Progress in Solid State Chemistry 54 (2019) 20–30

Contents lists available at ScienceDirect

Progress in Solid State Chemistry

journal homepage: www.elsevier.com/locate/pssc

Structure-magnetic property relations in FeNbO4 polymorphs: A spin glass T

perspective
N. Lakshminarasimhana,b,∗, A.K. Nanda Kumara,1, S. Selva Chandrasekarana,b,2, P. Murugana,b
a
Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi, 630 003, Tamil Nadu, India
b
Academy of Scientific and Innovative Research (AcSIR), CSIR-CECRI Campus, Karaikudi, 630 003, Tamil Nadu, India

A R T I C LE I N FO A B S T R A C T

Keywords: Spin glass state originating from the magnetic frustration due to the geometric arrangement or cation disorder is
FeNbO4 polymorphs an interesting topic of research. FeNbO4, exhibiting multifarious applications, crystallizes mainly in three dif-
Antiferromagnet ferent polymorphic forms with cation ordered and disordered structures. Despite their antiferromagnetic nature,
Spin glass the orthorhombic (o-FeNbO4) and monoclinic FeNbO4 (m-FeNbO4) polymorphs exhibit a difference in their
Memory effect
magnetic properties at low temperatures. Here, we report our observation of spin glass behaviour of o-FeNbO4
Antiphase domains
First principles calculations
with a cation disordered structure. Our work is a combined experimental and theoretical study of structure-
magnetic property relations of the antiferromagnetic o- and m-FeNbO4 with the Néel temperatures of 30 and
46 K, respectively. o-FeNbO4 contrasted itself from m-FeNbO4 as a spin glass by exhibiting field-dependent bi-
furcation in ZFC and FC magnetization, frequency-dependent AC susceptibility, memory effect, thermo-
remanence, and anamoly in the heat capacity. The presence of antiphase domains and boundaries due to cation
order/disorder in both the structural polymorphs was evidenced from the electron diffraction analyses that
account for the observed low temperature magnetic interactions. Further, modeling the structures with varying
amounts of cation disorder using first principles calculations revealed the structural stability and competing spin
interactions that support our experimentally observed spin glass behaviour of o-FeNbO4.

1. Introduction pyrochlore, and spinel structures also exhibit the spin glass behaviour
[5]. The disorder induced in an ordered lattice can lead to interchange
Spin glasses have been a fascinating class of magnets for more than of metal ions in their sites and this is known as antisite (AS) defects [6].
four decades and are still a topic of fundamental interest [1,2]. In spin Further, these AS defects can be either homogeneously distributed
glasses, the disorder in the lattice leads to frustrated interactions [3]. throughout the lattice or segregated into patches. The boundaries be-
The magnetic frustration and thus, spin fluctuation in magnets result in tween AS defect patches and the original ordered lattice are known as
interesting properties at low temperatures such as quantum spin liquids the antiphase boundaries (APBs) [7]. The interactions of spins at APBs
and spin ice [1]. The frustration in magnetic system can be either of can be of weak ferro- or antiferromagnetic. For example, the magnetic
geometric or of random in nature [4]. The geometric frustration is properties of A-site ordered 1322 perovskite CaCu3Fe2Nb2O12 showed a
known in triangular lattices with Ising spins. The random frustration is variation due to the B-site order/disorder of Fe and Nb cations and
of two types: dynamical or annealed frustration and quenched random antiphase boundaries [8]. Such order/disorder of Fe and Nb cations is
frustration. The dynamical or annealed frustration occurs in modulated known in FeNbO4 that was studied for its photoelectrochemical and
structures like stripes in the copper-oxide superconductors. In quenched magnetic properties [9–12]. FeNbO4 is also a material of recent interest
random frustration, the atomic positions are frozen in as in the case of due to its diverse applications as a photocatalyst, colossal dielectric and
Fe in Au matrix and this type of frustration is an essential component in electrode material for Li-ion batteries [13–17].
the physics of spin glass materials. Spin glass behaviour was originally FeNbO4 crystallizes mainly in three different polymorphic forms
observed in transition metal alloys and later it was found that transition [18]. The tetragonal rutile structure (space group P42/mnm) is stable in
metal oxides with triangular and square lattices, Kagomé lattices, the temperature range between 1450 and 1380 °C below which it

∗
Corresponding author. Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi, 630 003, Tamil Nadu, India.
E-mail addresses: [email protected], [email protected] (N. Lakshminarasimhan).
1
Present address: Department of Sciences, Amrita Vishwavidyapeetham, Coimbatore – 641 112, Tamil Nadu, India.
2
Present address: Laboratoire de Simulation atomistique (L_Sim), INAC, CEA Grenoble 17, France.

https://doi.org/10.1016/j.progsolidstchem.2019.03.001

Available online 23 March 2019

0079-6786/ © 2019 Elsevier Ltd. All rights reserved.
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

converts into Ixiolite (α-PbO2) structure (space group Pbcn) with an microsope (HR-TEM, Tecnai F20) operating at 200 kV. The powders
orthorhombic symmetry. The Ixiolite structure transforms into Wol- were dispersed in ethanol, and a few drops were allowed to dry over
framite-type (space group P2/c) with monoclinic symmetry below formvar coated copper grids. Due to the small particle size, and the
1085 °C. Monoclinic FeNbO4 (m-FeNbO4) is isostructural with cation limitations in tilting the specimen, the electron diffraction patterns
ordered FeWO4 in which the edge sharing FeeOeFe octahedral chains were recorded after observing the Kikuchi patterns on the phosphor
results in the infinite ferromagnetic (FM) [100] sheets [10]. The cross screen. Contrast simulations were performed for similar experimental
chains of FeeOeW(Nb)eOeFe results in the antiferromagnetic (AFM) conditions of the TEM (200 kV, with a focal spread of ∼7 nm and Cs of
ordering and hence results in a net antiferromagnetism. On the other 0.5 mm) by employing Kirkland algorithm using StemCell software
hand, the magnetic behaviour of cation disordered orthorhombic [20].
FeNbO4 (o-FeNbO4) differs from that of the monoclinic polymorph. The
cation disorder disrupts both the intra-chain and inter-chain super- 2.3. Computational methods
exchange pathways resulting in the absence of any magnetic ordering
down to 4.2 K [10]. However, Pourroy et al., while comparing the Density functional theory-based first principles calculations were
magnetic properties of o- and m-FeNbO4, observed a weak FM beha- carried out using Vienna ab initio simulation package (VASP) to study
viour in orthorhombic polymorph at low temperature due to an optimal the structural and magnetic properties of the o- and m-FeNbO4 poly-
amount of cation disorder [11,12]. Such cation disorder can lead to morphs [21,22]. Projector augmented-wave (PAW) formalism was used
magnetic frustration and thus induce the spin glass behaviour. This to describe the wavefunctions of the atoms present in both the struc-
motivated us to study the structure-magnetic property relations in or- tures [23]. The exchange and correlation energy terms were corrected
thorhombic and monoclinic polymorphs of FeNbO4. Interestingly, we by generalized gradient approximations (GGA) [24]. Kinetic cut-off
observed the spin glass behaviour in o-FeNbO4 which also exhibited the energy of 400 eV was set for plane waves in the calculations. The
characteristics of spin glass such as memory effect, thermoremanent Brillouin zone of both the unit cells were sampled by 8 × 6 × 8 k-mesh
magnetization, and anomaly in the heat capacity. To the best of our for optimization of lattice constants and the ionic and electronic opti-
knowledge, no such report on the spin glass behaviour in FeNbO4 is mizations were alternatively carried out until the force on each atom
available. A detailed electron diffraction analyses revealed the presence reaches below ± 10 meV/Å. The calculated lattice constants for both
of antiphase boundaries. Further, first principle calculations were em- the monoclinic and orthorhombic structures are a = 4.673 Å,
ployed to find the crystal as well as the magnetic structural stability of b = 5.638 Å, c = 5.001 Å, β = 89.81°, and a = 4.654 Å, b = 5.655 Å,
the cation disordered polymorph. c = 5.049 Å, β = 90.00°, respectively, and these values are in close
agreement with the experimentally reported values [18].
2. Experimental section
3. Results and discussion
2.1. Synthesis
3.1. Phase analyses
FeNbO4 polymorphs were synthesized by conventional high-tem-
perature solid state reaction method. Stoichiometric amounts of Fe2O3 The phase formation was confirmed using powder XRD technique
(Merck, > 99%) and Nb2O5 (Sigma-Aldrich, 99%) were thoroughly and the patterns are shown in Fig. 1. The powder XRD patterns of o- and
ground and calcined at 750 °C for 12 h and then at 1200 °C for 24 h with m-FeNbO4 were indexed based on the standard patterns 00-016-0358
an intermittent grinding. The orthorhombic phase was obtained by air and 00-016-0374, respectively, available in the ICDD database. The
quenching the sample from 1200 °C while the monoclinic phase was additional reflections observed at 19.08, 23.86, and 46.10° in the XRD
obtained by furnace cooling to room temperature. pattern of m-FeNbO4 correspond to (001), (110), and (−112) planes,
respectively, that are the characteristics of the monoclinic structure
2.2. Characterization [18]. Both the o- and m-FeNbO4 have closely related crystal structures
except for the cation ordering as shown in Fig. 2. In both the structures,
Phase formation and purity of FeNbO4 polymorphs were examined Fe and Nb are six-fold coordinated by oxygen atoms. In m-FeNbO4 with
by powder X-ray diffraction technique (XRD; Bruker D8 Advance) using Fe and Nb ordering, the Fe atoms are arranged by edge-sharing FeO6
Cu-Kα radiation (λ = 1.5418 Å). The chemical and electronic states of
the elements were analyzed by X-ray photoelectron spectroscopy (XPS;
Multilab 2000, Thermofisher Scientific) using Mg-Kα source
(1253.6 eV). The binding energies of all peaks were calibrated with
respect to adventitious carbon 1s line (284.6 eV). The temperature
dependence of magnetization was measured under zero field cooled
(ZFC) and field cooled (FC) warming conditions between 2 and 300 K
using Physical Property Measurement System (PPMS, Dynacool,
Quantum Design). The M − H measurements were made in the mag-
netic fields between −9 and +9 T at three different temperatures, just
above and below the transition temperature: at 60, 35 and 5 K for
monoclinic FeNbO4, and at 35, 20 and 5 K for orthorhombic poly-
morph. AC susceptibility measurements were carried out at different AC
frequencies and with an AC field of 10 Oe. The memory effect was
studied during ZFC and FC measurements by following a ‘stop-and-wait’
procedure during cooling [19]. The temperatures chosen were 20 and
10 K and the waiting duration was 9000 s at each temperature. Ther-
moremanent magnetization (TRM) measurement was carried out by
cooling the samples from 100 to 20 K under different magnetic fields
and the field was set to 0 Oe and then the moment was measured for
5400 s to obtain the decay in the moment. Microstructural observations Fig. 1. Powder XRD patterns of (a) monoclinic and (b) orthorhombic FeNbO4.
on the samples were made using a high resolution transmission electron The reference standard patterns are also shown.

21
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

3p3/2 level. In m-FeNbO4, the 3p3/2 and 3p1/2 levels are at 364.5 and
379.8 eV, respectively. The Nb-3d spectra (Fig. 3c) consist of two peaks
corresponding to 3d5/2 and 3d3/2 levels. The position of 3d5/2 is at
207.25 eV for o-FeNbO4 whereas it is at 207 eV in m-FeNbO4. A similar
shift towards lower binding energy was observed for the 3d3/2 level
which is at 209.75 eV for orthorhombic polymorph and at 209.65 eV in
m-FeNbO4. The observed peak positions of Nb 3p and 3d levels corre-
spond to Nb5+ state as observed in Nb2O5 [28]. The presence of sa-
tellite peak only in the case of o-FeNbO4 can be due to the cation dis-
order. The O 1s peak is at 529.75 and 529.35 eV in o- and m-FeNbO4,
respectively. Thus, the presence of satellite peaks in Fe 2p and Nb 3p
spectra of orthorhombic polymorph originates due to the cation dis-
order in the structure while such satellite peaks are absent in the cation
ordered m-FeNbO4.

3.2. Magnetic properties

The magnetization of o- and m-FeNbO4 was measured with in-

creasing temperature and the results are shown in Fig. 4. No difference
can be found between the ZFC and FC curves in cation ordered m-
FeNbO4 (Fig. 4a) and this result shows the lack of spin glass behaviour
in this compound. The sample is AFM with the magnetic ordering Néel
temperature (TN) of 46 K. This result can be explained based on the
similar AFM behaviour of isostructural FeWO4 with TN = 66 K [29]. In
cation ordered FeNbO4 with Wolframite structure, the magnetic layers
of FeeOeFe edge shared octahedral chains with FM interaction are
separated by a non-magnetic layer consisting of edge shared NbO6 oc-
tahedral chains. The interlayer interaction in FeeOeNbeOeFe is AFM
resulting in a net antiferromagnetism to the compound. The observed
sharp drop in ZFC and FC curves below TN reveals that the AFM in-
teraction is strong in m-FeNbO4 [30]. However, an increase in the
moment below 15 K can be attributed to a short-range spin ordering
with a small fraction of Fe3+ in the niobium chains [11]. The inverse
molar magnetic susceptibility (χ−1) data collected using the ZFC mode
as shown in the inset in Fig. 4a follows Curie-Weiss behaviour above
60 K and the data were fitted using the formula:
C
χ −1 =
T− θ (1)
Fig. 2. Crystal structures of (a) monoclinic and (b) orthorhombic FeNbO4 The obtained Curie constant (C) and Curie-Weiss temperature (θ)
drawn using VESTA program [42]. In (a), the red-colored octahedra are FeO6 are 2.71 emu.K/mol.Oe and −75 K, respectively. The average effective
and the blue ones are NbO6 octahedra revealing the ordered structure. In (b) the magnetic moment ( μeff exp
) was calculated from the obtained Curie con-
octahedra are either FeO6 or NbO6 with random arrangement. (For inter-
stant using the relation:
pretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.) exp
μeff = 8C μB (2)

octahedra forming a chain along the ‘c’ axis. These chains are in- where μB denotes Bohr magneton. The effective magnetic moment ob-
tervened by similar chains formed by edge-sharing NbO6 octahedra. On tained is 4.66 μB for Fe3+ in monoclinic FeNbO4. In contrast to the
the other hand, in o-FeNbO4, there is a disorder of Fe and Nb cations observed magnetic behaviour of m-FeNbO4, the orthorhombic poly-
that leads to the presence of some Fe atoms in the Nb-chain and vice morph exhibited a bifurcation between the ZFC and FC curves (Fig. 4b)
versa. The phase transition from orthorhombic to monoclinic structure which is an indication of spin glass behaviour. Long-range structural
is a reversible translationengleich-type due to cation ordering with re- disorder of competing magnetic interactions between different types of
duction in the symmetry [18]. Another less-known structural mod- magnetic ions and, competition between intrachain FM and interchain
ification was also reported to have AlNbO4-type structure (space group AFM interactions result in the spin glass state [31,32]. The cusp ob-
C2/m) that is stable at 700 °C [25]. However, it was not realized in later served at ZFC curve is at 30 K below which the moment decreases. The
studies related to the cation and domain structure, and antiphase FC curve is almost flat below the cusp and this shows that the exchange
boundaries in FeNbO4 polymorphs [26,27]. interaction between the particles is strong [33]. The presence of Fe3+
The XPS technique was used to find the chemical states of the ele- ions between two magnetic layers in the cation disordered o-FeNbO4
ments and the spectra are shown in Fig. 3. The Fe 2p spectrum (Fig. 3a) can result in the observed spin glass behaviour. The χ−1 vs.T plot in the
of o-FeNbO4 contains the 2p3/2 and 2p1/2 levels at 709.7 and 723.7 eV, inset (ii) of Fig. 4b shows Curie-Weiss behaviour and fitted using Eqn.
respectively. In addition to these levels, the 2p3/2 satellite peak is ob- (1). The obtained Curie constant and Curie-Weiss temperature are 2.28
served at 717.8 eV. The Fe 2p3/2 and 2p1/2 levels of m-FeNbO4 are at emu.K/mol.Oe and −12 K, respectively. The effective magnetic mo-
709.5 and 723.65 eV, respectively. Nb-3p spectra (Fig. 3b) show 3p3/2 ment calculated is 4.27 μB which is close to the value observed in m-
and 3p1/2 level peaks which are at 364.4 and 380.2 eV, respectively, in FeNbO4 (4.66 μB). Thus, the observed Curie-Weiss behaviour in both
o-FeNbO4. There is a peak at 373 eV which is the satellite peak of the the structural polymorphs above 60 K is similar to the reported beha-
viour in the literature [12]. A comparison of the Curie-Weiss

22
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Fig. 3. X-ray photoelectron spectra of (a) Fe-2p, (b) Nb-3p, (c) Nb-3d and (d) O-1s levels of orthorhombic and monoclinic FeNbO4.

temperature of o- and m-FeNbO4 clearly shows that the AFM interaction required to align the spins with the external field by overcoming the
is stronger in the latter polymorph with more negative Curie-Weiss strong spin interactions and results in the disappearance of bifurcation
temperature. The weaker AFM interaction in the o-FeNbO4 agrees well between ZFC and FC traces at 30 K. However, the bifurcation occurs at
with the earlier observation that it exhibits a weak FM interaction at 13 K revealing that the spin interactions occurring at this temperature is
low temperature [12]. much stronger (ferromagnetic). Thus, the spin glass state occurs at two
The cusp in the ZFC curve indicates the freezing temperature (Tf) at different temperatures in o-FeNbO4. The similar values of |θ| (12 K) and
which the spins are frozen randomly resulting in the spin glass state. Tf (13 K) confirm the absence of any geometric frustration [3]. As the
The ZFC and FC magnetization results of o-FeNbO4 obtained by ap- spin glass state in o-FeNbO4 arises due to magnetic frustration, the level
plying different magnetic fields of 50, 100 and 10 kOe fields are shown of frustration can be estimated using the relation [3]:
in Fig. 5a. The ZFC trace measured at 50 Oe field shows the TN (or
|θ|
Tf) = 30 K and a closer look at the trace reveals a small shoulder at f=
T (3)
∼13 K. This result shows that there are two types of spin ordering/
freezing occurring at two different temperatures in o-FeNbO4. It is in- where f is the frustration index, θ is the Curie-Weiss temperature and T
teresting to note that the bifurcation between the ZFC and FC traces is the Néel temperature or freezing temperature. The obtained f values
shows a field dependence and shifted to ∼13 K when the applied field are 0.4 and 0.92 for the spin freezing temperatures of 30 and 13 K,
was 10 kOe. The variation in the ZFC susceptibility (χ) with tempera- respectively, revealing a relatively higher level of magnetic frustration
ture measured under different applied magnetic fields for both the o- occurring at lower temperature. These results confirm that there are
and m-FeNbO4 are compared in Fig. 5b. The maximum in susceptibility two different kinds of spin interactions in o-FeNbO4 and the field-de-
(χmax) was observed at 46 K for m-FeNbO4 and it is independent of the pendent spin freezing can be related to the random disorder of Fe3+
applied field strength. On the other hand, χmax of o-FeNbO4 shifted ions in the lattice. The difference in the spin ordering is in agreement
from 31 to 29 K (for H = 50 and 100 Oe) to 26 K (for H = 1 kOe) and with the observed weak FM interactions at low temperature as evi-
shifted further to 13 K (for H = 10 kOe). A decrease in Tf with in- denced in χ−1 vs.T plot (inset in Fig. 4b) [12]. To further confirm this,
creasing magnetic field is a characteristic of spin glasses as the energy the M − H hysteresis was measured at temperatures just above and
barrier can be suppressed by the applied higher magnetic field [34,35]. below TN for both the polymorphs. The results are shown in Fig. 6 and
Thus, the observed shift in Tf confirms the spin glass behaviour in o- the coercive field (Hc) values are listed in Table 1. A weak FM inter-
FeNbO4. The shoulder observed at 13 K in the curves measured at low action in o-FeNbO4 was also reflected in low-temperature M − H hys-
magnetic fields becoming the major peak when H = 10 kOe reveals the teresis measured at 5 K in which Hc is larger (1414 Oe) when compared
different kinds of spin ordering/freezing in the sample. The alignment to that of in m-FeNbO4 (16 Oe). To confirm the spin glass behaviour of
of strongly interacting spins/domains requires relatively higher mag- o-FeNbO4, we carried out the temperature dependent AC susceptibility
netic fields. In o-FeNbO4, the magnetic fields up to 1 kOe are in- measurements under different frequencies with an AC field of 10 Oe
sufficient to align the spins that are strongly interacting and hence the and the results are shown for select frequencies in Fig. 7. o-FeNbO4
moment decreases below 30 K in ZFC measurement leaving the devia- exhibited a slight decrease in AC χ′ (Fig. 7a) and a shift in the peak with
tion between ZFC and FC traces. A higher applied field (10 kOe) is increasing the AC frequency confirming its spin glass nature while there

23
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Fig. 5. (a) ZFC and FC magnetization curves of o-FeNbO4 under different ap-
Fig. 4. Temperature dependent magnetization curves under zero field cooled plied magnetic fields. The arrows in the plots point the temperature at which
(ZFC) and field cooled (FC) conditions of (a) monoclinic and (b) orthorhombic the bifurcation between the ZFC and FC curves occurs. (b) ZFC susceptibilities
FeNbO4 polymorphs. The closer look at the data in the region near the transi- of (i) m-FeNbO4 and (ii) o-FeNbO4 measured under different applied magnetic
tion temperature [insets (i)], plots of inverse molar susceptibility vs. tempera- fields revealing a shift in χmax to lower temperatures in the case of o-FeNbO4.
ture and their Curie-Weiss fit [insets (ii)] are also shown.

stronger spin interactions that sustain even at higher magnetic fields as

is no shift observed with m-FeNbO4 (Fig. 7b) [35]. observed in the field-dependent ZFC curves (see Fig. 5a) of the o-
Spin glasses exhibit the characteristics of slow spin dynamics and FeNbO4. These results show that the energy states of the observed two
memory effect. To reveal the memory effect below Tf, both the o- and different spin ordered/frozen states are different and this can be related
m-FeNbO4 were subjected to magnetization measurements with a ‘stop- to the random distribution of Fe3+ in the lattice. Similarly, the FC
and-wait’ procedure [19]. The temperature-dependent magnetization of susceptibility (χFC) of the o-FeNbO4 was measured following a similar
both the samples was measured in ZFC mode. For the ‘stop-and-wait’ ‘stop-and-wait’ procedure and the results are shown in Fig. 8b. At
mode, the samples were cooled from 100 to 2 K in zero field with temperatures 20 and 10 K where the field was set to zero, the sus-
temporary stops for 9000 s each at 20 and 10 K. As a reference, ZFC ceptibility shows a dip and then it increases. Here, again the dip at 10 K
measurement was also carried out without any such stop during is deeper than the one at 20 K and this result is in agreement with the
cooling. The difference in the susceptibilities (χZFC-χZFCRef) measured ZFC measurements as explained above. At temperatures below 10 K, the
under these two modes for both the samples are shown in Fig. 8a. In susceptibility increases and this is similar to the FCW reference result
spin glasses, on reheating, a dip appears at the temperature at which the obtained without any stop. Thus, the memory effect in o-FeNbO4 is due
cooling was stopped under zero magnetic field [19]. From Fig. 8a, it is to the slow dynamics of spins and their different energy states. These
clear that o-FeNbO4 exhibits two dips each at 10 and 20 K at which results further confirm the spin glass behaviour due to magnetic frus-
temperatures the cooling was stopped whereas m-FeNbO4 did not reveal tration arising from the random distribution of Fe3+ in the lattice of o-
any such dip in the moment. The dip observed in the orthorhombic FeNbO4. The existence of magnetic remanence is another important
polymorph is due to the magnetic relaxation. As spin glass material is feature of spin glasses [35]. The thermoremanent magnetization (TRM)
left unperturbed at a constant temperature below its Tf, there occurs a of o- and m-FeNbO4 was measured in an FC mode with the applied field
spontaneous rearrangement of magnetic moment configuration towards ranging from 1 to 10 kOe at 20 K. After cooling the samples from 100
equilibrium through increase in the correlation length [36]. It is to be [well above their TN (or) Tf] to 20 K, the field was set to 0 Oe and the
noted that the dip observed at 10 K is deeper than the one at 20 K. This decay in the moment was measured. The TRM traces measured at 1 kOe
could be due to the spin ordering/freezing occurring at ∼13 K with field are shown in Fig. 9. m-FeNbO4 did not show any decay in the

24
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Fig. 6. M − H traces of (a) monoclinic and (b) orthorhombic polymorphs of

FeNbO4 measured at different temperatures and the insets show the low-tem-
Fig. 7. Variation in AC susceptibility (χ′) with frequency of (a) orthorhombic
perature results. A relatively larger hysteresis is seen at 5 K in the case of o-
and (b) monoclinic FeNbO4. Data obtained using select frequencies are only
FeNbO4.
shown for clarity.

Table 1
Fig. 10b. A shoulder observed at T ≈ 30 K in C/T vs. T result can be
Coercive fields obtained from the M − H traces of monoclinic and orthor-
hombic FeNbO4 measured at different temperatures.
related to the onset of short-range magnetic ordering below the freezing
temperature which is a characteristic of spin glasses. There is another
Temperature (K) Coercive Field (Hc, Oe) shoulder at T ≈ 10 K which can be attributed to the other spin ordered/
Monoclinic Orthorhombic
frozen state as observed in the ZFC results (see Fig. 5a). Thus, the
random cation disorder in o-FeNbO4 leads to different types of short-
60 16 – range magnetic ordering occurring at different temperatures. Also, the
35 10 15 cation disorder in FeNbO4 favours the inter-chain FeeFe exchange in-
20 – 114
5 16 1414
teraction over the intra-chain interactions [12]. However, increasing
the cation disorder will decrease the long range magnetic ordering by
introducing diamagnetic defects in the magnetic layer and hence the
moment whereas the moment of orthorhombic polymorph exhibited a cation disorder needs to be at an optimum level to observe the FM in-
slow decay in the remanence and a 57% of remanence even after 3000 s teractions at low temperatures [12].
confirms the spin glass state in the latter polymorph.
The spin glass state can also lead to anomaly in the heat capacity. To
3.3. Electron diffraction analyses
confirm this, heat capacity measurements were carried out for both the
o- and m-FeNbO4 and the results are shown in Fig. 10. A sharp transi-
The observed low temperature magnetic interactions in both the o-
tion at 43 K and a shoulder at ∼15 K were found in the case of m-
and m-FeNbO4 can originate from the presence of antiphase domains
FeNbO4 (Fig. 10a). These values are in good agreement with the mag-
and boundaries due to Fe and Nb order/disorder and to confirm this,
netization results as shown in Fig. 4a. There was no clear transition
the electron diffraction was carried out. The ordered Wolframite-type
observed in the heat capacity measurement of o-FeNbO4. The lack of
and disordered Ixiolite-type FeNbO4 are structurally very similar and it
any λ-anomaly (characteristics of ferro- and antiferromagnetism) and
is difficult to distinguish them by their microstructural appearances
any clear transition confirm the spin glass state of o-FeNbO4 [1,37,38].
under normal magnifications. This arises from the subtle changes in the
Hence the C/T vs. T was plotted and the results are shown as an inset in
occupancy of the 8d Wykoff sites of the anions and the 4c sites of the

25
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Fig. 9. Thermoremanent magnetization (TRM) of monoclinic and orthorhombic

FeNbO4 samples measured at 20 K. The samples were field cooled from 100 to
20 K in an applied magnetic field of 1 kOe and then the field was removed
before measuring the moment.

Fig. 8. (a) The χZFC–χZFCRef of orthorhombic and monoclinic FeNbO4. The ZFC
process was intermitted for 9000 s each at T = 20 and 10 K in the measurement
of χZFC. The χZFCRef was measured without such stops. (b) FCW susceptibility of
orthorhombic FeNbO4 recorded under two different conditions. The cooling
process was intermitted for 9000 s each at T = 20 and 10 K in the measurement
of FCW (Stop during cooling @ 10 & 20 K). The FCW (Reference) was measured
without such stops. In both (a) and (b) experiments, the cooling rate was 10 K/
min and the reheating rate was 5 K/min. The applied magnetic field was 1 kOe.

cations and symmetry breaking during the disorder-order (Pbcn → P2/

c) transition. The ordering in the low symmetry monoclinic lattice
changes the structure factor (for instance, in a set of {0k0}⇒k = 2n; in
{hk0} ⇒ h + k = 2n etc.), enabling one to identify the phases based on
the presence/absence of certain special reflections or through the oc-
currence of split reflections [26]. Fig. 11a and b shows the images ac-
quired from the monoclinic polymorph (that was processed to contain
only the low temperature, ordered P2/c phase). The diffraction showed
a clear pattern despite the fluctuating contrast in the bright field image.
The occurrence of certain forbidden reflections allowed us to index the
zone axis in this case to be [112] of P2/c. Interestingly, the contrast
levels were not uniform, and a high resolution image acquired from the
same particle showed a clear evidence of change in structural ordering
at a very fine scale, indicating a biphasic microstructure. Fig. 12a and b
Fig. 10. Heat capacity as a function of the temperature of (a) monoclinic and
shows the high magnification images from the same particle (imaged in
(b) orthorhombic FeNbO4. The insets show the corresponding C/T vs. T plots.
Fig. 11) recorded as part of a focal series imaging experiment across the
Scherzer defocus. While both the domains I and II are from the same
P2/c, the fringes are shifted by ½ < 110 > , leading to an antiphase symmetry is much higher in Pbcn space group containing two axial
→ → →
domain, an observation that is consistent with the one reported by glide planes with the glide vectors, g = b /2, c /2 along with a diag-
→ →
Theissamann et al. [27]. Crystallographically, the translational onal glide plane perpendicular to [001] with g = ½[→ a + b ], whereas

26
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Fig. 11. (a) HR-TEM bright field image of m-FeNbO4 with the region analyzed for electron diffraction marked with red square and (b) indexed pattern corresponding
the [112] zone axis. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 12. (a) A magnified HR-TEM image of

the region as marked with a red square in
Fig. 11 with two similar sets of lattice
fringes in the domains I and II. (b) The
junction between domains I and II shows
the shift in the lattice fringes and the inset
shows the power spectrum of the FT. (c) A
high resolution image inserted with the si-
mulated one.

→ → specimen, as can be seen in Fig. 14a. Apparently, cation ordering occurs

there is only one axial glide plane with g = c /2 in P2/c. Hence, the
orthorhombic Pbcn phase forms at the antiphase boundary (APB), since in a few layers between the predominantly disordered layers even in the
this accommodates the glide planes across which the P2/c antiphase orthorhombic specimen resulting in the antiphase domains. These do-
domains are created, leading to the ½ < 110 > fringe shifts, as cor- mains align with neighbouring domains across APB with the applica-
rectly observed in the lattice image. The non-uniform contrast arising tion of external magnetic field [6]. This alignment depends on the ap-
from the imperfect coherency between the APBs and the monoclinic plied magnetic field strength as shown in Fig. 5a and b and accounts for
domains resulted in the observed fluctuations. As can be seen in Fig. 12, the presence of the weak ferromagnetic ordering observed at 10 K.
the APBs are of quite narrow region, less than 5 nm connecting the Thus, the electron diffraction studies revealed the presence of antiphase
antiphase domains that are roughly 10 nm in size. These micro- domains and APBs in both the orthorhombic and monoclinic poly-
structural aspects resulted in serious implications in the observed morphs those account for the observed magnetic anomalies at low
magnetic properties as discussed earlier. The increase in the magneti- temperatures.
zation below 10 K in m-FeNbO4 can be attributed to the magnetic in-
teractions arising at the APBs. 3.4. Computational studies
Fig. 13a and b shows the two bright field images from the o-FeNbO4
(space group Pbcn). We note immediately that unlike the monoclinic Spin glass state arising from magnetic frustration due to cation
polymorph, the overall contrast in this specimen is rather uniform, disorder generates a large number of degenerate ground state config-
except for the bending and thickness extinction contours. Towards the urations and the magnetic moments can ‘freeze’ into these configura-
edges of the sample, inhomogenous contrast is visible indicating the tions upon cooling [2]. First principles density functional calculations
propensity for phase mixing although at a relatively minor scale. High were performed to explore the various possibilities of structurally dis-
resolution images recorded at the periphery of a particle (shown earlier ordered states of FeNbO4 and their magnetic properties as the structure
in Fig. 13b) are shown in Fig. 14. Due to the close lattice spacings and transforms from the cation ordered monoclinic (space group P2/c) to
symmetries between the two phases along certain crystallographic di-
cation disordered orthorhombic (space group Pbcn) structure. To study
rections, the corresponding diffraction pattern could be indexed to ei- these properties, a 2 × 2 × 2 supercell of the monoclinic structure with
ther [−3-12] of Pbcn or [2–13] of P2/c. But contrast simulations car-
16 formula units of FeNbO4 was considered. In this structure, the FeO2
ried out using both these zone axes clearly agree with the orthorhombic and NbO2 layers that are formed from the edge-shared NbO6 and FeO6-
symmetry of Pbcn space group rather than the monoclinic P2/c
octahedra, respectively, are alternately stacked along the [100]-axis.
(Fig. 14a). Yet, the spatial frequency is not similar everywhere in the The transformation from the monoclinic to orthorhombic structure was

27
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Fig. 13. HR-TEM images of o-FeNbO4 at two different magnifications. The region marked with red square in (b) is used for electron diffraction analyses. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 14. (a) HR-TEM image of o-FeNbO4 with crossed fringes and the inset is the indexed electron diffraction in the region marked with a dashed square. (b) A high
resolution image inserted with the simulated ones revealing the presence of both monoclinic (P2/c) and orthorhombic (Pbcn) lattices.

Fig. 15. Structural models (only Fe-octahedra are shown) of monoclinic (model 0) and orthorhombic (model 8) FeNbO4. The structures from 1 to 7 are modeled with
a gradual interchange (refer Table 2) of Fe and Nb in order to change from monoclinic to orthorhombic.

systematically performed by interchanging the Nb and Fe atoms in parameters, monoclinic angle (β) and relative volumes of all the models
eight steps that are shown in Fig. 15. Note that each step involves the are listed in Table 2. The variation in the monoclinic angle β and the
interchange of two Nb atoms with Fe atoms. Both the structural and relative energies of all these models are shown in Fig. 16a and b, re-
ionic relaxations of all the models were performed. The obtained lattice spectively. From the energetics, it is clear that the monoclinic structure

28
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

Table 2
The lattice parameters, angle β, and relative volume (V/V0) of the unit cells
with different amount of interchange of Nb and Fe. The monoclinic unit cell
with 0% interchange of Nb and Fe is taken as reference.
Interchange of Nb and Fe (%) a (Å) b (Å) c (Å) β (°) V/V0

00.0 9.347 11.276 10.000 89.10 1

12.5 9.354 11.278 10.019 89.31 1.003
25.0 9.349 11.282 10.049 89.35 1.006
37.5 9.353 11.281 10.056 89.38 1.007
50.0 9.347 11.316 10.069 89.53 1.011
62.5 9.335 11.310 10.085 89.73 1.011
75.0 9.324 11.304 10.101 89.85 1.010
87.5 9.303 11.305 10.127 89.95 1.011
100 9.308 11.311 10.098 90.00 1.010

is more stable than the cation disordered phases as well as the relative
energy gradually increases with increasing amount of intermixing of Nb
and Fe atoms. The relative energy almost saturates (Fig. 16b) when the
monoclinic phase is completely transformed to the orthorhombic
structure which is also confirmed by the measured β value of 90°
(Fig. 16a).
To understand the magnetic properties of cation ordered monoclinic
and cation disordered orthorhombic polymorphs of FeNbO4, both the
FM and AFM configurations were studied by first principles calcula-
tions. The energy difference (ΔE) between both the configurations for
all the models was calculated and is shown in Fig. 16c. It reveals that
both the monoclinic and orthorhombic phases favour AFM configura-
tion with ΔE of 28 and 86 meV/f.u., respectively. The higher value of
ΔE, in general, will not produce the frustration in the spin alignment of
Fe atoms. Hence, monoclinic phase and the nearby cation disordered
phases prefer to settle in AFM configuration. This theoretical result
resembles well with our experimental findings that showed a strong
AFM interaction in monoclinic FeNbO4 (Fig. 4) whereas a weak FM
state was found in cation disordered orthorhombic polymorph. From
our theoretical calculations, the lowest ΔE value (19 meV/f.u.) was
observed in slightly disordered orthorhombic phase (model-7, in
Fig. 15) which infers that the strength of the spin-spin interaction is
weaker and expected to have the spin frustrations [39]. Thus, the cation
disordered orthorhombic polymorph (model-7) leads to a spin glass
state. Also, in the structural model-7, the presence of Fe in the inter-
layer between two Fe chains with AFM interactions results in a situation
similar to a triangular lattice (Fig. 16d and e) that favours the magnetic
frustration. The intra-chain FM interactions and inter-chain AFM in-
teractions result in a net AFM state in m-FeNbO4 while the introduction
of Fe atoms in the diamagnetic layer of NbO6 chain results in a weak
inter-chain FM interaction in o-FeNbO4. The coupling of strong inter-
chain AFM interactions with the weak inter-chain FM interactions re-
sulted in the observed spin glass state in o-FeNbO4 [40,41]. This spin
glass state depends on the extent of AFM and FM state which in turn Fig. 16. (a) The optimized monoclinic angle β, (b) AFM ground state energies
depends on the amount of disordered Fe atoms in the NbO6 layer as of all the models (shown in Fig. 15) with respect to the model-0, and (c) dif-
revealed by the theoretical calculations. Neutron diffraction studies at ference in the energy between FM and AFM spin configurations of all the
low temperatures will give a more detailed magnetic structures and the models. (d) and (e) show the possible spin configurations of Fe atom in the Nb
extent of disorder in FeNbO4 polymorphs to explain the low tempera- layer for model 7.
ture magnetic interactions. Our results show that the magnetic prop-
erties, in particular the spin glass nature, of transition metal niobium behaviour. A shoulder at ∼13 K in the ZFC magnetization curve in-
oxides can be controlled by the extent of cation disorder which in turn dicated the presence of an additional magnetic interaction in the
depends on the synthesis conditions. sample. The transition temperature and the bifurcation in o-FeNbO4
exhibited a magnetic field dependence and shifted to 13 K with increase
in the applied magnetic field while m-FeNbO4 revealed no such de-
4. Conclusions pendence. The existence of a weak ferromagnetic interaction at low
temperature in o-FeNbO4 was reflected in the low temperature (5 K)
The detailed understanding of the structure-magnetic property re- magnetic hysteresis with a higher coercive field (1414 Oe) when com-
lationships in antiferromagnetic orthorhombic and monoclinic poly- pared to that of m-FeNbO4 (16 Oe). The spin glass behaviour of o-
morphs of FeNbO4 revealed the existence of spin glass state in the FeNbO4 originating from the cation disorder was further manifested in
former. The bifurcation observed between ZFC and FC magnetization the AC susceptibility, memory effect, slow spin dynamics and anomaly
curves with a cusp at 30 K in o-FeNbO4 revealed the spin glass

29
N. Lakshminarasimhan, et al. Progress in Solid State Chemistry 54 (2019) 20–30

in the heat capacity. All these characteristics distinguish o-FeNbO4 from [15] Li QJ, Xia SQ, Wang XY, Xia W, Yu Y, Cui YM, Zhang J, Zheng J, Cheng C, Li YD,
m-FeNbO4 as a spin glass due to cation disorder. The presence of an- Wang H, Huang SG, Wang CC. The colossal dielectric properties of FeNbO4. J Alloy
Comp 2014;616:577–80.
tiphase domains and boundaries in both the structural polymorphs as [16] Shim H-W, Cho I-S, Hong KS, Lim A-H, Kim D-W. Hydrothermal synthesis and
evidenced from the electron diffraction analyses are due to order/dis- electrochemical properties of FeNbO4 nanospheres. J Ceram Soc Japan
order of Fe and Nb atoms in them. The spin interactions at the antiphase 2012;120:82–5.
[17] Kumari TSD, Gandhi RV, Rahul G, Kamalanathan G, Kumar TP, Jeyakumar D,
boundaries are responsible for the low temperature weak ferromagnetic Lakshminarasimhan N. Electrochemical lithium insertion behavior of FeNbO4:
interactions especially in o-FeNbO4. The modeling of the structures structural relations and in situ conversion into FeNb2O6 during carbon coating.
with varying amount of Fe and Nb antisite disorder revealed the Mater Chem Phys 2014;145:425–33.
[18] Roth RS, Waring JL. Ixiolite and other polymorphic types of FeNbO4. Am Mineral
structural stability and the presence of competing ferro- and anti- 1964;49:242–6.
ferromagnetic interactions. This resulted in the experimentally ob- [19] Bedanta S, Kleemann W. Supermagnetism. J Phys D: Appl Phys 2009;42:013001.
served spin glass behaviour in o-FeNbO4. There is scope in realizing 1-28.
[20] Grillo V, Rotunno E. StemCell: a software for electron microscopy. Part I
interesting magnetic spin glass states arising out of cation disorder and
Simulations. Ultramicroscopy 2012;125:97–111.
microstructural variation in other transition metal niobium oxides. [21] Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy cal-
culations using a plane-wave basis set. Phys Rev B 1996;54:11169–86.
Acknowledgements [22] Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals. Phys Rev B
1993;47:558–61.
[23] Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-
The authors acknowledge the XII Five Year Plan project MULTIFUN wave method. Phys Rev B 1999;59:1758–75.
(CSC-0101) of Council of Scientific and Industrial Research (CSIR), New [24] Blöchl PE. Projector augmented-wave method. Phys Rev B 1994;50:17953–79.
[25] Harder VM, Müller-Buschbaum Hk. FeNbO4: untersuchungen an Einkristallen rnit
Delhi for PPMS and HR-TEM facilities. Mr. P. Kamaraj, CSIR-CECRI is Wolframit- und AlNbO4-Struktur. Z Anorg Allg Chem 1979;156:99–105.
acknowledged for his help during magnetic property measurements. Dr. [26] Theissmann R, Ehrenberg H, Weitzel H, Fuess H. Nanostructured cation distribution
Vijayamohanan K. Pillai, CSIR-CECRI is acknowledged for his constant in FeNbO4: a synchrotron powder diffraction and transmission electron microscopy
analysis. J Mater Sci 2002;37:4431–6.
encouragement and support. Central Instrumentation Facility division [27] Theissmann R, Ehrenberg H, Weitzel H, Fuess H. Domain structure and lattice
and High-performance Computing (HPC) cluster of CSIR-CECRI are strains in FeNbO4. Solid State Sci 2005;7:791–5.
acknowledged for characterization facilities and for performing the [28] NIST X-ray photoelectron spectroscopy database. http://srdata.nist.gov/xps,
Accessed date: 20 July 2016.
theoretical calculations, respectively. The structural models were [29] Noda Y, Shimada M, Koizami M, Kanamaru F. Magnetic and electrical properties
drawn using the software VESTA version 3 [42]. and Mössbauer effect in the solid solution Fe(Nb1-xWx)O4 (0 ≤ x ≤1). J Solid State
Chem 1979;28:379–84.
[30] Li M-R, Walker D, Retuerto M, Sarkar T, Hadermann J, Ktephens PW, Croft M,
References
Ignatov A, Grams CP, Hemberger J, Nowik I, Halasyamani PS, Tran TT, Mukherjee
S, Dasgupta TS, Greenblatt M. Polar and magnetic Mn2FeMO6 (M = Nb, Ta) with
[1] Binder K, Young AP. Spin glasses: experimental facts, theoretical concepts, and open LiNbO3-type structure: high-pressure synthesis. Angew Chem Int Ed
questions. Rev Mod Phys 1986;58:801–976. 2013;52:8406–10.
[2] Mydosh JA. Spin glasses: an experimental introduction. London: Taylor & Francis; [31] Auckett JE, Miiller W, Avdeev M, Kimpton JA, Ling CD. Structural disorder and
1993. classical spin-glass behaviour in Ba3Fe2SbO9. Aust J Chem 2014;67:1612–7.
[3] Ramirez AP. Strongly geometrically frustrated magnets. Annu Rev Mater Sci [32] Roy SB, Chattopadhyay MK. Contrasting the magnetic response between a magnetic
1994;24:453–80. glass and a reentrant spin glass. Phys Rev B 2009;79:052407. 1-4.
[4] Gardner JS, Gingras MJP, Greedan JE. Magnetic pyrochlore oxides. Rev Mod Phys [33] Sasaki M, Jönsson PE, Takayama H, Mamiya H. Aging and memory effects in su-
2010;82:53–107. perparamagnets and super spin glasses. Phys Rev B 2005;71:104405. 1-9.
[5] Greedan JE. Geometrically frustrated magnetic materials. J Mater Chem [34] Luo J, Zhu HT, Zhang F, Liang JK, Rao GH, Li JB, Du ZM. Spin-glass like behavior of
2001;11:37–53. K+-containing α-MnO2 nanotubes. J Appl Phys 2009;105:093925. 1-5.
[6] Meneghini C, Ray S, Liscio F, Bardelli F, Mobilio S, Sarma DD. Nature of “Disorder” [35] Song J, Zhao B, Yin L, Qin Y, Zhou J, Wang D, Song W, Sun Y. Reentrant spin glass
in the ordered double perovskite Sr2FeMoO6. Phys Rev Lett 2009;103:046403. 1-4. behavior and magnetodielectric coupling of an Ir-based double perovskite com-
[7] Goodenough JB, Dass RI. Comment on the magnetic properties of the system Sr2- pound, La2CoIrO6. Dalton Trans 2017;46:11691–7.
xCaxFeMoO6, 0≤x≤2. Int J Inorg Mater 2000;2:3–9. [36] Rivadulla F, López-Quintela MA, Rivas J. Origin of the glassy magnetic behavior of
[8] Senn MS, Chen W-t, Saito T, García-Martín S, Attfield JP, Shimakawa Y. B-Cation the phase segregated state of the perovskites. Phys Rev Lett 2004;93:167206. 1-4.
order control of magnetism in the 1322 perovskite CaCu3Fe2Nb2O12. Chem Mater [37] Rayaprol S, Singh K, Jammalamadaka SN, Mohapatra N, Gaur NK,
2014;26:4832–7. Sampathkumaran EV. Magntic anomalies in a new manganocuprate
[9] Koenitzer J, Khazai B, Hormadaly J, Kershaw R, Dwight K, Wold A. Preparation and Gd3Ba2Mn2Cu2O12. Solid State Commun 2008;147:353–6.
photoelectronic properties of FeNbO4. J Solid State Chem 1980;35:128–32. [38] Upadhyay SK, Paulose PL, Iyer KK, Sampathkumaran EV. Spin-glass behavior and
[10] Harrison WTA, Cheetham AK. Structural and magnetic properties of FeNbO4-II. pyroelectric anomalies in a new lithium-based oxide, Li3FeRuO5. Phys Chem Chem
Mater Res Bull 1989;24:523–7. Phys 2016;18:23348–53.
[11] Pourroy G, Riera AMI, Poix P, Poinsot R. Low temperature syntheses of NbFeO4 and [39] Ravindran P, Vidya R, Vajeeston P, Kjekshus A, Fjellvag H, Hauback BC.
TaFeO4: influence of recrystallization on the magnetic properties. J Solid State Antiferromagnetic vs. ferromagnetic interactions and spin-glass-like behavior in
Chem 1990;88:476–84. ruthenates. Solid State Commun 2002;124:293–8.
[12] Pourroy G, Coronado E, Sapiña F. Magnetic strudies of ordered and disordered [40] De Teresa JM, Ibarra MR, García J, Blasco J, Ritter C, Algarabel PA, Marquina C, del
NbFeO4 phases. J Alloy Comp 1992;188:234–6. Moral A. Spin-glass insulator state in (Tb-La)2/3Ca1/3MnO3 perovskite. Phys Rev
[13] Cho I-S, Lee S, Noh JH, Choi GK, Jung HS, Kim DW, Hong KS. Visible-light-induced Lett 1996;76:3392–5.
photocatalytic activity in FeNbO4 nanoparticles. J Phys Chem C 2008;112:18393–8. [41] Jonason K, Mattsson J, Nordblad P. Chaos in the ferromagnetic phase of a reentrant
[14] Babu R, Kelkar S, Kashid V, Achary SN, Salunke HG, Gupta NM. Photophysical, ferromagnet. Phys Rev Lett 1996;77:2562–5.
bandstructural, and textural properties of o-FeNbO4 in relation to its cocatalyst- [42] Momma K, Izumi F. Vesta 3 for three-dimensional visualization of crystal, volu-
assisted photoactivity for water oxidation. RSC Adv 2014;4:33435–45. metric and morphology data. J Appl Crystallogr 2011;44:1272–6.

30