(8) −0.0149 (5) −0.0166 (6) −0.0175 (4)
Biso (Å2) 0.44 (7) 0.25 (5) 0.31 (3) 0.30 (4) 0.26 (4)

Mn/Cr
Biso (Å2) 0.48 (8) 0.59 (6) 0.62 (4) 0.51 (3) 0.46 (3)

O1
x 0.4621 (8) 0.4663 (9) 0.4651 (6) 0.4623 (7) 0.4650 (5)
z 0.1096 (8) 0.104 (1) 0.1035 (6) 0.1043 (7) 0.1027 (5)
Biso (Å2) 1.11 (6) 0.67 (5) 0.46 (2) 0.38 (3) 0.29 (3)

O2
x 0.3251 (6) 0.3200 (7) 0.3161 (4) 0.3054 (5) 0.3024 (4)
y 0.0526 (4) 0.0546 (5) 0.0549 (3) 0.0550 (3) 0.0533 (2)
z −0.2997(7) −0.3005(8) −0.3046 (4) −0.3086 (5) −0.3053 (4)
Biso (Å2) 1.11 (6) 0.67 (6) 0.46 (2) 0.38 (3) 0.29 (3)

Mn-O1(Å) 1.943 (2) 1.947 (2) 1.951 (3) 1.968 (2) 1.965 (8)
Mn-O21(Å) 2.186 (4) 2.164 (4) 2.088 (3) 2.000 (3) 1.989 (2)
Mn-O22(Å) 1.899 (4) 1.909 (4) 1.946 (3) 1.988 (3) 1.979 (2)
Mn-O1-Mn (deg) 143.45 (7) 144.93 (7) 145.37 (5) 145.32 (5) 146.16 (3)
Mn-O2-Mn (deg) 144.6 (2) 144.4 (2) 144.6 (1) 145.25 (1) 146.46 (9)
〈Mn-O〉 (Å) 2.009 (1) 2.006 (1) 1.995 (1) 1.985 (1) 1.977 (4)
Δ(Mn-O) x10−4 39 (1) 31(1) 10.8 (7) 0.4 (1) 0.2 (2)
〈φ〉 (deg) 21.9(3) 21.6(3) 21.3 (3) 21.2(3) 20.5(3)
exp 11.6 11.4 11.4 11.0 10.9
μeff (µB)
cal
μeff (µB) 11.64 11.59 11.49 11.34 11.29
θCW (K) −16.3(2) −13.3(1) −19.5(4) −27.5 (2) −32.3 (1)
MCr (μB) (7K) FY 1.33(9) GY 2.55(6) GY 2.55(4)
GZ 1.89(4)
MHo (μB) (7K) CX 2.19(4) CX 2.30(6)
FZ 1.33(9) FZ 1.20(8)

χ2 5.13 6.79 3.66 2.51 2.74

RBragg (%) 3.77 10.4 6.84 6.98 8.52

HoMn1-xCrxO3 2.3
5.76 HoMn1-xCrxO3
Mn-O1

T = 300 K
Lattice Parameters ( )

224 T = 300K O21

Mn-
Bond Lengths ( Å)

a 2.2
5.60 Mn-
O22
V
222
V ( 3)

2.1 Mn-O21 (l)

5.44
220

b/ 2 2.0
5.28 Mn-O1 (m)
c 218

0.0 0.2 0.4 0.6 0.8 1.0 1.9

Mn-O22 (s)
x
Fig. 3. Variation of lattice parameters and unit cell volume as function of Cr
0.00 0.25 0.50 0.75 1.00
content at room temperature for the orthorhombic phase. x
Fig. 4. Variation of bond distances as a function of Cr content at room tem-
larger for higher values of x [23]. For x > 0.5, the appearance of Ho
perature. Continuous lines are a guide for the eye.
ferromagnetic moments causes a large change in the size of the ferro-
magnetic loops. It is also seen that magnetization does not saturate upto
external fields of 50kOe, due to dominant AFM interactions.

74
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

15 Table 3
HoMn 1-x Cr xO 3 x = 0.875
Parameters obtained from the modified Curie-Weiss fitting of the dc-suscept-

1/ (emu/mol Oe)-1
30 12
N (K), θ (K), C (emu K Oe
ibility data, the T Cr −1
mol−1), the fitting parameter TO
9 (K), the symmetric exchange constant Je(K) and the antisymmetric exchange
constant De.
M (emu/g)

6
x 1 0.875 0.75
20 3
Cr
TN (K) 139.6 (8) 134.6 (5) 134.6 (3)
0 TO (K) 138.9 (5) 134.0 (7) 134.3 (7)
120 135 150 165 180
θ′ (K) −32.3 (4) −27.5 (7) −20.4 (4)
T (K)
C′ (emu K Oe−1 mol−1) 15.3 (7) 16.5 (5) 16.6 (3)
10 0.375 J/kB (K) 9.26 (2) 8.3 (4) 7.7(1)
0.02 0.50 D/kB (K) 1.8 (3) 1.6 (3) 0.9 (5)
0.05 0.75
0.125 0.875
0.25 1
Here Z = 6 is the co-ordination number of Mn3+/Cr3+ relative to
0 other Mn3+/Cr3+ ions. We have taken the value of S to be given by the
0 50 100 150 200 250 300 expression, S = (1−x)(SMn)2 + x(SCr )2 where x is the concentration of
T (K) the Cr ions and SMn, SCr are the spin quantum numbers of the Mn3+ and
Cr3+ ions with the values 2 and 3/2 respectively. The parameters, Je
Fig. 5. Temperature variation of magnetization with temperature (ZFC) for and D denotes the magnitudes of symmetric and anti-symmetric M3+-
HoMn1−xCrxO3. M3+ (M = Mn3+/Cr3+) exchange interactions, respectively. The M3+-
M3+ exchange interactions can be extracted from the above parameters
6 as TNCr is far above rare earth ordering temperature and other exchange
interactions (Ho3+-M3+ and Ho3+-Ho3+) are very small. In the inset of
0.02
0.25 Fig. 4 we show 1/χ vs T data of x = 0.875 sample fitted to Eq. (1). The
4 0.50 fitted parameters such as the Curie constant (C′), TO and Weiss tem-
0.75 perature (θ′) are summarized in table 3. Our results for the parent
1.00 compound HoCrO3 are in good agreement with those reported earlier
2
/ f.u

[11]. The analysis performed clearly shows that the exchange constant
Je/kB increases with increasing Cr concentration. The Cr-Cr super-
exchange coupling depends on the bond angle Cr-O1-Cr and on the
)

0
B

2.0

HoMn1-xCrxO3 1.5 bond length 〈Cr-O〉, both of which change with increasing Cr con-
M(

1.0 centration. This clearly shows that a direct correlation between the
/ f.u

-2 T = 5K 0.5
structural and the magnetic properties. The reduction in the value of
0.0
B)

the D-M interaction term, responsible for the canting for the Cr spins, is
M(

-0.5
-1.0 also evident from this analysis. This leads to reduction in the net fer-
-4 -1.5 romagnetic moment obtained from the M(H) data.
-2.0
-3 -2 -1 0 1 2 3 The ferromagnetic behaviour in these samples is further probed
H (kOe) using neutron depolarization measurements. This technique measures
-6
-40 -20 0 20 40 spatial magnetic inhomogeneities on a length scale from 1000 Å to
several micrometers. In the present study we have measured the flip-
H (kOe) ping ratio R (ratio of transmitted intensities for two spin states of the
Fig. 6. Isothermal magnetization curves for HoMn1−xCrxO3 at 5 K. incident neutron spin), which is a measure of the transmitted spin po-
larization. R is expressed in the form [42],
1 − P DP
R = 1 + (2f − i1) PADP (4) where, Pi, D, PA, f are the incident neutron
The weak ferromagnetic nature of the compounds x = 0.75, 0.875 i A

and 1 below TN is due to the DM antisymmetric exchange interaction beam polarization, depolarization, polarizing efficiency of the analyzer,
whose effect was included by Moriya on the temperature dependence of and efficiency of the DC spin flipper, respectively. In the case of a ty-
the paramagnetic susceptibility using a molecular field approximation pical ferromagnetic or ferrimagnetic material, the magnetic domains
[41]. The theory states that the susceptibility along the easy-axis di- exert a dipolar field on the neutron polarization and depolarize the
rection obeys the CW law, whereas the susceptibility perpendicular to neutrons due to Larmor precession of the neutron spins in the magnetic
the easy axis also depends upon the DM interaction. For our poly- field of the domains. In ideal anti-ferromagnetic materials, there is no
crystalline samples, we could not measure the susceptibility along and net magnetization, hence no depolarization occurs. In paramagnetic
perpendicular to the easy axis separately. Thus we use the equation for materials, the neutron polarization is unable to follow the variation in
the dominant contribution from the perpendicular direction as modeled the magnetic field as the temporal spin fluctuation are very fast (10−12
by Moriya [41], s or faster), hence no depolarization is observed. However, depolar-
ization is expected in the case of clusters of spins with net magnetiza-
C'(T−TO) tion [42].
χ=
(T−θ)' (T−TCr
N) (1) Fig. 7 shows the temperature dependence of the transmitted neutron
beam polarization P in an applied field of 50 Oe applied parallel to the
where T is the temperature and TO and TN Cr
are fitting parameters,
incident neutron beam polarization. A large change in the transmitted
described as [41],
beam polarization is observed below 140 K for samples with x > 0.5,
2Je ZS(S + 1) indicating the ferromagnetic nature of these samples. The change in the
TO =
3kB (2) polarization becomes increasingly larger as the concentration of Cr ions
increases in the sample. This change indicates towards the presence of
' 2 1/2
2Je ZS(S + 1) ⎡ ⎛D⎞ ⎤ ferromagnetic domains present in the samples. The ferromagnetic
TCr
N = ⎢1 + Je ⎥
⎜ ⎟

3kB ⎣ ⎝ ⎠⎦ (3) nature of the samples x = 0.75–1, explains the increase in

75
P. Prakash et al.
1.0
0.8
Polarization
0.6
HoMn 1-x Cr xO 3
0.4
x=1
x = 0.875
x = 0.75
0.2 x = 0.50
x = 0.375
0.0
0 50 100 150 200 250
T (K)
Fig. 7. Temperature dependence of transmitted neutron beam polarization (P)
for HoMn1−xCrxO3 (0.375 ≤ x≤1) in H = 50 Oe.
magnetization in the M(T) measurement below T = 140 K for these
samples. An estimate of the domain size in the ferromagnetic region of a
polycrystalline sample, is obtained using the expression
Pf = Piexp −α ( ( ) ) < ϕ >[43,44] where P
d
δ δ f and Pi are the transmitted
beam and the incident beam polarization, respectively, α is a di-
mensionless parameter (=1/3), d is the sample thickness, δ is a typical
−2
domain length and the precession angle ϕδ = (4.63x10−10Oe−1Å ) λδ B
[43]. The domain magnetization B is obtained from the bulk magneti-
zation. This expression is valid in the limit where the domains are
randomly oriented in a low field far away from saturation field and
therefore satisfy the assumptions of this model. The absence or low
value of depolarization indicates reduction in ferromagnetic domain
size and/or domain magnetization, which is the case for samples with
x ≤ 0.5. For the x = 1 sample, two clear transitions can be seen at
T ∼ 47 K and T ∼ 20 K from the depolarization data which gradually
shift to lower temperatures and disappear as the concentration of the
Mn ions is increased. These two transitions in HoCrO3 have not been
reported before. The partial recovery of polarization in this sample is
indicative of the two transitions arising from Ho ordering (discussed
later). The estimated domain size for x = 1 at 80 K is ∼1.8 µm. Cr spins
were found to order in the GY configuration at T ∼ 70 K and Ho spin
ordering below ∼30 K from the neutron diffraction data. Thus neutron
depolarization measurements clearly give evidence of ferromagnetic
domains co-existing in an antiferromagnetic matrix in the samples
0.5 < x ≤ 1.
3.2. Magnetic structure
The neutron diffraction pattern for all the samples has been re-
corded at selected temperatures in the range 6 K ≤ T≤300 K and in an
angular range of 5o ≤ θ ≤ 120o. In samples with x = 0.02 and 0.05, the
refinement was carried out in a mixed phase of hexagonal (P63cm) and
orthorhombic (Pnma) structures. Fig. 8 shows the diffraction pattern at
300 K, 50 K, and 6 K for the x = 0.02 sample. The volume fraction of the
hexagonal phase was found to decrease with increasing Cr content, the
phase fraction falling from 78% to 58% for the x = 0.02 and 0.05
samples respectively. Due to the low volume fraction of the orthor-
hombic phase in the case of x = 0.02 sample, the magnetic contribution
to the reflections from the orthorhombic phase was not taken into ac-
count. An increase in the superlattice reflection (1 0 1) at TN ∼ 55 K is
observed, marking the onset of the AFM order in the hexagonal phase.
→ at T ∼ 15 K, which was not found to be present in the 0.02 sample. We
The (1 0 1) reflection was indexed using propagation vector, k =0 in
the P-1 space group. There are six possible irreducible representations
Journal of Magnetism and Magnetic Materials 465 (2018) 70–80
(113)
(002)
(100)
100 T = 6K
(110)
(102)
50
0
Intensity (arb units)
-50
(101)
100 T = 50K
50
0
-50
300
100 T = 300K
50
0
10 20 30 40 50 60
(deg)
Fig. 8. Neutron diffraction pattern for HoMn1−xCrxO3 (x = 0.02) at 6 K, 50 K,
and 300 K. The markers from top to bottom indicate nuclear (hexagonal), nu-
clear (orthorhombic) and magnetic (hexagonal) positions, respectively.
(Г1-Г6) that are compatible with the space group P63cm corresponding
→
to k = 0. In line with the reported magnetic structure of h-HoMnO3
[45], we obtained the best fit using Г4 IR, assuming that only Mn spins
are ordered (Г2 and Г4 are homometric configurations). The ordering
temperature was found to be lowered as compared to hex-HoMnO3 [13]
which orders at TN ∼ 78 K. This might be due to inclusion of Cr atoms
in the Mn-O triangular lattice which weakens the exchange interaction
between the Mn-spins.
On further reducing the temperature, below TSR ∼ 20 K, for
x = 0.02, the intensity of the (1 0 0) reflection gains in intensity with
concomitant gradual weakening of (1 0 1) reflection indicating a spin
reorientation behavior in the sample. The magnetic structure below this
temperature is observed to be best described by Г1 IR, similar to that
observed in the parent compound at low temperature. Fig. 9 shows a
schematic representation of the magnetic structures found in the hex-
agonal phase at 7 and 300 K respectively. The spin reorientation tem-
perature is observed to be lowered as compared to h-HoMnO3 (TSR ∼
38.8 K). In contrast to the ordering of the Ho ions in h-HoMnO3 in the
(0, 0, AZ) configuration at 25.4 K [13], we did not observe evidence of
ordering of the Ho-spins down to 7 K in the doped compounds. The
spin-reorientation in hex-HoMnO3 is attributed to Ho-Mn coupling
arising out of an trigonal anisotropy term present in the total Ha-
miltonian of the system [15]. Thus our results show that even 2% ad-
dition of Cr atoms leads to weakening of the Mn-O-Mn superexchange
interactions and the trigonal anisotropy between the Ho-Mn spins
thereby lowering both TN and TSR respectively.
Fig. 10 shows the neutron diffraction pattern of x = 0.05 sample at
300 K, 50 K, and 6 K. The magnetic structure of the hexagonal phase for
TN < T < TSR and T < TSR are identical to that observed in the case
of x = 0.02 sample. In addition, the orthorhombic phase of the 0.05
sample was seen to exhibit an additional superlattice reflection (0 1 0)
found this reflection to be associated with an incommensurate order in
76
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

Fig. 9. Configuration of Mn spins in the hexagonal phase corresponding to the irreducible representations (a) Г1 and (b) Г2.
(113)

Integrated Intensity
HoMn1-xCrxO3 (110)
(100)
(010)

10 Ho
TN
(020)

(011)
100 T = 6K x = 0.875
(110)
(102)

(110)
T = 6K 8
3

Intensity (arb units)

50 TN
Cr

(001)
6

0
0 20 40 60
2
Intensity (arb units)

T (K)
-50
0.875
100
(101)

T = 50K 1
0.50
50

0 0 0.25

100 10 12 14 16 18 20 22 24
T = 300K
2 (deg)
50 Fig. 11. (a) Neutron diffraction patterns for HoMn1−xCrxO3 (x = 0.875, 0.5,
0.25) at 6 K. The blue and green markers show the position of Bragg peaks for
0 the nuclear and magnetic phase respectively. Inset shows the integrated in-
tensity plot of the (1 1 0) peak for the x = 0.875 sample.

10 20 30 40 50 60 superlattice or enhancement of the fundamental reflections indicating

(deg)
Fig. 10. Neutron diffraction pattern for HoMn1−xCrxO3 (x = 0.05) at 6 K, 50 K,
and 300 K. The markers from top to bottom indicate nuclear (hexagonal), nu-
clear (orthorhombic), magnetic (hexagonal) and magnetic (orthorhombic) po-
sitions, respectively. The peak marked as (0 1 0) corresponds the in-
commensurate peak indexed by the wave vector k = (0.4, 0, 0) at T = 6 K.
the orthorhombic phase characterized by the wave vector
→ On increasing the Cr concentration to x = 0.375 and 0.5, an in-
k = (0.4,0,0). It should be noted that Mn spins in o-HoMnO3 order in
→ crease in the intensity of forbidden Bragg reflections in the Pnma space
an similar incommensurate structure with k ∼ (0.4,0,0) at T ∼ 30 K
[46]. A similar reflection was not observed for the 0.02 sample possibly
due to the low phase fraction (22%) of the orthorhombic phase. Any
signature of short range ordering in the hexagonal phase was found to
be absent in the neutron diffraction data, which clearly shows the
suppression of frustration parameter which occurs with Cr doping in
these compounds.
Rietveld refinement of the room temperature data for all the sam-
ples with x ≥ 0.125 has been carried out in the Pnma space group. As
can be seen in Fig. 11, for x = 0.125 and 0.25 we did not observe any
that these samples are paramagnetic down to 7 K. A similar result was
obtained from our M(T) measurements where the χ vs T data was seen
to follow Curie-Weiss law down to 5 K. Although a small hysteresis loop
was obtained in the M(H) measurements indicating towards a weakly
ferromagnetic sample. Similar results have been reported in the case of
LaMn1−xCrxO3, which completely loses its G-type magnetic order with
only 15% Cr doping [47], and in YMn1−xCrxO3 [16,23],
NdMn1−xCrxO3 [31] both of which show increasing ferromagnetic
character with increase in Cr concentration.
group was observed with the lowering of temperature below TN. These
superlattice reflections were indexed as (1 1 0) and (0 1 1), shown in
→
Fig. 11, in the P-1 space group with the propagation vector ( k = 0).
The basis vectors for the various possible magnetic structures were
obtained using the SARAH program [48]. The best fit to the x = 0.5
data could be obtained in Г4 IR with Mn/Cr in GZFY configuration. It
should be mentioned here that the end compound of the series HoCrO3,
below TN, exhibits Г2 IR as its ground state magnetic structure with Cr
spins in the GYFZ configuration and Ho spins in CYFZ configuration.

77
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

Thus in order to confirm the orientation of Cr spins we tried fitting our Table 4
x = 0.5 data with Cr spins in Г2 configuration (Rmag = 29.5), Г2 + Ho Irreducible representations for the transition metal and rare earth atoms in the
→
(Rmag = 21.6) moments and in a mixed representation of Г2 + Г4 Pnma space group for = k 0 [49]. The Mn ions occupy the positions (0,0,1/2),
(Rmag = 17.9). But the best fit to the data could be obtained with only (1/2,0,0), (0,1/2,1/2), (1/2,1/2,0), and Ho ions are in the positions (x,1/4,z),
(1/2−x,3/4,1/2 + z), (x,3/4, z ), (1/2 + x,1/4,1/2−z).
Г4 configuration giving a minimum Rmag of 13.9. No evidence of Ho
ordering was observed in these samples. Transition Metal (Mn/Cr) Rare Earth (Ho)
With further increase in Cr concentration to x = 0.75, 0.875 and 1
Г1 AX GY CZ — — CZ
the magnetic structure below the respective TN is described by Г2 IR as
Г2 FX CY GZ FX CY —
against Г4 IR found in the case of samples with x < 0.75. In addition, Г3 CX FY AZ CX FY —
the superlattice reflection (0 0 1) was observed to gain in intensity Г4 GX AY FZ — — FZ
(absent for samples with x < 0.75) below 30 K, in the neutron dif- Г5 — — — GX AY —
Г6 — — — — — AZ
fraction pattern together with a significant increase in the intensity of
Г7 — — — — — GZ
the (0 1 1) reflection as compared to the (1 1 0) reflection. The tem- Г8 — — — AX GY —
perature evolution of the neutron diffraction for x = 0.875 is shown in
Fig. 11. On lowering of temperature an increase in the intensity of
(0 0 1) reflection is observed together with change in the relative in-

(110)

(011)
(001)
tensities of (1 1 0) and (0 1 1). The magnetic structure factor calculation 4
6K
shows that Cr/Mn spins contribute to the (0 0 1)m and (1 1 0) (0 1 1)

Intensity (arb uints)

reflections with C-type and G-type spin arrangement respectively and
similarly Ho site moment contributes to (0 0 1) reflection pre-
dominantly. However an analysis of the diffraction data for T < 30 K
with moments on the Cr/Mn site alone gives a poor fit (RMag = 16.9) as
compared to the moment on both Ho and Cr/Mn sites (RMag = 10.8).
Thus we find that the samples in the Cr rich end have a moment on Ho
in addition to Cr and the magnetic structure in this case changes from Г4
to Г2. Fig. 12 shows a schematic representation of both the magnetic
structures for the orthorhombic phase. According to the representation
→ 1
theory, for the Pnma space group ( k = 0) there are eight different
possible representations (Г1-Г8) on consideration of moments only on
the Ho site, whereas out of these eight only four (Г1-Г4) are valid on
consideration of moments both on the Mn/Cr and the Ho sites si-
multaneously [49]. Table 4 lists the various possible magnetic re-
presentation allowed by the representation theory for the Pnma space
group. We find that the magnetic structure of 0.75, 0.875 and 1 samples
at 6 K is best described in the Г2 IR with Cr/Mn spins in the CXGYFZ and
Ho spins in the CXFY configuration. The values of the moment on the Cr
and Ho are summarized in Table 2. We find that the moments on Mn/Cr
are close to the expected value of moment for mixture of S = 3/2 (3 µB)
and S = 2 (4 µB). However, the moment value in the case of Ho is far
lower in value as compared to expected value of 10.6 µB. This is pos-
sible if not all the spins on Ho are ordered. This is also evident from the
large paramagnetic contribution observed in M(T). However, our re-
sults are different from the early neutron diffraction studies on HoCrO3,
where the moment at ∼2 K was observed to be close to 7µB [30].
Fig. 13 shows the thermal evolution of the neutron diffraction pattern
for the x = 0.875 sample which clearly shows the development of su-
perlattice reflections with the lowering of temperature.
The variation of integrated intensity with temperature of (1 1 0)
10K
3 15K
20K
30K
2 40K
50K
60K
75K
100K
0
10 20 30 40
2 (deg)
Fig. 13. A selected portion (10° ≤ θ ≤ 40°) of neutron diffraction pattern at
various temperatures for HoMn0.125Cr0.875O3 (x = 0.875) sample is shown. The
increase in the intensity of the superlattice reflections (1 1 0) and (0 1 1) is
evident from 75 K whereas (0 0 1) is seen to gain intensity from 30 K.
reflection is shown in the inset of Fig. 11. The drop in intensity at 30 K
and 70 K is attributed to the TN of Ho and Cr/Mn moments respectively.
In contrast to the earlier reports on the parent compound HoCrO3
[12,30,39], we did not observe any ferromagnetic moment on the Cr
site. However a large drop in the intensity of the (0 0 1) reflection has
been observed near 30 K which is in agreement with our case. Below TC
∼ 140 K we did not observe any enhancement of intensity in the low
angle fundamental Bragg reflections, which indicates an absence of

Fig. 12. Configuration of Mn spins in the orthorhombic phase corresponding to the irreducible representations (a) Г4 (AxFyGz) and (b) Г2 (CxFyGz).

78
P. Prakash et al. Journal of Magnetism and Magnetic Materials 465 (2018) 70–80

h+O' Ho3+-Cr3+ anisotropic interactions in stabilization of the Г2 phase,

HoMn 1-xCrxO3
TC causing the interaction energy of the Cr3+ spins with the effective field
125
(P63cm + Pnma)
to exceed the anisotropy energy of the Cr3+ ion. With increase in Mn
O-type content these interactions get diluted and weakened, leading to a re-
100 (Pnma) duction in the effective field at the Cr3+ site. With 50% substitution
with Mn ions the anisotropy energy again dominates and stabilizes the
Г4 phase. Based on our analysis of the magnetization and neutron dif-
T (K)

TCr
75 N fraction results a magnetic phase diagram for the entire series is pre-
Thex
N sented in Fig. 14.

50 2
(Gy) Temperature dependent dielectric measurements, εr(T), were per-
formed for 0.05, 0.5 and 0.875 samples in the frequency range 1 Hz to
4
1 MHz. In Fig. 15 we show the representative curves for the samples at
hex
25 TSR TNHo 1 kHz frequency. The dielectric constant is almost independent of
1
temperature up to 170 K above which it increases with a steep rise
wFM 4
(FyGz) 2
(CxGyFz) which is associated with a large frequency dependent Maxwell-Wagner
i.c.
0 polarization. Though we do not observe a dielectric anomaly in the
0.02 0.25 0.50 0.75 1.00 vicinity of transition at ∼140 K for the 0.875 sample, the derivative of
x εr(T) shows a clear anomaly at ∼73 K and ∼32 K shown in Fig. 15(a).
Cr
Both these temperatures are close to the THo N (30 K)and T N (70 K) ob-
Fig. 14. Magnetic phase diagram for the series HoMn1−xCrxO3.
tained from neutron diffraction studies indicating magnetoelastic cou-
pling at the transition temperatures. A similar plot for the 0.5 sample is
shown in Fig. 15(b). However, in this case the derivative plot is very
broad at ∼40 K suggesting a weakening of the coupling. On the other
hand, for the 0.05 sample a clear dielectric anomaly can be seen in εr(T)
at spin reorientation temperature TSR (15 K). The dielectric behaviour
of this compound is very similar to that of o-HoMnO3 [51]. The distinct
anomalies in the dielectric constant and its closeness to the magnetic
transition temperatures suggests weak magnetodielectric coupling in
these compounds.

4. Conclusions

The structural and magnetic properties of HoMn1−xCrxO3

Fig. 15. Variation of dielectric constant with temperature at 1 kHz. Insets show
the dielectric anomaly at TSR and TN.
(0 < x ≤ 1) have been studied using neutron diffraction, neutron de-
polarization and magnetization measurements. For x = 0.02, 0.05 there
is co-existence of both hexagonal (P63cm) and orthorhombic phases,
with the fractional volume of the orthorhombic phase being 22%, 42%
respectively. The hexagonal phase, present in the 0.02 and 0.05 sam-
ples, orders at 55 K in the Г4 IR and undergoes a spin reorientation to
the Г1 phase at 15 K. The orthorhombic phase gives an incommensurate
magnetic ordering corresponding to the wave vector (0.4, 0, 0) for the
0.05 sample. The compounds with x ≥ 0.125 are isostructural and
crystallize in distorted orthorhombic perovskite structure with space
group Pnma. With increase in Cr concentration volume, tolerance factor
and octahedral distortions decrease. It has been observed that rare earth
moment induces spin reorientation (Г4 → Г2) of Cr/Mn moments for
x > 0.5. Based on our results a magnetic phase diagram for the series is
presented. Dielectric data indicates presence of weak mangetodielectric
coupling present in these compounds.
Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the

long range ferromagnetic ordering from the present neutron diffraction
online version, at https://doi.org/10.1016/j.jmmm.2018.05.080.
experiment. However, M(T,H) and neutron depolarization data below
T ∼ 140 K for x = 0.75,0.875 and 1 samples shows hysteresis and de-
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