Journal of Alloys and Compounds 804 (2019) 401e414

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Structural, morphological, thermal and optical investigations on Mn

doped GdCrO3
Aref Alqahtani, Shahid Husain*, Anand Somvanshi, Wasi Khan
Department of Physics, Aligarh Muslim University, Aligarh, 202002, India

a r t i c l e i n f o a b s t r a c t

Article history: Perovskite-type GdCr1-xMnxO3 (0.0
x
0.4) nano-crystalline samples are synthesized using sol-gel auto
Received 18 April 2019 combustion process. The effect of Mn-doping in GdCrO3is investigated in term of structural, morpho-
Received in revised form logical, optical and thermal properties. X-ray diffraction (XRD) patterns confirm orthorhombic crystal
16 June 2019
structure of all the samples. The lattice parameters bond lengths and bond angles as obtained from
Accepted 3 July 2019
Rietveld refinement analysis are found to vary systematically with Mn concentration. The crystallite sizes
Available online 4 July 2019
as calculated from the Scherrer's equation are found to decrease with Mn content. The Williamson-Hall
(WeH) analysis reveals that the crystallite sizes decrease whereas lattice strain, stress, and energy
Keywords:
Orthochromites
density become more with the increase in Mn doping except for x ¼ 0.3.The particle size estimated using
Williamson Hall analysis transmission electron microscopy (TEM) are consistent with that obtained through WeH analysis.
Optical properties Scanning electron microscopy (SEM) images with energy dispersive x-ray (EDX) analysis exhibit sig-
Differential thermal analysis nificant change in the surface morphology with Mn doping and ensure the elemental compositions of the
samples. The Fourier transform infrared (FTIR) spectra of these samples confirm the formation of desired
crystal structure with two main characteristic bands at 476 and 586 cm1. The optical band gap is found
to reduce whereas Urbach energy increases with the increase in Mn concentration. The values of
refractive index decrease in the ultraviolet region as a function of wavelength for all the samples and
minimizes at the main absorption peak position as observed in the UV/Vis. spectra. The value of heat
capacity at constant pressure (Cp) decreases with Mn doping except for 30% Mn concentration. Therefore,
the present investigation suggests that the properties of GdCrO3 system can be tuned with the appro-
priate doping of Mn for the potential applications.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction performance of perovskite oxides because perovskite oxides are

new type of electrode materials. In another work, Apostolov et al.
The presence of transition metal and rare earth ions in the [6] have investigated the magnetic and dielectric properties of
crystal lattice and stabilisation of novel oxidation states make the YCrO3 and GdCrO3 nanoparticles by employing the microscopic
perovskite family (ABO3) to exhibit a wide spectrum of fascinating model and Green's function technique. They have observed effect of
electrical, dielectric, magnetic and optical properties [1].There are particle size on the magnetic and dielectric properties of these
various combinations of A and B cations that produce perovskite- compounds associated with different surface exchange in-
type oxides. Partial replacement of other cations for both (A) and teractions. In comparison with the typical cubic perovskite ABO3,
(B) sites is achievable with no effect on the fundamental crystal the real perovskites exhibit lattice distortion of varying degrees and
form [2]. However, deficiencies of cations at the A- or B-sites or of thereby resulting in the transformation of various crystal phases.
oxygen anions are frequent, which result in defective perovskites. Most metal elements found in periodic table are considered to be
The non-stoichiometry in perovskites has been deeply explored stably located in ABO3 structures, and multi component ABO3
and discussed earlier [3,4].Qing Lin et al. [5] have studied Mg- materials are easily combined by partial replacement of cations at
doped La1-xMgxFeO3 perovskites to improve the electrochemical both (A) and (B) sites. In this context, rare-earth orthochromites
(RCrO3) with the orthorhombic Pnma structure, display a multitude
of different properties ranging from p-type semiconductor behav-
* Corresponding author. iour [7] catalytic activity toward the decomposition of N2O gas into
E-mail address: s.husaincmp@gmail.com (S. Husain). N2 and O2 [8] and doping of alkali-earth metals into the structure

https://doi.org/10.1016/j.jallcom.2019.07.028
0925-8388/© 2019 Elsevier B.V. All rights reserved.
402 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414

gives rise to properties ideal for solid oxide fuel cell interconnect thermal analyzer in the temperature range of 30e1000  C with a
materials [9,10]. A variety of synthesis processes have been heating rate of 20  C min1 under nitrogen atmosphere.
employed to prepare RCrO3 and their doped counterparts. These
include hydrothermal [11], solid-state reaction route [12], sol-gel 3. Results and discussion
[13], microwave-assisted solid state reaction route [14], self prop-
agating high temperature synthesis [15], polyol-mediated synthesis 3.1. Structural analysis
[5] processes. These orthochromites display very rich magnetic
properties as a result of the interaction between Rþ3 and Crþ3 ions X-ray diffraction data for GdCr1-xMnxO3(0.0
x
0.4) samples
associated with different kinds of magnetic ordering at lower were gathered at room temperature that agreed well with the
temperatures. The antiferromagnetic ordering temperature is standard data from crystallography open database (COD) as pre-
greatly influenced by the rare earth ionic radius and linearly goes sented in Fig. 1(a).An orthorhombic crystal structure with space
up with the ionic radius increase in the lanthanide series from 135 group Pbnm is confirmed by (011), (111), (020), (112), (200), (021),
to 289 K for ErCrO3 and LaCrO3 respectively. This increase in the (211), (022), (202), (113), (220), (004), (221), (131), (131), (024),
ordering temperature might be related to the increase in the lattice (312), (113), and (224) diffraction peaks with highest intensity of
distortion and a decrease in the Cr3þ-O2-Cr3þ angle, thereby (112). Fig. 1(b) indicates a slight shift in the most intense peak (112)
varying the inter-cationic superexchange interaction with the size associated with the Mn doping in GdCrO3. Structural Rietveld re-
increase of the rare earth ion [16]. Perovskite type chromites are finements from XRD patterns of all GdCr1-xMnxO3 samples were
very beneficial in low temperature magnetic refrigeration that performed utilizing FullProf software. Rietveld refinement analysis
opened a new window for the development of magnetic refriger- of the XRD patterns (Fig. 2) confirms the formation of single phase,
ation technology based on magnetocaloric effect. This technology is with no characteristic reflection peaks from any impurity phase of
more efficient, inexpensive and harmless as compared to the con- GdCr1-xMnxO3 samples. The refined structural parameters are
ventional ones [17]. In this framework, gadolinium chromite tabulated in Table 1.The values of weighted profile factor Rwp are
(GdCrO3) belongs to the same family of rare earth orthochromites found within the limit that further ensure quality of the refinement.
and is found to crystallize in a distorted perovskite structur- The c2values near about one establishes the goodness of the fitting
e.GdCrO3 exhibits multiferroism with coupling between magnetic [19,20].The dissimilarity between the intensities of the calculated
ordering and electrical polarization. In this system three dissimilar and measured patterns is observed to increase with the increase in
kinds of interactions take place, namely the CreCr, CreGd and Mn concentration, indicating the distortion of the structure. We
GdeGd, but as their magnitudes differ considerably, these in- have also shown schematic representation of perovskite structure
teractions dominate in different temperature ranges. Above 100 K of GdCrO3 with the help of refined structural parameters (Fig. 2).
the CreCr interaction predominates in determining the magnetic Moreover, the peaks of doped samples are shifted as compared
properties, generating magnetic ordering of the Cr system at 170 K. to the pristine sample and the peak at 2q ¼ 23.2 transform into a
Below 100 K the impacts of the CreGd interaction turn to be sig- duplet with the increase in Mn content, where extra peak corre-
nificant, whereas at temperatures in the liquid helium range Gd-Gd sponds to Gd2MnO4. Initially, the most intense peak shifts toward
interaction dominates [18]. higher value of 2q but further doping (x ¼ 0.3 and 0.4) results in
On the basis of above discussion, we undertook synthesis of shifting of the most intense peaks toward the lower 2q value. The
GdCr1-xMnxO3 (0.0
x
0.4) samples using sol-gel process and peak shifting indicates the lattice relaxation due to replacement of
studied their structural, morphological, thermal and optical prop- the Cr by Mn ions leading to the distortion of Cr/MnO6 octahedra.
erties to observe the effect of Mn doping. To the best of our Table 2 shows the broadening (b) and 2q values of selected peaks.
knowledge, no reports are available on the structural, thermal and The unit cell parameters a and b are found to increase systemati-
optical properties of Mn doped GdCrO3. cally while c reduces with the increase in Mn content. This is
attributed to the larger size of Mn2þ(0.67 Å) ions as compared to
2. Experimental Cr3þ (0.62 Å) ions. The decrease in the c parameter indicates to-
wards cooperative stretching of ab plane of Cr/MnO6 octahedra.
The samples of GdCr1-xMnxO3(0.0
x
0.4) were synthesized Consequently, the unit cell volume should increase with Mn
by solegel process using the stoichiometric amounts of highly pure doping which is confirmed by the experimental values as obtained
Gd(NO3)2.6H2O, Mn(NO3)2.4H2O and Cr(NO3)3.9H2O in 50 ml of using Rietveld refinement analysis. Fig. 3 displays the variation of
deionized water. The citric acid was added to the solution in the lattice parameters and unit cell volume with Mn content for the
molar ratio of 2:1 with respect to the metal cation in order to
convert the nitrates into citrates. The uniform solution added with
ethylene glycol was heated at 70  C to get voluminous precursor.
The precursor was ground and sintered at 600  C for 12hours. The
crystalline phases of the samples were tested by x-ray diffractom-
eter (Shimadzu Lab XRD-6100) with Cu-Ka radiation (l ¼ 1.5406 Å)
in the 2q range of 20e80 with a step size of 0.02. UV/Vis spectra
are recorded using (Lambda 850, PerkinElmer) spectrophotometer
in the wavelength range of 200e800 nm. FTIR spectrometer
(Bruker Tenser 37) is used to record the transmission mode FTIR
spectra in the wavenumber range of 400e4000 cm1with a step
size of 2 cm1. The surface morphology of the selected samples was
investigated by the scanning electron microscope (SEM) equipped
with energy dispersive x-ray(EDX) analyzer on JEOL JSM-6510 LV
system. The particle sizes of the samples were estimated by the
Transmission electron microscope (TEM) with JEOL JSM-2100 sys-
tem operating at 200 kV. The thermal properties of GdCr1-xMnxO3 Fig. 1. (a) XRD patterns, and (b) The shift in the most intense peak of GdCr1-xMnxO3
(0.0
x
0.4) were analyzed using STA-8000 (PerkinElmer) (0.0
x
0.4) samples.
 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414 403

Fig. 2. (a) Schematic representation of perovskite structure of GdCrO3 (bef) Rietveld refined XRD patterns of GdCr1-xMnxO3 (0.0
x
0.4).
404 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414

Table 1
Structural parameters for GdCr1-xMnxO3 (0.0
x
0.4) as obtained from Rietveld refinement.

Structural parameters x ¼ 0.0 x ¼ 0.1 x ¼ 0.2 x ¼ 0.3 x ¼ 0.4

a(Å) 5.3131 5.3164 5.3192 5.3222 5.3222

b(Å) 5.5211 5.5262 5.5414 5.5575 5.5715
c(Å) 7.6044 7.6013 7.5935 7.5862 7.5899
V (Å)3 223.066 223.269 223.826 224.387 225.060
DS(nm) 28.31 24.88 23.14 20.87 19.67
c2 1.10 1.10 1.13 1.20 1.29
r (g/cm3) 7.660 7.660 7.652 7.641 7.620
<Mn/CreO>(Å) 1.976 1.976 1.978 1.980 1.982
Mn/Cr-(O1) eMn/Cr1 150.22 150.19 150.14 150.10 150.11
Mn/Cr-(O2) e Mn/Cr1 150.77 150.78 150.82 150.85 150.87

Table 2
Peak broadening (b) and 2q values of selected peaks used in Scherrer equation and Williamson-Hall analysis.

Mn conc. (x) Miller indices

(111) (112) (202) (312) (131)

2q b 2q b 2q b 2q b 2q b
0.0 26.020 0.2549 33.179 0.2384 41.439 0.2586 59.913 0.4267 54.06 0.4368
0.1 26.035 0.2858 33.202 0.2577 41.446 0.3266 59.935 0.4667 54.050 0.4947
0.2 26.039 0.2899 33.203 0.2968 41.425 0.3490 59.901 0.5021 53.898 0.5235
0.3 25.983 0.3364 33.177 0.3431 41.376 0.4212 59.873 0.5075 53.856 0.5024
0.4 25.915 0.3534 33.108 0.3237 41.366 0.4376 59.864 0.5449 53.825 0.6638

GdCr1-xMnxO3 (0.0
x
0.4).The charge neutrality of the system is of Cr/MneO bond lengths [24]. The average value of <Cr/MneO>
disturbed by the substitution of Mn2þions in place of Cr3þions in bond length becomes more with the increase in Mn content from
GdCrO3, which creates charge imbalance. To preserve the charge 1.976 to 1.982 Å because of slightly larger ionic radius of Mn2þ than
neutrality of the system, Cr3þions convert into Cr2þ ions with the that of the Cr3þions.
creation of oxygen vacancies; this means an increased concentra-
tion of Mn leads to the increased number of oxygen vacancies in the
3.1.1. Williamson-Hall analysis
system which favours the formation of Gd2MnO4 phase [21].The
Williamson-Hall method [25] is one of the most reliable tech-
average crystallite size (Ds)as estimated from the line broadening of
niques of strain/size estimation. It assumed that the broadening
(111), (112), (202), (312) and (131) peaks using Scherrer's equation
from the two dissimilar sources has different angular relationships.
[22] is given in Table 1 for all the samples. The crystallite size is
For instance, the size broadening as described in the Scherrer's
found to decrease with the increase in Mn concentration for all
equation has a 1/cosq dependence while the strain (bhkl ¼ 4ε tanq)
samples. This variation may be attributed to the fact that the ionic
has a tanq function.
radius of the dopant ion, Mn2þ (0.67 Å) is slightly larger than Cr3þ
WilliamsoneHall approach for line broadening can be
(0.62 Å). The tolerance factor also gives an indication of the ex-
computed using the formula,
pected distortion in GdCrO3 structure and its value decreases from
0.827 for GdCrO3 to 0.806 for GdMnO3 [23], indicating that kl
distortion increases with the increase in Mn content. Consequently, bhkl cosq ¼ þ 4εsinq (1)
D
the distortion of the perovskite structure observed through varia-
tion of CreOeCr bond angles and CreO bond lengths. Table 1 where ε is the lattice strain. This equation consists of two parts, the
contains the selected Cr/MneOeCr/Mn bond angles and averages first part is related to the size and the second one is related to the
strain. A plot was drawn with 4sinq along the x-axis and bhklcosq on
the y-axis for GdCr1-xMnxO3(0.0
x
0.4) as shown in Fig. 4. From
the linear fit to the data, the crystallite size was determined from
the y-intercept and the strain by the slope of the fit line. Equation
(1) is referred as uniform deformation model (UDM), where the
strain was supposed to be uniform in all crystallographic directions,
thus considering the isotropic nature of the crystal.
Based on Hooke's law, there is a linear proportionality relation
between the stress (s) and strain (ε), s ¼ Eε, where E is the elasticity
modulus or Young's modulus [26].This equation is valid for the
significantly small strain. So, it is assumed that a small strain to be
present in the GdCr1-xMnxO3 (0.0
x
0.4) samples. Applying the
Hooke's law approximation to UDM, the modified equation is given
by

kl 4ssinq
bhkl cosq ¼ þ (2)
Fig. 3. The variation of lattice parameters and unit-cell volume of GdCr1-xMnxO3 D Ehkl
(0.0
x
0.4) as a function of the Mn concentration.
 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414 405

Fig. 4. Williamson-Hall plots of GdCr1-xMnxO3 (0.0
x
0.4) assuming uniform

deformation model (UDM).
Fig. 5. Williamson-Hall plots of GdCr1-xMnxO3 (0.0
x
0.4) assuming uniform
deformation stress model (UDSM).
The above equation is called uniform deformation stress model
(UDSM). Here, Ehkl is Young's modulus in the direction normal to
the set of (hkl) planes. Young's modulus Ehkl for samples with and homogeneous. The presupposition of homogeneity and isot-
orthorhombic crystal symmetry is given by; ropy is not justified for all cases. The proportionality constants for

1 h 
¼ a4 h4 S11 þ 2a2 h2 b2 k2 S12 þ 2a2 h2 c2 l2 S13 þ b4 k4 S22 þ 2b2 k2 c2 l2 S23 þ c4 l4 S33 þ b2 k2 c2 l2 S44 þ a2 h2 c2 l2 S55 þ a2 h2 b2 k2 S66 =
Ehkl
#
 2
2 2 2 2 2 2
a h þb k þc l (3)

the strain-stress relationship are not widely used when studying

the deformation energy density (u). For an elastic system that is
The calculated values of elastic compliances Sij for orthorhombic based on Hooke's law, the density of energy can be calculated from
crystal system are 272.0, 263.8, 323.2, 73.0, 67.4, 94.3, 162.9, 130.5 the relation, u ¼ ðε2 Ehkl Þ=2. So, UDM equation can be modified
and 110.0 GPa for S11, S22, S33, S44, S55, S66, S12, S13, and S23, according to the energy and strain relationship as following;
respectively [27].UDSM plots were drawn with 4sinq/Ehkl along the
x-axis and bhklcosq along the y-axis for all the samples as shown in kl
bhkl cosq ¼ þ 4sinq ð2u=Ehkl Þð1=2Þ (4)
the Fig. 5. The slope of the straight line gives the uniform stress and D
the crystallite size was determined from the intercept [28].Another The bcosq versus 4sinq(2/Ehkl)1/2graphs are plotted and fitted
model used to identify the energy density of a crystal is called the linearly to determine the crystallite size and anisotropic energy
uniform deformation energy density model (UDEDM). In the pre- density (u) for all the samples as shown in Fig. 6. The calculated
vious models (UDSM and UDM), crystals are assumed as isotropic values of crystallite size, strain, stress and energy density obtained
406 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414

contribution to the crystallite size is smaller, leading to the larger

value in Williamson-Hall analysis as compared to Scherrer's
equation [29,30].
The mean values of crystallite size extracted from WeH
methods (UDM, UDSM, and UDEDM) are close to each other,
which mean that the strain in different forms of WeH methods has
a very small impact on the mean crystallite size of GdCr1-xMnxO3
(0.0
x
0.4) samples. The lattice strain, stress and energy density
values give an indication of the expected distortion in GdCrO3s-
tructure. It can be noticed that the lattice strain, stress and energy
density values get larger with the increase in Mn concentration.
This increase is ascribed to the large density of oxygen vacancies in
their crystal structures, which are produced due to structural dis-
tortions on Mn doping.

3.1.2. Morphological studies

In order to study the internal microstructure and particle size,
TEM images of GdCr1-xMnxO3 (x ¼ 0.0 and 0.30) were captured at
50,000 magnification as shown in Fig. 7(a and b) and 8(a, b).
These images reveal that the particles are almost spherical in shape
and having smooth surfaces. High resolution transmission electron
microscopy (HRTEM) lattice images (insets of Figs. 7(b) and 8(b))
show that each particle has a single crystalline structure. From
lattice fringes, we have determined the interplanar spacing that
found to be 3.83 and 2.78 Å which are associated with the (110)

Fig. 6. Williamson-Hall plots of GdCr1-xMnxO3 (0.0
x
0.4) assuming uniform

deformation energy density model (UDEDM).

using WeH analysis are listed in Table 3. It is observed that the

crystallite size in this case is larger as compared to that obtained
from Scherrer's equation. This may be due to the fact that in
Scherrer's equation whole of the broadening is ascribed to the size
of crystallites whereas in Williamson Hall analysis the broadening
of diffraction peaks is due to the lattice size and strain. As the
Fig. 7. (a,b) TEM images, (c) Particle size distribution, and d) SAED pattern of GdCrO3
crystallite size is inversely proportional to the broadening, hence its
nanoparticles. Inset in (b) represents HRTEM image of the same.

Table 3
Particle size and other structural parameters of GdCr1-xMnxO3 (0.0
x
0.4) samples as estimated from the Williamson-Hall Analysis.

Mn conc. UDM UDSM UDEDM Average particle size using TEM

(x) (nm)
Crystallite size Lattice strain Crystallite size Lattice stress Crystallite size Energy density u
(nm) (103) (nm) (MPa) (nm) (kJm3)

0.0 99.7 2.59 89.0 104.9 97.6 140.0 53

0.1 81.5 2.85 75.3 117.0 81.1 172.0 e
0.2 78.3 3.09 78.8 131.5 81.5 209.0 e
0.3 37.8 2.13 38.6 92.9 38.6 101.6 28
0.4 59.0 3.50 57.3 146.6 59.7 263.7 e
 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414 407

[33].The band at 1020 cm1is due to the symmetric CreO stretching

[34].The bands between 1700 and 1300 cm1 are associated with
the C¼O and CeOeC stretching vibrations for the ester groups due
to the esterification between citric acid and ethylene glycol. The
presence of the band around at 3420 cm1 is due to the stretching
mode of the hydroxyl group of bound water molecules.The spectra
of doped samples display slight shifting of the bands and variation
in the intensity of transmittance as shown in the Fig. 10. The bands
at 479 and 585 cm1 show a significant variation in intensity with
Mn doping. The band at 479 cm1 shows a slight shift towards the
lower wavenumber while the band at 3420 cm1exhibits a slight
shift towards the higher wavenumber with the increase in Mn
doping. These shifting may be attributed to the replacement of Cr
by Mn ions leading to the distortion of Cr/MnO6 octahedra.

3.2. Optical properties

The UV/Vis. diffused reflectance spectra (DRS) of all the samples

are recorded at room temperature in the wavelength range of
200e800 nm. We have used the most popular method to deter-
mine the absorption coefficient (a) from the diffuse reflectance
spectrum(DRS) using Kubelka-Munk function, F(R) given as [35].
Fig. 8. (a, b) TEM images, (c) Particle size distribution, and d) SAED pattern of
ð1  R∞ Þ2
GdCr0.7Mn0.3O3 nanoparticles. Inset in (b) represents HRTEM image of the same. FðRÞ ¼ fðaÞ (5)
2R∞

plane of GdCrO3 and (020) plane of GdCr0.7Mn0.3O3 samples where, R∞ represents the diffuse reflectance of the sample that has
respectively. The values of interplanar spacing are well matched infinite thickness.
with those obtained from the powder XRD data analysis. The par- In Fig. 11, we have shown the UV/Vis. reflectance spectra (R%)
ticle size distribution of GdCrO3nanoparticles varies from 40 to observed for GdCr1-xMnxO3(0.0
x
0.4) samples. It can be
80 nm with an average size of 53 nm while from 15 to 40 nm with noticed from the spectra that the reflectance in the visible region
an average particle size of 28 nm for GdCr0.7Mn0.3O3 sample. for the doped samples is lower as compared to the pristine one.
Figs. 7(c) and Fig. 8(c) represent particle size distribution obtained These spectra exhibit main broad dip at around 310 nm for all the
from TEM images. The corresponding selected area electron samples with a red shift on Mn doping. In GdCrO3, the Gd3þ has
diffraction (SAED) patterns are also shown in Figs. 7(d) and 8(d) electronic configuration of 4f7 and it could have 4f /4f, 4f/5d
respectively. These patterns confirm polycrystalline nature of the transitions as well as charge transfer transitions in different energy
samples. ranges. The broad dip present at 310 nm is due to the 8S7/2 / 6I11/2
The microstructure and morphology of the samples were absorption of Gd3þ ion [36]. Generally, four transitions are observed
examined using scanning electron microscope (SEM) with an en- at 454, 617 and 692, 735 nm arising from crystal field splitting of 4f
ergy dispersive x-ray (EDX) spectrometer attachment for the and 2G levels of Cr3þ ion in GdCrO3 and originating from the
4
elemental composition analysis. SEM images along with EDX A2g/4T1g, 4A2g/4T2g and 2A2g/2T1g, 2A2g/ 2E2g transitions
spectra of GdCr1-xMnxO3(x ¼ 0, 0.1 and 0.3) are shown in Fig. 9, respectively [37].These bands could be explained in terms of crystal
which represent uniform distribution of grains and variation in field splitting. According to it, the octahedral crystal field around
morphology with the increase in Mn concentration. It is evident the Cr3þ ion in GdCrO3 splits the 4F level into a ground state orbital
that the nanoparticles are more uniform and tightly interconnected singlet 4A2 and excited state orbital triplets 4T2 and 4T1. Additionally,
to each other in low Mn doped samples. Moreover, boundaries due to the crystal field, splitting of the free-ion excited state 2G gave
between the grains are clearly visible and the morphology of the rise to level 2E.
particles is more regular. We have also observed decrease in par- The spectroscopy of Cr3þ ions in octahedral crystal fields is
ticle size with the increase in Mn concentration. This suggests that shown in Fig. 12 [38],which exhibits the variation of crystal field
the increase in Mn2þ concentration inhibits the growth of particles, energy of the d3 configuration as a function of the octahedral field
resulting decrease in particles size for the higher Mn doped sam- strength. The broad bands of Cr3þobserved at 454 and 617 nm are
ples [31,32]. The EDX spectra exhibit only Gd, Cr, and O in pristine due to the transitions from level 4A2 to the level 4T2 (band centred at
sample while additional element Mn in doped samples. We have 617 nm) and 4T1 (band centred at 454 nm). Additionally, the tran-
coated our samples with gold to prevent charging of the specimen, sitions from the ground state 2A2 to the level 2T1 and 2E led to the
so some gold peaks are visible and no other impurity peak is pre- broad bands centred at 692 and 735 nm, respectively [39].
sent that signify purity of the synthesized samples. The optical energy gap (Eg) is determined using the Tauc's
relation:
 n
3.1.3. Fourier transform infrared (FTIR) spectroscopy ahn ¼ A hn  Eg (6)
The FTIR spectra of GdCr1-xMnxO3 (0.0
x
0.4) samples are
shown in Fig. 10. The formation of GdCrO3 structure was confirmed where a is the absorption coefficient, A is a characteristic parameter
by the two main absorption bands at 479 and 585 cm1.These independent of the photon energy, hn represents the incident
bands are attributed to the stretching of GdeO bonds in GdCrO3 photon energy and n represents the transition type which depends
408 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414

Fig. 9. SEM micrographs and corresponding EDX spectra of GdCr1-xMnxO3(x ¼ 0.0, 0.1 and 0.3) nanoparticles.

on the nature of the material. The values of n are 1/2 for direct a valuable optical parameter used to investigate the localized states
allowed, 3/2 for direct forbidden, 2 for indirect-allowed and 3 for in the band gap [43]. According to Urbach law the absorption co-
indirect forbidden transitions [40].As the absorption coefficient a is efficient at the photon energy under the optical band gap depends
proportional to the KubelkaeMunk function F(R),we have plotted exponentially on the photon energy as:
the graphs between [F(R)hn]2 versus hn as shown in Fig. 13. The
intersect of the extrapolation of the linear region of this plot, at
hn
[F(R)hn]2 ¼ 0 gives the energy band gap (Eg) [41]. a ¼ a0 eEu (7)
The values of band gap obtained using Tauc's relation are given
in Table 4. It can be noticed that band gap values fell in the range of where ao is a constant.
wide band gap semiconductors and substitution of Cr by Mn results Taking the logarithm on both sides of the equation (7), we get a
in the decrease of energy gap from 3.83eV for pristine GdCrO3 to straight line equation given as:
3.69eV for GdCr0.7Mn0.3O3. This decrease can be attributed to the
creation of localized states in the band-gap region due to effect of lna ¼ lnao þ (hn/Eu) (8)
possible defects or vacancies on doping. The optical absorption
spectra near the absorption band edge are widely used for char- Since Kubelka-Munk function, F(R) is directly proportional to
acterization of semiconductor materials [42]. Urbach energy (Eu) is absorbance coefficient (a), we have plotted lnF(R) against the
incident photon energy hn to obtain Urbach energy (Eu) from the
 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414 409

drawn with 1/l along the x-axis and (A/l)2 along the y-axis for
GdCr1-xMnxO3 (0.0
x
0.4) as shown in Fig. 16. The intersection
of the extrapolated linear portion of the plot with the x-axis gives
the value of threshold wavelength. The threshold wavelength is
found to increase with the increase in Mn concentration which
means that the less energy is required to eject the electrons from
Mn doped samples. The estimated results were matched with the
energy gap determined using Tauc's relation as we have seen
earlier. As we know that when light passes through a medium,
some part will be attenuated. This can be easily kept into consid-
eration by clarifying a complex refractive index (n* ¼ n þ ikÞ, Here,
the refractive index is the real part n, while k is the imaginary part
and called the extinction coefficient, also it can be referred as the
coefficient of mass attenuation.
We have determined the refractive index (n) of our samples
using the following relation [47].

ðn  1Þ2 þ k2
R¼ (10)
Fig. 10. FTIR spectra of GdCr1-xMnxO3(0.0
x
0.4). ðn þ 1Þ2 þ k2
For transparent media, extinction coefficient, k≈0 and we can
slope of the straight line as illustrated in Fig. 14 [44]. The obtained rewrite the equation (10) as,
values of Urbach energy for the samples are tabulated in Table 4.  pffiffiffi 
The formation of the Urbach tail and the relationship of the band R1þ
gap with Urbach energy for GdCr1-xMnxO3 (0.0
x
0.4) are n¼ pffiffiffiffiffi (11)
shown in Fig. 15. Urbach energy of these samples is found to in- ð1  RÞ
crease with Mn doping, which indicates the inverse dependence The spectral distribution of real part of refractive index n, for
with energy band gap. The increase in Urbach energy with the in- GdCr1-xMnxO3 (0.0
x
0.4) samples are illustrated in Fig. 17. As
crease of Mn content is ascribed to the number of defect levels observed, in the range 200e352 nm (anomalous dispersion), the
generated under the conduction band edge of the samples. So as refractive index decreases with the increase in wavelength and
band gap decreases, the magnitude of defect energy increases. approaches its minimum value at about 310 nm which corresponds
Also the bands of material can be characterised by the to the strong absorption and then increases up to 352 nm.
maximum wavelength (threshold wavelength) that is a function of The doped samples show almost similar behaviour and further
the nanoparticle size. The values of threshold wavelength (ls) were increase in wavelength results in slight increase of refractive index
estimated using UV/Vis. spectrum according to the following that confirms the normal dispersion characteristic in the higher
equation [45]. wavelength range (transparent region). Pristine sample shows
higher values and variations of refractive index as compared to the
(A/l)2 ¼ G(1/l  1/ls) (9) doped samples due to anomalous dispersion of absorption peaks.

Here A and G stand for the absorption and empirical constant

respectively. The reflectance (R) was converted into the apparent
absorbance (A) using the relation, A ¼ log (1/R) [46]. A plot was

Fig. 11. The variation in reflectance (R) as a function of the wavelength for the GdCr1- Fig. 12. Plots of the crystal field energy d3 configuration as a function of strength of the
xMnxO3(0.0
x
0.4) samples. octahedral field.
410 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414

Fig. 13. (F(R)hn)2 versus hn plots of GdCr1-xMnxO3(0.0
x
0.4) samples.

Table 4
Energy gap, Urbach energy and threshold wavelength of GdCr1-xMnxO3 (0.0
x
0.4).

Mn conc. (x) Energy gap, Eg (eV) Urbach energy, Eu (meV) Threshold wavelength, ls (nm)

0.0 3.83 486 355.87

0.1 3.77 740 364.96
0.2 3.72 1386 379.92
0.3 3.69 1443 384.32
0.4 3.71 2275 377.50

The normal dispersion can be discussed on the basis of a single temperature with that of the reference material under similar
oscillator model but the anomalous dispersion can be described on conditions. DTA provides valuable information about the thermo-
the basis of the multi-oscillator model [48]. dynamics, kinetics and transition temperature of the material [49].
In the present work, we have studied the heat flow and the specific
heat capacity (Cp) as a function of the sample temperature. The
3.3. Thermal analysis
results from this study are presented in Fig. 18 for all samples of
GdCr1-xMnxO3 (0.0
x
0.4). It exhibits exothermic and endo-
Differential thermal analysis (DTA) is a technique used to mea-
thermic events for the observed heat flow in the DTA curves and
sure thermal properties of the material by comparing its
 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414 411

Fig. 14. Plots of lnF(R) versus hn to determine the Urbach energy (Eu) for GdCr1-xMnxO3 (0.0
x
0.4) samples.

their values are displayed in Table 5.

It can be noticed that all the samples exhibit two exothermic DQ
Cp ¼ (12)
peaks except GdCr0.8Mn0.2O3 that has only one peak. These peaks mb
shift towards the higher temperature in Mn doped samples. The
exothermic peaks can be attributed to the evaporation of water and where DQ is the heat flow in the system, m is the mass of the
organics inside GdCr1-xMnxO3 (0.0
x
0.4) samples. As the ex- sample and b is the heating rate. The exothermic and endothermic
change interaction depends on the bond angles and the bond peaks are also reflected in Cp versus temperature plots at the same
lengths. The variation of Cr/MneOeCr/Mn bond angle and <Mn/ positions as displayed in heat flow plots. The variation of specific
CreO> bond length as shown in the Table 1 will make exchange heat of our samples may be attributed to the different density of the
interaction stronger, leading to the structural transition. The material associated with Mn doping as shown in the Table 1.
endothermic peak that manifest for all the samples may be asso-
ciated to a high temperature structural phase transition [50]. 4. Conclusions
We have also studied the variation of heat capacity at fixed
pressure (Cp) as a function of temperature using the following Single phase samples of GdCr1-xMnxO3 (0.0
x
0.4) were
equation (Fig. 18(b)) synthesized from the sol gel auto combustion process. The Rietveld
refinement of the XRD patterns confirms that all the samples are
412 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414

Fig. 15. The variation in band gap and Urbach energy as function of Mn doping for
GdCr1-xMnxO3(0.0
x
0.4) samples.
Fig. 17. The variation of refractive index with incident wavelength for GdCr1-xMnxO3
(0.0
x
0.4) samples.

Fig. 16. (A/l)2 versus 1/l plots for GdCr1-xMnxO3(0.0
x
0.4) samples.
 A. Alqahtani et al. / Journal of Alloys and Compounds 804 (2019) 401e414 413

Fig. 18. (a) The variation in heat flow and (b) heat capacity at constant pressure (Cp) as a function of sample temperature for GdCr1-xMnxO3 (0.0
x
0.4).

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