Enhancement in magnetocaloric properties

of holmium chromite by gadolinium

substitution
Cite as: J. Appl. Phys. 120, 043906 (2016); https://doi.org/10.1063/1.4959253
Submitted: 04 May 2016 . Accepted: 11 July 2016 . Published Online: 27 July 2016

S. Yin, and M. Jain

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 JOURNAL OF APPLIED PHYSICS 120, 043906 (2016)

Enhancement in magnetocaloric properties of holmium chromite

by gadolinium substitution
S. Yin1 and M. Jain1,2,a)
1
Department of Physics, University of Connecticut, Storrs, Connecticut 06269, USA
2
Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269, USA
(Received 4 May 2016; accepted 11 July 2016; published online 27 July 2016)
HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3 bulk powder samples were prepared by citrate route. The
phase purity and the structural properties of the samples were examined by x-ray diffraction and
Raman spectroscopic measurements. The dc magnetization data revealed that the Cr3þ ordering tem-
peratures (Neel temperature) for the HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3 samples are 140 K,
148 K, and 167 K, respectively, while the ac magnetization data revealed that the rare-earth (Ho)
ordering occurs at 8 K for HoCrO3 and Ho0.67Gd0.33CrO3 samples. Temperature-induced magnetiza-
tion reversal and spin reorientation were observed in GdCrO3 bulk sample, which depends on applied
magnetic field and disappears at 1500 Oe and 500 Oe, respectively. By fitting the dc magnetic data
with Curie-Weiss law, the effective magnetic moments were calculated to be 11.66 lB, 10.23 lB, and
9.90 lB for the HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3 samples, respectively. The isothermal magne-
tization data showed that the magnetic behavior changed from canted antiferromagnetic in low tem-
perature region (below Neel temperature) to paramagnetic at high temperature. It was found that Gd
substitution considerably improves the magnetocaloric effect of HoCrO3. Pure GdCrO3 bulk sample
showed giant magnetocaloric entropy change (31.6 J/kg K at temperature 5 K and at 70 kOe),
which is higher than that for polycrystalline RMnO3, RCrO3, and RFeO3 bulk powder samples. This
renders GdCrO3 useful for potential applications in low-temperature magnetic refrigeration. Published
by AIP Publishing. [http://dx.doi.org/10.1063/1.4959253]

I. INTRODUCTION ordering temperature increased (261 K) compared to that of

In the past decade, magnetoelectric multiferroics (ME
MFs) with both ferroelectric and magnetic orders have been
considered attractive for their potential applications in devices
such as random access memory, magnetic field sensors,
and capacitors.1–5 A few rare earth manganites (RMnO3) have
been regarded as single phase ME MFs with strong coupling
between ferroelectric and magnetic orders;1,6,7 however, they
become MF only at relatively low temperatures (e.g., 27 K
for TbMnO3).7 Recently, great attention has been paid to rare-
earth chromites (RCrO3) since their magnetically driven ferro-
electricity temperatures are much higher than their manganite
counterparts.8–12 These RCrO3 materials have also been inten-
sively investigated due to their magnetocaloric effect (MCE),
which is the basis of magnetic refrigeration, a prospective
technology to replace conventional vapor-compression refrig-
eration that contributes to a global energy problem.13–15 For
example, bulk DyCrO3 was reported to have a large MCE
value at 8.4 J/kg K and relative cooling power (RCP) 217 J/
kg at 20 K and at 4 T, which renders it useful for refrigera-
tion application below 30 K.10 In order to further improve the
MCE property of DyCrO3, substitution at the A-site (by
another rare-earth element) or at the B-site (Mn, Fe, etc.) has
been considered.16–18 For example, B-site substituted
DyCrO3, i.e., bulk powder DyCr0.5Fe0.5O3 sample, was found
to have a larger MCE value 10.5 J/kg at 5 K and 4 T than
that of pure DyCrO3 powder sample, meanwhile the Cr3þ
a)
Author to whom correspondence should be addressed. Electronic mail:
menka.jain@uconn.edu
pure DyCrO3 (146 K).17 On the other hand, A-site substitution
in DyCrO3 has resulted in mixed MCE values. For example,
the A-site substituted DyCrO3, i.e., bulk Dy0.7Y0.3CrO3 or
Dy0.7Ho0.3CrO3 showed slightly lower MCE values than pure
DyCrO3, while Dy0.7Er0.3CrO3 showed larger MCE value
(10.92 J/kg K) than DyCrO3 or even DyCr0.5Fe0.5O3.16
Another rare earth chromite, HoCrO3, was also reported
to have a large MCE value 7.2 J/kg K and RCP 408 J/kg
at 20 K and at a magnetic field of 7 T.19 B-site substitution in
HoCrO3 has also been considered to further explore the
resulting MCE properties. Fe substitution at the B-site in
HoCrO3 (i.e., bulk HoCr0.7Fe0.3O3) has, however, resulted in
smaller MCE (6.8 J/kg K) and RCP (387 J/kg) values at
20 K and at a magnetic field of 7 T.19 On the other hand, the
effect of A-site substitution on the MCE properties of
HoCrO3 has not been explored yet. So, it is worthwhile to
investigate how the MCE properties of HoCrO3 are altered
by substitution at the A-site. To select a suitable rare earth
element as an A-site dopant, we note that among all rare
earth elements, Gd based materials have been investigated
widely and they also exhibit excellent MCE properties. For
example, Gd single crystal was shown to have MCE value of
8.9 J/(kg K) and RCP value of 461.6 J/kg at room temper-
ature and at a field of 5 T, and thus it is considered useful for
magnetic refrigeration near room temperature.20–22 Also, Gd
alloys were reported to have superior MCE property.13,22,23
A large MCE value was reported for Gd5(Si2Ge2) with an
improvement of MCE value by a factor of 2 compared to Gd
single crystal, which is attributed to arise due to a first-order

0021-8979/2016/120(4)/043906/8/$30.00 120, 043906-1 Published by AIP Publishing.

043906-2 S. Yin and M. Jain J. Appl. Phys. 120, 043906 (2016)

phase transition at 276 K and unique magnetization depen-

dence on field.20 Recently, Ren et al.24 showed that (Gd, In)
solid solution has slightly smaller MCE values than Gd
single crystal, but the transition temperature is lower and
tunable making the solid solution suitable for magnetic
refrigeration at lower temperatures. Moreover, the MCE
properties of Gd based complex oxides have also been stud-
ied. Yu et al. reported GdMnO3 single crystal shows the
MCE value of 31 J/(kg K) at 19 K and at a magnetic field of
7 T along the c-axis.25 In another recent study, Yin et al.
reported giant MCE value at 31.6 J/kg K for a field of 4.4 T
in single crystal GdCrO3 along c-axis. However, the usage of
single crystals for practical magnetic refrigeration is envi-
sioned to be limited owing to the direction dependent MCE
properties along with the difficulty in synthesizing single
crystals. Guided by the observation of superior MCE proper- FIG. 1. The x-ray diffraction data and the Rietveld refinement of (a) HoCrO3
ties in Gd containing single crystalline materials in the afore- (HCO), (b) Ho0.67Gd0.33CrO3 (HGCO), and (c) GdCrO3 (GCO) samples.
mentioned studies, we believe it would be worthwhile
exploring the effect of Gd substitution (A-site dopant) on the III. RESULTS AND DISCUSSION
resulting MCE properties in bulk HoCrO3. The experimental XRD patterns obtained for HCO,
In the current work, we employed a citrate route to pre- HGCO, and GCO bulk powders along with the Reitveld
pare HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3 bulk powder refined patterns are shown in Figures 1(a)–1(c). For each sam-
samples. Their structural, magnetic, and magnetocaloric ple, the experimental XRD pattern could be refined with an
properties have been investigated in detail and are presented orthorhombically distorted perovskite structure (space group
here. MCE value of the polycrystalline GdCrO3 bulk powder Pbnm). No extra peaks and the goodness of the Reitveld
sample was found to be higher than that of all polycrystalline refinements suggests that the samples were phase pure.
RMnO3 and RCrO3 bulk powder materials. Various structural parameters, such as the lattice constants,
Cr-O-Cr bond angles, and strain parameters, as obtained from
II. EXPERIMENTAL the Reitveld refinements, are summarized in Table I. The lat-
tice parameters of HCO and GCO agree well with the previous
In order to make phase-pure HoCrO3 (HCO),
reports26,27 and those of HGCO are intermediate between
Ho0.67Gd0.33CrO3 (HGCO), and GdCrO3 (GCO) bulk pow-
the end compositions (HCO and GCO). The orthorhombic dis-
der samples, first the stoichiometric amounts of high-purity
tortions of the unit cell from the ideal cubic structure, defined
Ho(NO3)3, Gd(NO3)3, and Cr(NO3)3 precursors were sepa-
by the orthorhombic strain factor S ¼ 2(ba)/(bþa),28 were
rately dissolved in water and then mixed together. Citric acid
calculated and summarized in Table I as well. Table I also lists
was then added to this mixture followed by drying on a hot the average ionic radii (Ra,avg) of the A-site ion, where Ra,avg
plate at 100  C. The resultant dry powder was annealed at qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
of HGCO is calculated by 0:33  rGd 2 þ 0:67  r 2 , consi-
900  C in oxygen atmosphere for 2 h. The crystal structure Ho
and phase purity of the samples were characterized by x-ray dering the atomic number ratio and ionic radii of Ho3þ and
diffraction (XRD) (Bruker D2 x-ray diffractometer using Gd3þ ions. As can be seen in Table I, the lattice parameters
Cu-Ka radiation k ¼ 1.542 Å). The structural parameters
(lattice constants, bond angle/length, etc.) of the samples TABLE I. Lattice parameters, Cr-O bond lengths, and Cr-O-Cr bond angles
were obtained by Rietveld refinement of the experimental obtained from the Rietveld refinement of the XRD data along with the calcu-
lated orthorhombic strain parameter (S) and average ionic radii (Ra,avg) of
XRD data performed using Fullprof Suite software. The the A-site ion for HoCrO3 (HCO), Ho0.67Gd0.33CrO3 (HGCO), and GdCrO3
room-temperature Raman spectroscopic measurements (GCO) samples.
were performed by Renishaw System 2000 using a 514 nm-
wavelength Ar-ion laser. The dc magnetic property was mea- Parameter HCO HGCO GCO
sured using the Vibrating Sample Magnetometer (VSM) a (Å) 5.248 5.273 5.322
attached to the Evercool physical property measurement sys- b (Å) 5.525 5.530 5.531
tem (PPMS) manufactured by Quantum Design. The temper- c (Å) 7.545 7.571 7.618
ature dependent magnetization was measured from 5 K to V (Å3) 218.77 220.78 224.27
300 K with an applied field of 50 Oe. The field dependent S 0.0514 0.0476 0.0385
magnetization measurement was performed with the applied Cr1-O1 (Å) 1.976 1.968 1.975
field up to 7 T from 5 K to 145 K (5 K step). The ac suscepti- Cr1-O2 (Å) 2.019 2.009 2.010
Cr1-O2 (Å) 1.975 1.974 1.966
bility was recorded using the ac susceptibility option
In-plane Cr1-O1-Cr1 (degrees) 146.64 148.12 149.02
attached to the PPMS from 5 K to 300 K under an applied ac Out-of-plane Cr1-O2-Cr1 (degrees) 145.34 147.10 147.88
magnetic field (amplitude 10 Oe, frequencies of 500 and Ra,avg (Å) 1.107 1.084 1.072
5000 Hz).
043906-3 S. Yin and M. Jain
and hence the lattice volume increase with Ra,avg, i.e., with
increasing Gd substitution at the Ho-site. The sizable mis-
match between R–O and Cr–O bond lengths in the
Goldschmidt tolerance factor {t  (R–O)/[冑2*(Cr–O)]} of < 1
results in significant cooperative rotations of the CrO6 octahe-
dra, which decreases with increasing Ra,avg. This leads to the
bending of the Cr–O–Cr angle and hence distortion. It should
be noted that with the addition of Gd at the Ho-site in HCO,
bond angles (in-plane Cr1–O1–Cr1 and out-of-plane
Cr1–O2–Cr1) increase and the strain factor (S) decreases,
indicative of the less distortion in the structure when higher
ionic radius Gd-ion is substituted in place of the smaller ionic
radius Ho-ion. This behavior is similar to that observed in the
rare earth manganite (RMnO3) counterparts.29 However, the
main difference between RMnO3 and RCrO3 compounds is
that RCrO3 compounds form orthorhombically distorted
perovskite structure for all R, whereas RMnO3 compounds
have that structure only for R ¼ La-Dy.30
Raman spectroscopy is also very useful to study the
phase purity and crystal structural distortion. Previous study
indicates that orthorhombic Pbnm perovskite structure has
24 active Raman modes: 7Agþ5B1gþ7B2gþ5B3g, 12 of
which occurs in the 100–600 cm1 range.31 Figure 2 shows
the Raman spectra of HCO, HGCO, and GCO bulk powders,
where all the observed peaks can be assigned to Raman pho-
non modes according to the report of Weber et al.,31 further
confirming that the bulk samples in the present study are
phase pure. The Raman modes, such as B2g(1), B2g(2),
Ag(4), Ag(6), show the systematic shift towards lower wave
number with increasing Gd substitution in HCO. This result
is consistent with the report of Weber et al., which presented
a systematic shift in the position of these modes with
decreasing A-site ionic radius. With decreasing average ionic
radius at the A-site, the modes below 200 cm1 not only shift
toward the lower wave numbers but also become more
intense. Moreover, the two groups of adjacent modes—
(B1g(1) and Ag(3), B1g(2) and Ag(5)) of HCO sample—are
observed slightly closer in HGCO sample and finally form
FIG. 2. Room temperature Raman spectra of HoCrO3 (HCO),
Ho0.67Gd0.33CrO3 (HGCO), and GdCrO3 (GCO) samples. Arrows in the figure
show the shifts in the wavenumber for the Raman modes with Gd substitution
at the Ho-site in HoCrO3.
J. Appl. Phys. 120, 043906 (2016)
an indistinguishable broad peak in Raman spectrum of GCO
sample.31 Since both the XRD patterns and the Raman spec-
tra show a systematic shift in the positions of the observed
peaks without noticeable broadening, it is clear that the pre-
sent synthesis method was successful in substituting Gd for
Ho in HCO without phase separation or impurity phases.
To study the effect of Gd substitution on magnetic prop-
erties of HCO, the temperature-dependent dc magnetization
data in both zero field-cooled (ZFC) and field cooled (FC)
conditions were measured with a magnetic field of 50 Oe as
presented in Figure 3. For all samples, divergence of the
ZFC and FC modes was observed below a certain tempera-
ture (Neel temperature, TN), which is caused by a weak G-
type antiferromagnetic ordering of the Cr3þ ions. By plotting
the derivative of FC magnetization data (dM/dT) as a func-
tion of temperature, as shown in the insets of Figure 3, the
TN (where Cr3þ orders) values were determined to be 140,
148, and 167 K for HCO, HGCO, and GCO samples, respec-
tively. The TN values for HCO and GCO are in good agree-
ment with previous reports on bulk samples in literatures.9,32
The maximum value of magnetization was found to be 30.8,
18.8, and 1.5 emu/g for bulk HCO, HGCO, and GCO,
respectively. Magnetic moments of Ho3þ and Gd3þ ions are
10.6 lB and 7.94 lB, respectively.33 The higher magnetic
moment of the Ho3þ ions along with cooperative alignment
between Ho3þ moments and the net Cr3þ moments at applied
field of 50 Oe leads to higher magnetization in HCO sample.
On the other hand, lower magnetic moment of Gd3þ ion,
which anti-aligns with the net Cr3þ moments,34 leads to the
lowering of magnetization values in Gd based samples as
seen in Figures 3(b) and 3(c). We also note that the TN and
maximum magnetization values for HGCO sample lie
between those of the two parent compounds, HCO and GCO,
FIG. 3. The temperature dependent zero field cooled (open red circle sym-
bols) and field cooled (closed black square symbols) dc magnetization data
of (a) HoCrO3 (HCO), (b) Ho0.67Gd0.33CrO3 (HGCO), and (c) GdCrO3
(GCO) samples at an applied field of 50 Oe show the effect of Gd substitu-
tion on the magnetic property. The insets show the derivative of magnetiza-
tion of FC mode versus temperature (dM/dT).
043906-4 S. Yin and M. Jain
FIG. 4. Cr-O1-Cr bond angle (black square) and average radii of A-site ions
(Ra,avg, blue squares) as a function of Neel temperature (TN). In the figure,
Ho, (Ho, Gd), Gd, Nd, and La stand for HoCrO3, Ho0.67Gd0.33CrO3,
GdCrO3, NdCrO3,36 and LaCrO3, 36 respectively.
which suggests that these values could be made tunable by
controlling the Ho3þ/Gd3þ ratio in the Ho1xGdxCrO3 solid
solution.
In RMnO3, the Mn-O-Mn bond angles have been shown
to have tremendous impact on their structure and magnetic
properties.6,35 In RCrO3 system studied here, the Cr-O-Cr
bond angle and Ra,avg (from Table I) were also found to
directly influence the TN. As presented in Figure 4, the in-
plane Cr-O-Cr bond angle and Ra,avg of RCrO3 (R ¼ Ho, Gd,
Nd, and La, where the data of NdCrO3 and LaCrO3 are
extracted from Reference 36) have almost linear relationship
with the experimentally measured TN of the samples.
Therefore, the effect of Gd substitution on the magnetic
property of HCO is directly correlated with the modifications
in its crystal structure.
Applied dc magnetic field dependence of the magnetiza-
tion data for both ZFC and FC modes as a function of tem-
perature is shown in Fig. 5 for GCO. The ZFC magnetization
FIG. 5. (a) The temperature dependent magnetization of GdCrO3 sample in
the zero-field cooling (ZFC) mode at different applied magnetic fields
50–1500 Oe. (b) Temperature dependent magnetization of GdCrO3 sample
in the field-cooling (FC) mode at different applied magnetic fields
50–1500 Oe and the inset of (b) shows the linear fitting of the temperature
where the magnetization is zero (T0 and T00 ).
J. Appl. Phys. 120, 043906 (2016)
data in Fig. 5(a) maximize at 7 K for the data with applied
field of 50–300 Oe when the temperature is decreased from
300 K and then it decreases with further lowering of temper-
ature. This maximum at 7 K is interpreted by the spin reori-
entation of Cr3þ and Gd3þ ions from high-temperature
C4(Gx, Ay, Fz) phase to low-temperature C2(Fx, Cy, Gz)
phase.37 Moreover, the spin reorientation behavior is applied
field-dependent and only exists at field 50–300 Oe, whereas
at field 500 Oe, the spin reorientation behavior was found
to be suppressed, because the rotation of the magnetic
moments or magnetic domain becomes more oriented at
higher fields.38 Figure 5(b) shows that on lowering the tem-
perature from 300 K, the FC magnetization data with an
applied field of 50 Oe first decrease to zero at 125 K and
then the magnetization value becomes negative. Upon fur-
ther lowering of temperature, the magnetization value
becomes positive again at 10 K and reaches maximum
value of 1.5 emu/g at 5 K. This phenomenon is called
temperature-induced magnetization reversal (TMR)32 that
arises from the competition of the two magnetic subsystems
(Cr3þ ions and Gd3þ ions) whose magnetic ordering is in
anti-parallel directions. However, it should be noted that the
TMR behavior does not exist in pure HCO and in Gd
substituted HCO (i.e., HGCO), this is because of the larger
magnetic moment and mass ratio of the Ho3þ ions as com-
pared to that of the Gd3þ ions. Note that in GCO single crys-
tal, the TMR behavior was found to be dependent on the
applied magnetic field and it disappeared with field higher
than 300 Oe applied along c-axis.32 In the present work,
the TMR behavior of GCO bulk (polycrystalline) sample
under different magnetic fields (50–1500 Oe) was measured
and is presented in Figure 5(b). With increasing applied
magnetic field from 50 to 1500 Oe, the magnetization value
at low temperature increases systematically. To describe
TMR behavior, the two temperatures, where the magnetiza-
tion reaches zero (lower one defined as T0 and higher one as
T00 as marked for 50 Oe data in the Figure 5(b)), are plotted
in the inset of Figure 5(b). It can be seen that T0 and T00
change linearly with the applied field from 50 to 1000 Oe. At
applied field of 1500 Oe, the TMR behavior disappears
because of stronger remnant magnetization in the sample,
which could not be reversed by the temperature change. This
critical field of 1500 Oe observed in present polycrystalline
bulk GCO sample is higher than 300 Oe reported for the
GCO single crystal. This could be because in GCO bulk sam-
ple, the magnetization is isotropic and the net magnetization
is smaller than that in single crystal at the same field, and
thus, higher magnetic field is required to reverse the direc-
tion of magnetization. It is noted that the TMR and spin
reorientation behavior were not observed in HGCO sample
because of large mass ratio of Ho3þ.
Above TN, the samples show paramagnetic behavior and
FC susceptibility (v) can be fitted by the Curie-Weiss law:
v ¼ C/(T-h), where magnetic susceptibility v ¼ M/(m*H),
(M—magnetic moment, m— the mass of the sample, H—the
applied magnetic field), C is Curie constant, and h is the
Weiss temperature. The fitting results are summarized in
Table II. The effective magnetic moment (leff) was
043906-5 S. Yin and M. Jain J. Appl. Phys. 120, 043906 (2016)

TABLE II. The magnetic parameters obtained by fitting the Curie-Weiss temperature, TN, of HCO and HGCO were 140 and 148 K,
law to the dc susceptibility data in paramagnetic region. The Neel tempera- respectively, which were in good agreement with the dc
ture TN (K), the Weiss temperature h (K), Curie constant C (emu K/(Oe
mol)), effective magnetic moment leff (lB), and l0 eff (calculated by free
magnetic results mentioned above. For HCO and HGCO
ionic moment) are presented here. bulk samples, an additional anomaly at 8 K was observed
due to the ordering of rare-earth ions Ho3þ, which was not
Sample GCO HGCO HCO revealed in dc magnetic measurement presented above.
TN (K) 167 148 140
To further investigate the magnetic properties, the field-
h (K) 71.89 6 2.13 15.48 6 0.77 36.47 6 0.60 dependent magnetization at 5, 50, 100, 145 K of the present
C (emu K/(Oe mol)) 12.26 6 0.10 13.10 6 0.04 17.01 6 0.04 samples was measured and is presented in Figure 7. Below
leff (lB) 9.90 6 0.04 10.23 6 0.02 11.66 6 0.01 TN, all the present samples show antiferromagnetic behavior
l0 eff (lB) 9.68 10.63 11.23 due to the canted antiferromagnetic ordering of Cr3þ ions.
Comparatively, the samples are paramagnetic above TN
qffiffiffiffiffiffiffiffi because of the linear paramagnetic behavior of Cr3þ and
calculated by C values using lef f ¼ 3kB C
where kB is the Ho3þ/Gd3þ ions. At 5 K and 40 kOe, the magnetization val-
N ,
ues of HCO, HGCO, and GCO are 85.3, 96.3, and 100.3
Boltzmann constant and N is the Avogadro constant.33 The
emu/g, compared to the respective values of 40.1, 34.4, and
values of leff for different samples were also compared
21.6 emu/g at 50 K and 40 kOe. It can be seen that the mag-
with the theoretical values calculated using the free ionic
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi netization value of GCO is largest at 5 K but smallest at 50 K
moments: l0ef f ¼ l2Cr þ ð1  xÞl2Ho þ xl2Gd , where lCr, of the three samples, which can be interpreted by the spin
lHo, and lGd are the free ionic moments of Cr3þ (3.8 lB), reorientation at 8 K in the GCO sample (Fig. 3(c)). The
Ho3þ (10.4 lB), and Gd3þ (8.9 lB), respectively, and x is the magnetization values of HGCO are intermediate between
Gd substitution fraction [Ho1xGdxCrO3]. The calculated those of HCO and GCO because of Gd substitution.
values of leff and l0 eff for all the samples are also included in Furthermore, HCO shows bigger magnetic hysteresis than
Table II. Close agreement between the leff and l0 eff values GCO, which is in good agreement with literature.9,32 This is
for each composition suggests that the present samples are probably because Gd3þ moments align antiparallel with
phase-pure and in the correct substitution ratio. The Weiss Cr3þ moments and Ho3þ moments aligns with Cr3þ
temperature, h, for all the present samples are negative, moments near the rare-earth ordering temperature.34 To
which is indicative of the antiferromagnetic behavior for all characterize the magnetic hysteresis, the temperature depen-
the samples studied here. The value of h of the present GCO dence of coercive field (Hc) and remnant magnetization (MR)
sample (71.9 K) is smaller than what has been reported ear- of the samples were extracted from the magnetic hysteresis
lier for GCO bulk sample (35 K).38 data and are shown in Figures 8(a) and 8(b), respectively. Of
Complementary to the dc magnetic measurement, the ac immediate note is the qualitative similarity between HCO
magnetization data can provide additional magnetic proper- and HGCO data, which probably arises from the dominant
ties.19,39 In Figure 6, the temperature dependent ac magneti- contribution of heavier Ho ions present in these composi-
zation data (real part v0 , imaginary part v00 ) of the HCO, tions. For HCO and HGCO, Hc shows a plateau 2600 Oe in
HGCO, and GCO samples under an applied ac magnetic field the temperature range 5–100 K and then quickly decreases to
(amplitude 10 Oe, frequencies 500 and 5000 Hz) are pre- zero near TN. On the other hand, the coercive field, Hc, for
sented. The v0 (T) and v00 (T) data also revealed that the Neel GCO increases with increasing temperature and reaches a
maximum (1300 Oe) at 40 K followed by gradual reduction
to zero near TN. Also, note that for GCO, Hc values are much

FIG. 6. The real part v0 (closed symbols, left y-axis) and imaginary part v00
(open symbols, right y-axis) of the temperature dependent ac magnetic sus-
ceptibility data for (a) HoCrO3 (HCO), (b) Ho0.67Gd0.33CrO3 (HGCO), and
(c) GdCrO3 (GCO) samples measured at ac magnetic field of amplitude
10 Oe and at frequency of 500 and 5000 Hz.
FIG. 7. Isothermal magnetization data at 5 K, 50 K, 100 K, and 145 K for (a)
HoCrO3 (HCO), (b) Ho0.67Gd0.33CrO3 (HGCO), and (c) GdCrO3 (GCO)
samples.
043906-6 S. Yin and M. Jain
FIG. 8. The temperature dependent (a) coercive field (Hc) and (b) remnant
magnetization (MR) values of HoCrO3 (HCO), Ho0.67Gd0.33CrO3 (HGCO),
and GdCrO3 (GCO) samples.
smaller than those of HCO (or HGCO) in the entire tempera-
ture range studied may be due to smaller magnetic moment
of Gd-ion (compared to Ho ions). At lower temperatures, the
weaker R3þ–Cr3þ exchange coupling becomes operative due
to the lowering of thermal energy. Thus, the magnetic
moment of the Gd-ion can now rotate with the Cr3þ moment,
thereby lowering the measured HC. This effect becomes
increasingly important with decrease in temperature, provid-
ing a qualitative interpretation of the data in Fig. 8(a). The
R3þ-R3þ interaction in these compounds is weak and is not
expected to significantly affect the magnetic properties
above the rare-earth ordering temperature, leaving only the
anisotropic component of R3þ-Cr3þ interaction to account
for the observed differences in the Hc values of the present
samples. In addition, the MR values of all three samples
decrease monotonically with increasing temperature from a
maximum of 33.5 emu/g (for HCO), 20.1 emu/g (for
HGCO), and 7.4 emu/g (for GCO) at 5 K to zero at 150 K.
The MR values for HGCO lie in between those for HCO and
GCO at all temperatures. Both Hc and MR values become
nearly zero for all three samples near their respective TN, fur-
ther illustrating their paramagnetic behavior above this
temperature.
The MCE properties of the present samples were evalu-
ated by calculating two factors: (i) magnetic entropy change
DSM(T,H) given by13
ðH   Figures 3(a)–3(c)) is observed. Second, HCO sample exhibits
@MðT; H Þ
DSM ðT; H Þ ¼ dH
0 @T H (see Fig. 7) and thus more energy is lost in the thermal process,
X Miþ1 ðTiþ1 ; H Þ  Mi ðTi ; H Þ
 DH (1)
i
Tiþ1  Ti
and (ii) relative cooling power (RCP) calculated by
ð T2
RCP ¼  jDSM;H jdT;
T1
where T1 and T2 are the high and low temperature limits in the
refrigeration cycle.16 Figure 9 shows the temperature
J. Appl. Phys. 120, 043906 (2016)
FIG. 9. The temperature dependent entropy change (DS) of (a) HoCrO3
(HCO), (b) Ho0.67Gd0.33CrO3 (HGCO), and (c) GdCrO3 (GCO) samples.
dependent DSM(T,H) values for the present samples at differ-
ent applied magnetic fields (1–7 T) derived from Eq. (1). The
value of DSM(T,H) for HCO enhances with increasing temper-
ature and reaches a maximum at 20 K and then decreases
with increasing temperature, whereas the value of DSM(T,H)
for GCO maximizes at 5 K and then decreases with increasing
temperature. Note that DSM(T,H) values of HGCO lie in
between that of HCO and GCO not only in magnitudes but
also in the temperature dependent behavior. At 1 T and 2 T,
DSM(T,H) values for HGCO shows a maximum at 20 K,
similar to the trend for HCO. On the contrary, DSM(T,H) val-
ues for HGCO decrease monotonically with increasing tem-
perature for applied fields above 2 T, similar to the trend for
GCO. At an applied field of 7 T, the maximum value of
DSM(T,H) for HCO, HGCO, and GCO is 7.2 J/kg K at 20 K,
14.0 J/kg K at 5 K, and 31.6 J/kg K at 5 K, respectively.
Therefore, Gd substitution at the A-site of HCO was found to
considerably improve the MCE properties of pure HCO, and
GCO showed very large MCE values. Several factors might
contribute towards the beneficial effects of Gd substitution in
improving the MCE properties of HCO. First, the MCE value
(DSM(T,H)) is proportional to the derivative of magnetization
versus temperature (dM/dT) according to Eq. (1). The dM/dT
value of HCO is smaller because M changes monotonically
with temperature, whereas the spin-reorientation in GCO
results in large dM/dT value and thus larger MCE value (see
much larger magnetic hysteresis compared to the GCO sample
resulting in smaller MCE values for HCO as compared to
GCO. This agrees well with the report of Phan and Yu13 that
materials with zero magnetic hysteresis are better suited for
magnetic refrigeration. Third, it has been noted that the MCE
value tends to reach maximum at 2 K in GCO single crystal,
which is close to the ordering temperature of Gd3þ (2.3 K).32
(2)
Thus, the large MCE in GCO and HGCO may have contribu-
tions arising from the Gd3þ-Gd3þ magnetic interactions.
The MCE values of HCO, HGCO, and GCO bulk sam-
ples are summarized and compared with earlier reports in
043906-7 S. Yin and M. Jain J. Appl. Phys. 120, 043906 (2016)

TABLE III. A comparison of the temperature (Tmax) and magnetic field IV. CONCLUSIONS
(Hmax) where the maximum entropy change (DSM,max) and the relative cool-
ing power (RCP) were obtained for rare-earth chromites, manganites, and In conclusion, HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3
single crystals. powder samples were synthesized via a solution route. X-ray
diffraction data revealed that the crystal structure of each
DSM,max Tmax Hmax RCP
composition was orthorhombically distorted perovskite
Material (J/kg K) (K) (T) (J/kg) Reference
(space group Pbnm) and no impurity phase was observed.
HoCrO3 7.2 20 7 408 19 The dc magnetic measurement showed that the ordering
HoCr0.7Fe0.3O3 6.83 20 7 387 temperature of Cr3þ ions (TN) is 140 K, 148 K, and 167 K
DyCrO3 8.4 15 4 217 10
for HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3 samples,
Dy0.7Y0.3CrO3 5.97 5 4 174 16
respectively, indicating that Gd substitution increased TN of
Dy0.7Er0.3CrO3 10.9 5 4 237
Dy0.7Ho0.3CrO3 7.46 5 4 211
HoCrO3. The ac magnetic measurements confirmed the Cr3þ
GdCrO3 (single crystal) 26.1 5 4 … 32 ordering temperatures of HoCrO3 and Ho0.67Gd0.33CrO3 and
GdCrO3 (this work) 31.6 5 7 546 This also revealed ordering temperature of rare-earth ions at 8 K
19.0 5 4 245 work in HoCrO3 and Ho0.67Gd0.33CrO3. The isothermal magneti-
Ho0.67Gd0.33CrO3 13.9 5 7 490 zation data indicated that the magnetic behavior of the pre-
(this work) 7.9 5 4 218 sent samples changed from low-temperature (below TN)
GdMnO3 (single crystal) 31 19 8 … 25 canted antiferromagnetic to high-temperature (above TN)
HoMnO3 12.5 10 7 312 41
paramagnetic. These features were characterized by the tem-
perature dependent coercive field and remnant magnetization
Table III. This MCE value of the present GCO bulk is higher behavior. At an applied field of 7 T, the maximum magneto-
than that of all RMnO3 and RCrO3 bulk (polycrystalline) caloric values were 7.2, 14.0, and 31.6 J/kg K, and the rela-
materials. However, the value of DSM(T,H) for GCO bulk tive cooling power were 408, 490, and 546 J/kg for the
powder (19.0 J/kg K at 4 T) is lower than that of the GCO HoCrO3, Ho0.67Gd0.33CrO3, and GdCrO3 samples, respec-
single crystal, which was reported to be 26.1 J/kg K at a tively. Therefore, Gd substitution at the Ho-site was found to
field of 4 T.32 As the MCE property is direction-dependent considerably improve the magnetocaloric properties of
for single crystals, smaller MCE values for bulk powder HoCrO3. Further, present GdCrO3 bulk sample exhibits giant
samples (compared to single crystals) are expected because magnetocaloric properties, which is higher than the reported
of averaging effect.40 values for RCrO3 and RMnO3 bulk (polycrystalline) sam-
Figure 10 shows the figure of merit for magnetic refrig- ples, making it promising for applications in low-
eration, the RCP values of the samples (T1 was chosen as temperature magnetic refrigeration.
150 K for calculation using Eq. (2)). At 5 K and an applied
field of 7 T, the RCP values of HCO, HGCO, and GCO ACKNOWLEDGMENTS
bulk samples are 408, 490, and 546 J/kg, respectively (also
This work was funded by the National Science
summarized in Table III). Again, the RCP value of HCO
Foundation under Grant No. DMR-1310149.
improves considerably by Gd substitution at the A-site. DSM
and RCP values of the present GCO bulk sample were the 1
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