Effect of Gd substitution on the structural,

magnetic, and magnetocaloric properties of

HoCrO3
Cite as: J. Appl. Phys. 123, 053904 (2018); https://doi.org/10.1063/1.5003637
Submitted: 06 September 2017 . Accepted: 17 January 2018 . Published Online: 07 February 2018

Shiqi Yin, Wei Zhong, Curtis J. Guild, Jianhang Shi , Steven L. Suib, Luiz Fernando Cótica, and Menka
Jain

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 JOURNAL OF APPLIED PHYSICS 123, 053904 (2018)

Effect of Gd substitution on the structural, magnetic, and magnetocaloric

properties of HoCrO3
Shiqi Yin,1 Wei Zhong,2 Curtis J. Guild,3 Jianhang Shi,2 Steven L. Suib,2,3
Luiz Fernando Co tica,4 and Menka 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
3
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, USA
4
Physics Department, Maring a State University, Av. Colombo, 5790, Maring a, PR 87020-900, Brazil
(Received 6 September 2017; accepted 17 January 2018; published online 7 February 2018)
Rare-earth chromites are a new type of magnetoelectric multiferroics. In this work, a
Ho0.33Gd0.67CrO3 powder sample was synthesized via a citrate route, and the structural properties
were characterized by X-ray diffraction, scanning electron microscopy, and the Raman technique.
The UV-Visible optical absorbance spectra were also measured in the wavelength range of
200–800 nm. The valence state of Cr was found to be purely 3þ according to the X-ray photoelec-
tron spectroscopy. The temperature-dependent dielectric constant and loss tangent data measured
between the frequencies of 1 kHz and 1 MHz show no anomalies around the magnetic transition
temperature of the material. The dc magnetization measurements show that the ordering tempera-
ture of Cr3þ (TNCr ) is 155 K for Ho0.33Gd0.67CrO3, which is larger than 140 K for HoCrO3. The posi-
tive slope of the Arrott plots from 0 T to 7 T reveals that the antiferromagnetic-paramagnetic phase
transition is second-order in nature. At a field of 7 T, the Ho0.33Gd0.67CrO3 sample showed a giant
magnetocaloric entropy change, DS, of 23.3 J/kg K at 5 K, and a refrigeration capacity of
481.2 J/kg, which are much higher than those of pure bulk HoCrO3. This renders this material
prospective for magnetic refrigeration in the low temperature (<30 K) range. Published by AIP
Publishing. https://doi.org/10.1063/1.5003637

I. INTRODUCTION need to investigate magnetocaloric materials for cryogenic mag-

Refrigeration is crucial to modern society for domestic
life, industrial manufacturing, scientific research, etc.1
Current refrigerators are mostly based on vapor compression
refrigeration, which, however, has two main disadvantages:
it is reaching theoretical efficiency limits, and it produces
greenhouse gases that contribute to global climate change.2
Therefore, it is necessary to explore and develop alternative
refrigeration technology. One potential technology is mag-
netic refrigeration, which is based on the magnetocaloric
effect (MCE).3,4 When a magnetic field is applied adiabati-
cally to a material, its magnetic entropy changes, along with
its thermal entropy (i.e., temperature). Increasing magnetic
entropy results in a decrease of thermal entropy and vice
versa. By applying and removing a magnetic field in a
Carnot cycle, a target material can be continuously cooled
down. There are three parameters to evaluate the MCE: mag-
netic entropy change (DS), refrigeration capacity (RC), and
adiabatic temperature change (DTad).5,6 These parameters
can be measured directly or calculated indirectly by using
heat capacity or magnetization measurements.
In the past decade, the search for magnetocaloric materials
has aimed at room-temperature applications and has been
focused on materials that contain rare-earth elements with large
magnetic moments, such as Gd5(Si2Ge2),7 MnAs1–xSbx,8
ErNiBC and GdNiBC,9 and TmZn.10 Meanwhile, there also is a
a)
Author to whom correspondence should be addressed. Electronic mail:
menka.jain@uconn.edu
netic refrigeration. Recently, a new type of magnetoelectric
multiferroics, rare-earth chromites (RCrO3), were found to
exhibit remarkable MCEs at low temperatures, around
30 K.11–17 The bulk DyCrO3 sample has a large DS, of
8.4 J/kg K and a RC of  217 J/kg at temperatures of 20 K
and magnetic fields of 4 T, which renders DyCrO3 useful for
magnetic refrigeration below 30 K.18 With a perovskite structure
(ABO3), RCrO3 can accommodate host ions of various ionic
radii, and, therefore, chemical substitution/doping is an effective
way to tune their structural and magnetic properties. There have
been a few attempts to improve the MCE of DyCrO3, either by
rare-earth substitution at the A-site or by iron substitution at the
B-site. For example, an iron substituted DyCr0.5Fe0.5O3 sample
displays a DS of  10.5 J/kg at 5 K and 4 T, and a Cr3þ order-
ing temperature (Neel temperature: TNCr ) was observed at 261 K;
both are larger than those of DyCrO3.19 Besides, the A-site
substituted Dy0.7Er0.3CrO3 bulk sample exhibited an even larger
DS, of 10.92 J/kg K, at 5 K and at a magnetic field of
4 T.20,21 Among RCrO3 compounds (where R is a rare-earth
ion), HoCrO3 is of interest as Ho3þ ion has large magnetic
moment. A large DS (7.2 J/kg K) and RC (408 J/kg) at
20 K and 7 T have been reported in bulk HoCrO3.22 Fe substitu-
tion at the B-site (i.e., HoCr0.7Fe0.3O3) was found to enhance
TNCr , from 140 K to 174 K, but resulted in a smaller DS
(6.8 J/kg K) and RC (387 J/kg) values at 20 K and 7 T.22
So, the next obvious step is to try a rare-earth substitution at the
A-site of HoCrO3 based on the report by McDannald and Jain21
of rare-earth substitution at the A-site of DyCrO3.

0021-8979/2018/123(5)/053904/6/$30.00 123, 053904-1 Published by AIP Publishing.

053904-2 Yin et al. J. Appl. Phys. 123, 053904 (2018)

photoelectron spectroscopy (XPS) to identify the chemical

composition and valence state of the Cr ion. The Casa XPS
program was used to fit the XPS peaks with a linear back-
ground. Only for dielectric measurements, polyvinyl alcohol
solution was added to the annealed Ho0.33Gd0.67CrO3 pow-
der sample as a binder. After the mixed solution was dried in
a mortar, the resultant powder was compressed into a pellet
and then annealed in the air at 1300  C for 4 h. The dielectric
constant and loss tangent (tan d) as a function of temperature
(10–295 K) at various frequencies (f ¼ 1 kHz–1 MHz) with a
heating rate of 1 K/min were measured by using an Agilent
Impedance analyzer. Temperature- and field-dependent dc
magnetization was measured by using a vibrating sample
magnetometer attached to an Evercool physical property
measurement system (from Quantum Design).

III. RESULTS AND ANALYSIS

FIG. 1. (a) The X-ray diffraction data and Rietveld refinement, (b) structural
pattern (red, blue, and green spheres stand for the oxygen, holmium/gadolin-
ium, and chromium atoms, respectively), (c) Scanning Electron Microscopy
(SEM) image, and (d) Raman spectra in the energy range from 100 cm1 to
600 cm1 of the Ho0.33Gd0.67CrO3 sample.
From the literature, it was noted that Gd-based materials
exhibit excellent MCE properties, such as a Gd single crys-
tal,23 Gd alloys,5,24,25 GdMnO3 (Ref. 26), and GdCrO3 (Ref.
27) single crystals. Therefore, it is worthwhile to try enhanc-
ing the MCE of HoCrO3 by Gd substitution. In this work, the
effect of Gd substitution on the magnetic and magnetocaloric
properties of a HoCrO3 powder sample was investigated,
with an aim to enhance our understanding of the multiferroic
and magnetocaloric properties of RCrO3 that may lead to
fabrication of magnetoelectric multiferroic material with TNCr
close to room temperature.
II. EXPERIMENTAL DETAILS
High-purity Ho(NO3)3, Gd(NO3)3, and Cr(NO3)3 precursors
were mixed in the stoichiometric ratios Ho(0.33)Gd(0.67)Cr(1)
in water, with the addition of citric acid as a chelating agent.
After the solution was dried, the resultant powder was
grounded and then annealed at 900  C in oxygen for 2 h. The
crystalline structure of the sample was examined by using
X-ray diffraction (XRD) and the Raman scattering tech-
nique. Scanning electron microscopy (SEM) was used to
observe the morphological features. Room-temperature opti-
cal absorbance in the wavelength range of 200–800 nm was
measured via a diffuse reflectance integrating sphere
attached to a Shimadzu UV-2450 UV-Vis Spectrometer. The
PHI 595 Multiprobe System was used to record X-ray
The XRD h–2h scans in Fig. 1(a) show that the sample
(900  C annealed) is phase pure, with an orthorhombic crystal
structure (space group Pbnm). It should be noted that the
1300  C annealed sample (used for dielectric measurements)
was also phase pure with the Pbnm space group. From
Rietveld refinement by using Fullprof software, the atomic
positions, lattice parameters (a, b, and c), the in-plane Cr-O1-
Cr and out-of-plane Cr-O2-Cr bond angles, and Cr-O bond
length were obtained and are summarized in Table I. The lat-
tice parameters are a good match with those of pure HoCrO3
and GdCrO3.28 The crystal structure of the sample is further
visualized in Fig. 1(b) by using the VESTA package,29 with
four formula units in each unit cell. It is composed of a corner
sharing CrO6 octahedra, with a Cr atom in the center of the
octahedral and a Ho/Gd atom at the cubic center formed by
the CrO6 octahedra. The octahedra is distorted, which can be
characterized by the in-plane Cr-O1-Cr and out-of-plane Cr-
O2-Cr bond angles. Because of the distortion, the unit cells
deviate from the ideal cubic structure, which is evaluated by
the orthorhombic strain factor, S ¼ 2ðb  aÞ=ðb þ aÞ (see
Table I). The morphology of the sample was recorded by
using SEM and is shown in Fig. 1(c). No obvious impurity
exists and the particle sizes are more or less uniform.
The room-temperature Raman spectrum (when using a
514 nm laser) of the Ho0.33Gd0.67CrO3 sample in the range
from 100 cm1 to 600 cm1 was plotted in Fig. 1(d). The
orthorhombic RCrO3 with a Pbnm perovskite structure
exhibits 24 Raman-active modes, C ¼ 7Ag þ 5B1g þ 7B2g
þ 5B3g, which are activated by the broken cubic symmetry
that results from the three distortions: A-cation displacement,
tilting, and CrO6 octahedra distortion.30 In Fig. 1(d), there

TABLE I. The lattice parameters, orthorhombic strain (S), Cr-O bond length, in-plane Cr-O1-Cr, out-of-plane Cr-O2-Cr bond angles, and atomic positions
obtained from Rietveld refinement of the experimental XRD data for the Ho0.33Gd0.67CrO3 samples annealed at 900  C.

a (Å) b (Å) c (Å) V(Å3) S Cr1-O1 (Å) Cr1-O2 (Å) Cr1-O2 (Å) Cr1-O1-Cr1 (deg) Cr1-O2-Cr1 (deg)

5.301 5.533 7.599 222.88 0.04283 1.98 1.9873 2.0011 147.25 147.71

Ho(x/a) Ho(y/b) Ho(z/c) Cr(x/a) Cr(y/b) Cr(z/c) O1(x/a) O1(y/b) O1(z/c) O2(x/a) O2(y/b) O2(z/c)

0.0163 0.0608 0.250 0.500 0.000 0.000 0.0986 0.468 0.250 0.303 0.297 0.0516
053904-3 Yin et al.
TABLE II. Positions and assignment of the Raman modes of the Ho0.33Gd0.67CrO3 sample in comparison with pure HoCrO3 and GdCrO3 from the literature.
Sample Ag(2) B2g(1) B1g(1) Ag(3)
HoCrO3 (Ref. 22) 141.8 163.0 261.1 275.1
Ho0.33Gd0.67CrO3 142.6 161.1 249.5 261.7
GdCrO3 (Ref. 30) 142.2 159.3 245.3 255.5
are prominent Raman modes at 142.6, 161.1, 249.5, 261.7,
295.3, 331.3, 397.4, 482.2, and 562.8 cm1, which are well
matched with the report by Weber et al.30 and were assigned
accordingly. Table II summarizes the positions and assign-
ments of these Raman modes, in comparison with those of
pure HoCrO3 (Ref. 22) and GdCrO3.30 Phonon frequencies
below 350 cm1 depend on Ho3þ/Gd3þ ions, and phonon fre-
quencies above 440 cm1 depend on Cr3þ ions because the
heavier Ho3þ/Gd3þ ions vibrate at a lower wavenumber than
Cr3þ ions, paccording
ffiffiffiffiffiffiffiffi to the harmonic oscillator approxima-
tion, x ¼ k=l (k—force constant, l—reduced mass).30
Particularly, the Ag(2) and B2g(1) modes centered at
142.6 cm1 and 161.1 cm1 arise from Ho3þ/Gd3þ vibra-
tion, whereas the B2g(2) and Ag(3) modes centered at
295.3 cm1 and 261.7 cm1 are related to the Ho3þ/Gd3þ
cationic shift and in-phase rotation of the CrO6 octahedra.
Moreover, the Ag(5) and B1g(2) modes belong to the same
symmetry group and correspond to mode-mixing and cross-
ing.30 In addition, the modes at higher frequency are subject
to the Cr-O bending and anti-stretching vibration modes of
the CrO6 octahedra and, therefore, should undergo a
temperature-dependent shift at TNCr .31
To determine the band energy of the sample, UV-
Visible absorbance spectra were measured and are presented
in Fig. 2(a). The rare earth ions Ho3þ/Gd3þ have half-filled
4f7 electronic configurations and could have 4f-4f and 4f-5d
transitions. There are three primary peaks, at 297 nm,
456 nm, and 611 nm, which were attributed to the transitions
of 4f-5d, 4A2 to 4T1, and 4A2 to 4T1, respectively.32 It can be
seen that there is a direct band gap (Eg), which is related to
FIG. 2. (a) Optical absorption spectra of the Ho0.33Gd0.67CrO3 sample, (b)
(ah)2 vs. h by following Eq. (1) with the extrapolated red line determining
the direct energy gap, (c) x-ray photoemission spectroscopy (XPS) survey
spectrum, and (d) high-resolution XPS spectra for Cr 2p.
J. Appl. Phys. 123, 053904 (2018)
B2g(2) Ag(4) B1g(2) Ag(5) Ag(6) B3g(3)
315.0 342.7 403.0 420.1 493.5 564.5
295.3 331.3 397.4 … 482.2 562.8
284.5 324.9 388.7 392.4 477.0 568.7
the optical absorption coefficient (a) and energy of the inci-
dent photon (h) according to the Tauc equation33
ah ¼ Aðh  Eg Þ1=2 : (1)
In the plot of (ah)2 vs. h of Fig. 2(b), the value of Eg was
determined to be 2.81 eV by extrapolating the linear part of the
absorption-edge curve to the (ah)2 ¼ 0 axis. This is smaller
than that of HoCrO3 (3.1 eV by computation22 and 3.26 eV by
experiment34) and larger than that of GdCrO3 (2.7 eV).35 Thus,
it can be inferred that Eg of HoCrO3 is reduced by Gd substitu-
tion, and this tunability by A-site substitution may inspire its
photocatalytic and light-harvesting applications.36
Before exploring its magnetic property, it is noted that
chemical doping might vary the valence states of Cr ions
between Cr2þ, Cr3þ (magnetic), and Cr6þ (non-magnetic).
For instance, Desai et al.37 doped LaCrO3 with divalent Sr
and monovalent Ag, and the Cr valence changes from Cr3þ
to Cr6þ. Thus, to verify the valence state of Cr, room-
temperature XPS data of the present sample were recorded.
As shown in Fig. 2(c), the general survey scan signal arises
from Cr 2p, O 1s, C 1s, and Ho/Gd 4d, respectively, which
were calibrated with a binding energy of 286 eV of carbon
(C 1s). The Cr 2p core level binding energy spectrum in Fig.
2(d) was further resolved into three peaks centered at
576.4 eV, 586.4 eV, and 588.8 eV, respectively, attributed to
the characteristic spin-orbit splitting of the 2p level into 2p3/2
and 2p1/2.38 In particular, the peaks at 576.4 eV and 586.4 eV
are correlated to Cr3þ 2p3/2 and Cr3þ 2p1/2, respectively,
whereas the peak at 588.8 eV results from a small shake-up
contribution.38 Consistent with the XRD and Raman data,
the XPS further confirms that the present sample is phase
pure, absent of oxygen vacancies or any Cr related impurity
(such as HoCrO4, GdCrO4, CrO3, etc.). It should be noted
that the existence of Cr6þ is not rare in chromium perovskite
oxides. For instance, an extra peak at 579 eV correlated to
Cr6þ 2p1/2 was reported in DyCrO3 (Ref. 38) and YCrO3.31
To investigate the dielectric response in the proximity of
TNCr , the dependence of dielectric and loss tangents of the
Ho0.33Gd0.67CrO3 sample on temperature and frequency was
measured. Figure 3(a) shows the real part of the dielectric
constant (e0 ) at various frequencies (f ¼ 1 kHz–1 MHz).
Below 135 K, e0 displays little dependence on f or T.
Above 135 K, e0 increases significantly with increasing tem-
perature. At T ¼ 295 K, f ¼ 1 kHz, e0 shows a large value
e0 max of  3649. In the report of Ghosh et al.,39 temperature-
dependent e0 of a HoCrO3 powder sample shows a similar
trend, and no convincing anomaly was observed near TNCr ,
but its e0 max (1000) is smaller. However, e0 max of the pre-
sent sample is smaller than 6000 reported for
YFe0.5Cr0.5O3.40 The dependence of loss tangent (tan d) on
temperature was plotted in Fig. 3(b). At f ¼ 1 kHz, the value
053904-4 Yin et al.
FIG. 3. Thermal variation of (a) the real part of the dielectric constant (e0 )
and (b) loss tangent (tan d) of the Ho0.33Gd0.67CrO3 sample measured at var-
ious frequencies (1 kHz–1 MHz). The inset of (b) shows the dependence of
lnf on 1/T (data shown with solid black squares), and it is fitted to the
Arrhenius law (solid red line).
of tan d maximizes at 211 K, which is called the characteris-
tic temperature (Tm). Tm rises with the increase of f, and this
variation obeys the Arrhenius law
f ¼ f0 expðE0 =kB T Þ; (2)
where f is the alternating current frequency, f0 is a prefactor,
and E0 is the activation energy. The fitting parameters (f0
¼ 5.16  1010 Hz, E0 ¼ 0.323 eV) are in good agreement
with the reports of f0 ¼ 3.6  1010 Hz, E0 ¼ 0.335 eV in
YFe0.5Cr0.5O3,40 and E0 ¼ 0.314 eV in NdCrO3.33 This
frequency-dependent feature of tan d may be ascribed to hop-
ping conduction of localized charge carriers in the grains.40
The temperature-dependent zero-field cooled (ZFC) and
field cooled (FC) magnetic susceptibility (v) measured at the
50 Oe field is shown in Fig. 4(a). Due to the ordering of rare-
earth Ho3þ/Gd3þ ions, the FC data show a peak at 8 K, simi-
lar to the report in HoCrO3 and HoCr0.7Fe0.3O3 powder sam-
ples.22 In addition, there is an anomaly at 155 K in the
present sample related to the ordering of Cr3þ ions (Neel tem-
perature: TNCr ). TNCr was determined to be 156 K by the peak of
the d(v)/dT  T plot in the inset of Fig. 4(a), which is between
those of HoCrO3 (140 K)22 and GdCrO3 (166 K).27 Below
TNCr , v decreases gradually with increasing temperature due to
the antiferromagnetic behavior of Cr3þ ions. Nevertheless,
above TNCr , v is almost stable because of the paramagnetic
behavior of Cr3þ ions, which can be fitted to the Curie–Weiss
law: v ¼ C/(T  h). The fitting is shown in Fig. 4(b), and the
Curie constant (C) and Weiss temperature (h) were deter-
mined to be 11.72 emu K/(Oe mol) and 32.65 K, respec-
tively. A negative value of h here indicates that the transition
J. Appl. Phys. 123, 053904 (2018)
FIG. 4. (a) The temperature-dependent dc susceptibility (v) data of the
Ho0.33Gd0.67CrO3 sample under the (black square) zero-field-cooled (ZFC)
and (red cycle) field-cooled (FC) protocols with applied field H ¼ 50 Oe.
The inset shows a derivative of v with respect to temperature (dv/dT) from
140 K to 180 K to reveal the Cr3þ ordering temperature. (b) Temperature
dependence of the inverse magnetic susceptibility (1/v) measured under
H ¼ 50 Oe of the FC mode (represented by the black hollow circles) were fit-
ted to the Curie–Weiss law (the red line). (c) Magnetic hysteresis loops (M
vs. H) measured at various temperatures. (d) The temperature dependence of
a magnetic coercive field (HC, black circles data) and remnant magnetization
(MR, blue squares data) of the Ho0.33Gd0.67CrO3 sample.
is antiferromagnetic. From the fitted C value, the effective
magnetic moment (leff) was calculated to be 9.68 lB by
qffiffiffiffiffiffiffiffi
using the equation leff ¼ 3kNB C (kB—Boltzmann constant,
N—Avogadro constant).41 Alternatively, leff was calculated to
be 9.61 lB by using the free ionic moments of Ho3þ (10.4
lB), Gd3þ (7.94 lB), and Cr3þ (3.8 lB)22
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
leff ¼ l2Cr þ 0:33  l2Ho þ 0:67  l2Gd : (3)
The good agreement of leff calculated by these two methods
further confirms the correct chemical composition and phase
purity of the present Ho0.33Gd0.67CrO3 sample.
The magnetic hysteresis loop (M–H) of the present sam-
ple measured at 5 K, 50 K, 100 K, and 145 K is presented in
Fig. 4(c). As the temperature gradually increases and reaches
above TNCr , the sample shows paramagnetic behavior, as evi-
dently shown in the data measured at 150 K. It should be men-
tioned that, at 5 K and 40 kOe, the magnetization (98.0 emu/g)
is larger than that of a pure HoCrO3 sample (86.0 emu/g)
under similar conditions.22 Moreover, the dependence of coer-
cive field (HC) and remnant magnetization (MR) on tempera-
ture was extracted from the M–H curve and is shown in Fig.
4(d). Notably, in the present Ho0.33Gd0.67CrO3 sample, the
temperature-dependent HC curve shows a plateau area of
2000 Oe in the temperature range of 20–110 K and then
decreases to zero quickly near TNCr with an increase in temper-
ature. In comparison, MR increases as the temperature rises,
reaches its maximum of 2.95 emu/g at 15 K, and then
decreases gradually to zero near TNCr . Similar behavior was
reported in a DyCrO3 bulk sample and was attributed to the
superimposing Cr3þ and Dr3þ magnetic sublattices.18 In
053904-5 Yin et al.
addition, the Ho0.33Gd0.67CrO3 sample shows a much smaller
magnetic hysteresis than a pure HoCrO3 sample, with a plateau
of 2500 Oe in the HC curve and a maximum MR of
33.5 emu/g.22 In the ensuing discussion, the effect of a Gd
substitution on the MCE property of HoCrO3 will be discussed.
Figure 5(a) shows the isothermal M–H curve of the
Ho0.33Gd0.67CrO3 sample. It can be seen that, at a fixed temper-
ature, the magnetization rises with increasing magnetic field.
The MCE property considerably depends on the nature of the
corresponding magnetic phase transition: a first-order field-
induced paramagnetic to ferromagnetic transition can generate
a large MCE in a narrow temperature range, whereas a second-
order magnetic transition generates MCE that spreads over a
broad temperature range and is beneficial for magnetic refriger-
ation.5 In order to understand the nature of the magnetic phase
transition of the sample, Fig. 5(b) displays the Arrott plots, the
slope of which indicates the order of magnetic transition (a
positive slope for second-order transition and a negative slope
for first-order transition).19,42 The positive slope of the Arrott
plots in the present case reveal that the antiferromagnetic-
paramagnetic phase transition is second-order in nature.5
From isothermal M–H data of Fig. 5(a), the MCE can be
evaluated primarily in terms of two parameters: magnetic
entropy change (DS)5,24
ðH  
@MðT; H Þ
DSðT; H Þ ¼ dH
0 @T H
X Miþ1 ðTiþ1 ; H Þ  Mi ðTi ; H Þ
 DH; (4)
Tiþ1  Ti
i Ho0.33Gd0.67CrO3 sample, one peak was observed at 8 K,
and refrigeration capacity (RC)
ð T2
 
RC ¼ DSM;H dT;
T1
where T1 ¼ 5 K and T2 ¼ 150 K were taken as the tempera-
tures of the cold and hot sources, respectively. Figures 5(c)
FIG. 5. (a) Isothermal magnetization curves (in the first quadrant) at temper-
atures of 5–150 K and (b) Arrott plot constructions, temperature-dependent
(c) magnetic entropy change (DS), and (d) refrigeration capacity (RC) of
the Ho0.33Gd0.67CrO3 sample. The inset of (c) shows the low temperature
DS, from 5 K to 10 K.
J. Appl. Phys. 123, 053904 (2018)
and 5(d) show the temperature-dependent DS and RC,
respectively, of the present sample with different applied
magnetic fields. The inset of Fig. 5(c) shows the low temper-
ature DS, from 5 K to 10 K. It can be seen that, with
increasing the applied magnetic field, both DS and RC
increase because of larger magnetization induced under a
higher magnetic field. At 5 K and H ¼ 7 T (1 T ¼ 10 000 Oe),
DS is maximum of 23.3 J/kg K, and RC is 481.2 J/kg,
which are much larger than those of pure HoCrO3 (DS of
7.2 J/kg K, RC of 408 J/kg).22 The third parameter is adi-
abatic temperature change (DTad), calculated by
ðH  
T @M T
DTad ¼ l0 dH  DS: (6)
CH @T H CP
0
The above approximation was based on the precondition that
CH/T shows little dependence on the magnetic field, as reported
by Su et al.43 The maximum DTad is calculated by using
CH/T  0.8 J/(mol K2) at 20 K for the Ho0.33Gd0.67CrO3 sam-
ples. Under the magnetic field change of 7T, DTad for
Ho0.33Gd0.67CrO3 samples is 7.71 K, which is larger than
DTad of 2.39 K for a HoCrO3 sample.15 Thus, it should be
noted that all three parameters that evaluate a material for
the MCE enhance with 67% Gd substitution in HoCrO3.
Hence, Gd substitution significantly improved MCE in
HoCrO3, consistent with the giant DS previously reported
in a pure GdCrO3 sample of 31.6 J/kg K at 3 K and 4.4 T.27
In the temperature-dependent magnetic data of the present
which could be due to Cr3þ spin-reorientation temperature
(TSR) as observed in GdCrO3 single crystal data27 or order-
ing temperature for Ho3þ as the Gd3þ ordering temperature
(5) in a single crystal is 2.3 K (lower than our measured range).
The peak observed, 8 K, is suppressed when a higher mag-
netic field is applied (not presented here). From Figs. 5(a)
and 5(c), it can be clearly seen that the magnetization, curva-
ture of the M-H curves, and magnetic entropy change (DS)
keep increasing even below 8 K (the lowest measurement
temperature is 5 K). This may indicate that the larger MCE
in the present Ho0.33Gd0.67CrO3 sample compared with pure
HoCrO3 is likely to be mainly related to the Gd3þ-Gd3þ
interaction (now present in a Gd doped sample) and partially
due to magnetic entropy induced by the spin-reorientation of
Cr3þ and Gd3þ ions due to the Cr3þ-Gd3þ magnetic interac-
tion. It has also been reported that the Gd substitution in a
HoCrO3 sample decreases the magnetic hysteresis.22
Therefore, less energy loss is generated in the thermal pro-
cess, which results in larger MCE values for the
Ho0.33Gd0.67CrO3 sample compared with a HoCrO3 sample.
This enhancement of MCE in HoCrO3 by Gd substitution
provides important insights on its applications for magnetic
refrigeration in a low-temperature region.
IV. CONCLUSION
A Ho0.33Gd0.67CrO3 powder sample was synthesized by
using a citric sol-gel method. Analysis of X-ray diffraction
data demonstrates that the phase-pure sample has an
053904-6 Yin et al.
9
orthorhombically distorted crystal structure with a space
group of Pbnm. The micro structure of the sample was exam-
10
ined by Scanning Electron Microscopy. Analysis of Raman
scattering data further confirms that the sample is phase 11
pure. By measuring the UV-Visible spectra, the band gap is
12
determined to be 2.81 eV and weakened by Gd substitution.
By using X-ray photoelectron spectroscopy, the valence of 13
Cr was determined to be þ3 and not varied by Gd substitu-
14
tion. The real part of the dielectric constant e0 and loss tan-
gent tan d show little dependence on frequency or 15
temperature below 135 K, but they both rise rapidly with
16
increasing the temperature above 135 K. The characteristic
17
temperature where tan d maximizes was observed to increase
with increasing frequency, which obeys the Arrhenius law. 18
The dc magnetic measurement shows that the ordering tem- 19
perature of Cr3þ (TNCr ) was increased to 156 K by Gd substi- 20
tution. The magnetic behavior of the sample changes from
canted antiferromagnetic below TNCr to paramagnetic above 21
TNCr . The magnetization data above TNCr was fitted to the 22
Curie-Weiss law, and the effective magnetic moment was
23
determined to be 9.68 lB, in good match with the result
when using free ionic moments (9.61 lB). The positive slope 24
of the Arrott plots shows that the antiferromagnetic-
25
paramagnetic phase transition is second-order in nature, and
the present sample should be more suitable for active mag- 26
netic refrigeration. At H ¼ 7 T, the maximum magnetic
entropy change is 23.3 J/kg K at T ¼ 5 K and the refrigera- 27
tion capacity is 481.2 J/kg, which are much larger than those
28
of pure HoCrO3. Hence, Gd substitution significantly 29
enhanced MCE in HoCrO3, which is enlightening to the 30
design of new materials suitable for applications in magnetic
31
refrigeration. Detailed heat capacity measurements in the
32
presence of a magnetic field and direct DTad measurements 33
can shed more light on the fundamental nature and potential
34
application of these Gd substituted HoCrO3 materials. 35
ACKNOWLEDGMENTS 36
37
This work was supported by a research grant from the
U.S. National Science Foundation (No. DMR-1310149). 38
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