Coexisting nanoscale inverse spinel and rock salt crystallographic phases in NiCo2O4

epitaxial thin films grown by pulsed laser deposition

H. Sharona, B. Loukya, U. Bhat, R. Sahu, B. Vishal, P. Silwal, A. Gupta, and R. Datta

Citation: Journal of Applied Physics 122, 225301 (2017); doi: 10.1063/1.4998776

View online: https://doi.org/10.1063/1.4998776
View Table of Contents: http://aip.scitation.org/toc/jap/122/22
Published by the American Institute of Physics

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 JOURNAL OF APPLIED PHYSICS 122, 225301 (2017)

Coexisting nanoscale inverse spinel and rock salt crystallographic phases

in NiCo2O4 epitaxial thin films grown by pulsed laser deposition
H. Sharona,1,2 B. Loukya,1,2 U. Bhat,1,2 R. Sahu,1,2 B. Vishal,1,2 P. Silwal,3 A. Gupta,4
and R. Datta1,2,a)
1
International Centre for Materials Science, Jawaharlal Nehru Centre for Advanced Scientific Research,
Bangalore 560064, India
2
Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research,
Bangalore 560064, India
3
Department of Physics and Engineering Physics, Tulane University, New Orleans, Louisiana 70118, USA
4
Center for Materials for Information Technology, University of Alabama, Tuscaloosa, Alabama 35487, USA
(Received 3 August 2017; accepted 24 November 2017; published online 12 December 2017)
The origin of alternating wavy dark-bright stripe-like contrast in strain contrast transmission elec-
tron microscopy images of NiCo2O4 (NCO) epitaxial thin films grown by pulsed laser deposition
has been investigated. The nanoscale stripe-like pattern is determined to be associated with coexist-
ing rock salt (RS) and inverse spinel crystal phases. The presence of two different phases, not
addressed in previous reports, is experimentally confirmed by both electron diffraction and high
resolution transmission electron microscopy imaging. First principles based calculations, together
with compressive strain present in the films, support the formation of such coexisting crystallo-
graphic phases in NCO. Similar microstructural patterns and RS structure are not observed in epi-
taxial films of two other oxides of the spinel family, namely, NiFe2O4 and CoFe2O4. A correlation
between the coexisting structures and the macroscopic physical properties of NCO is discussed.
Published by AIP Publishing. https://doi.org/10.1063/1.4998776

I. INTRODUCTION formula unit). However, experimentally, thin film samples

grown at 250, 350, and 550  C show lower magnetic
NiCo2O4 (NCO) is an electrochemically active material
moments of 1.58, 1.76, and 0.26 lB /f. u., respectively, indi-
and is a promising candidate for various applications such as
cating the possibility of mixing of cations and charges
in oxygen catalysis and water electrolysis and as photo-
between A and B sites of the structure. Previous neutron dif-
detectors, fuel cell electrodes, infrared transparent electro-
fraction studies of the bulk NCO sample by Battle et al. also
des, etc.1–7 For example, NCO crystals with different indicated reduced magnetization as compared to the
morphologies have been explored for super-capacitor appli- expected theoretical values. They explained the reduction by
cations.2 In several studies, the preparation method is considering the formula unit as Co(3-d)þ[Ni(2þd)þCo3þ]O2 4 ,
observed to influence the composition and the performance where A sites are occupied by magnetic Co2þ along with
of the material, for example, in the reduction of oxygen on nonmagnetic Co3þ, while B sites are occupied by magnetic
Ni-Co oxides.8,9 Similarly, depending on the growth condi- Ni3þ along with non-magnetic Ni2þ.14 More recently, the
tions, NCO thin films exhibit wide variations in their mag- presence of mixed cations and charges has been confirmed
netic and transport properties.8,10–12 While thin films grown by Raman spectroscopy studies of epitaxial NCO thin films
by pulsed laser deposition (PLD) at lower temperatures by Iliev et al.11 In fact, 25% mixed structure is theoretically
(<500  C) are ferrimagnetic and exhibit p-type metallic determined to be the most stable configuration, with other
behavior, those grown at higher temperatures (>500  C) are configurations also showing comparable stability.13 High
nonmagnetic and insulating.10 Oxide thin films exhibiting resolution transmission electron microscopy (HRTEM)
both magnetism and electrical conductivity are attractive for imaging of NiFe2O4 (NFO) and CoFe2O4 (CFO) spinel oxide
spin-based device applications, e.g., in magnetic tunnel junc- films reveals areas with missing A-site cation defects and
tions. Previous theoretical and experimental investigations antiphase domains.15–17 The existence of such A site cation
concluded that the nonmagnetic NiCo2O4 (NFO) films grown defects can lower the net magnetization per f. u. of NCO
at higher temperatures have the ideal inverse spinel (IS) although their presence is found not to be energetically
structure. In contrast, films grown at relatively lower temper- favorable in this system.13
atures (250–350  C) exhibit a structural deviation from ideal In our previous publication on NCO thin films grown by
inverse spinel towards mixed cations at the tetrahedral A pulsed laser deposition, we merely mentioned the observation
sites along with mixing in the charge state (þ2 and þ3) in of nanometer length scale alternate dark-bright contrast in
both the tetrahedral A and octahedral B sites.8–14 The theoret- strain contrast TEM images.11 While ripple-like patterns are
ically predicted magnetic moment for the ideal inverse spinel visible for films grown at 250  C (NCO250) and 350  C
structure ðF43mÞ is 2 lB /f. u. (where f. u. stands for the (NCO350), the contrast pattern is vertical along the growth
direction for the film grown at 550  C (NCO550). These fea-
a)
Author to whom correspondence should be addressed: ranjan@jncasr.ac.in tures are very different from the dark diffused contrast areas

0021-8979/2017/122(22)/225301/8/$30.00 122, 225301-1 Published by AIP Publishing.

225301-2 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

we had observed earlier in NFO, CFO, and CoO epitaxial thin g ¼ h400i diffraction condition, and the details of data analy-
films.15,17,18 We did not understand the source of the dark- sis can be found in Ref. 20.
bright contrast observed in the images of NCO thin films, and Electronic structure calculations of various structural
hence, we did not provide any explanation for their occur- configurations were carried out using the WIEN2k code
rence. However, we have now examined the source of the which uses full potential linear augmented plane waves
image contrast through detailed diffraction and high resolution (LAPW) þ local orbitals (LO) as basis sets. The lattice
imaging analysis. Our study convincingly reveals that the ori- parameters of all the structures were fully relaxed using a
gin of such contrast is due to the formation of alternate layers generalized gradient approximation-Perdew Burke Ernzerhof
of the common inverse spinel (IS) phase, with a possible devi- (GGA-PBE) exchange correlation functional below
ation from the ideal configuration, and a previously unre- 0.0001 Ry, 1 m Ry/au, and 0.001 e, corresponding to energy,
ported defective rock salt (RS) phase of NCO. It is not force, and charge convergence criteria, respectively.22,23
actually possible to visually distinguish the RS phase from A Core and valence states were separated by 6 Ry energy.
site cation defect regions of the inverse spinel phase since The Rmtkmax parameter was set to 7. For energy convergence,
both appear similar in the projected high resolution transmis- 1000 k points were used in the first Brillouin zone during the
sion electron microscopy (HRTEM) images. Nevertheless, spin polarized self-consistent field (SCF) cycle. To correct
from the separate set of spots in the electron diffraction pat- for the bandgap of the systems, the modified Becke-Johnson
terns and different lattice parameters and with the aid of first (mBJ) potential was used.24 Additionally, X-ray magnetic
principles based calculation, it is possible to confirm the exis- chiral dichroism (XMCD) spectra were simulated after intro-
tence of the RS phase. This phase is different from the high ducing spin orbit coupling and orbital polarization.21,25,26
temperature (>650  C, insulating) RS phase observed recently The XMCD spectra provide an indication of the atom-
in NCO films.8 In the present case, the RS phase is detected in specific relative dichroic signal percentage for various
the films irrespective of the growth temperature (250–550  C), structural configurations and help in understanding the
and they consist of Ni vacancies (VNi) in the structure. The experimental EMCD spectra. The XMCD and EMCD signals
co-existence of IS and RS phases can be attributed to become equivalent under the dipole selection rule.20,27,28
substrate-induced strain, which controls the thermodynamic We considered the following structures for the present
stability of the two phases. With the aid of density functional investigation: (a) RS NiCo2O3 [Fig. 1(a)], (b) RS NiFe2O3,
theory based calculations, we discuss the effects of coexisting (c) RS CoFe2O3, (d) RS NiCo2O3 with one of the Ni and Co
phases on the macroscopic properties of NCO. Our findings atoms being swapped [Fig. 1(b)], (e) Ni vacancy in RS
add to the complexities of already established structural varia- NiCo2O3, and (f) Co vacancy in RS NiCo2O3. Previous
tions in this material, but the improved understanding can reports on IS NCO showed that cation vacancies influence its
help better control and exploit its unique properties. magnetic and electronic properties.13 Therefore, we have
created cation defects (5.56%) in the RS NCO structure (e)
II. EXPERIMENTAL TECHNIQUES AND THEORETICAL and (f), with the total cation to anion ratio in these two struc-
CALCULATION tures being 1:(1.05) and 1:(1.06), respectively, and shifted
Epitaxial films of NCO were grown at temperatures 250, the stoichiometry towards IS NCO. In the RS structure with-
350, and 550  C on (100) oriented MgAl2O4 (MAO) sub- out cation defects, the cation to anion stoichiometry is 1:1
strates (lattice parameter a ¼ 8.083 Å) using the pulsed laser which is different from that of IS, where the ratio is 1:(1.33).
deposition (PLD) technique. Details of the film growth can To alter the stoichiometry further towards IS NCO, cation
be found in Refs. 11 and 12. Magnetic and electrical meas- vacancies in the structure are increased in terms of 2VCo þ
urements on these samples showed ferrimagnetic p-type VNi [1:(1.2)] and VCo þ 2VNi, but these result in less stable
metallic characteristics for NCO250 and NCO350 films and configurations [supplementary material, Fig. S1].
non-magnetic insulating characteristics for NCO550 films
with a metal-insulator transition at 450  C.10
Cross-sectional transmission electron microscopy sam-
ples were prepared by first mechanical thinning and then Ar
ion milling to obtain an electron transparent thin area. All
the TEM imaging was performed using an FEI TITAN
80–300 kV double aberration corrected transmission electron
microscope. HRTEM images were recorded with a negative
Cs of 38 lm and a positive defocus Df of 8 nm, which
image atoms with white contrast that allows for intuitive
interpretation.20
Electron magnetic chiral dichroism (EMCD) experimen-
tation on the TEM was carried out at a nanometer length FIG. 1. Schematic representation of example structures considered for theo-
scale under two beam diffraction conditions which provide a retical calculations; (a) NCO RS and (b) NCO RS with Co and Ni atoms
swapped in positions in {111} planes as indicated by A and B. 1 and 2 are
higher dichroic signal due to equal intensities of direct
the lattice positions where Ni and Co vacancies are created for the calcula-
and diffracted beams.20,21 Co and Ni L3,2 absorption edge tion as indicated in (a). The magnetic spin configuration is of AFM-II type,
spectra were collected from different areas with the where the spin orientation alternates between neighboring {111} planes.
225301-3 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

FIG. 2. Cross-sectional bright field TEM images (a)–(c) with g ¼ h400i and (d)–(e) with g ¼ h220i diffracting vectors for NCO250, NCO350, and NCO550
films, respectively. Ripple-like alternate dark-bright contrast can be observed. The contrast is straight for NCO550 films. The periodicity of ripples is approxi-
mately 3–7 nm.

It is known that AFM-II spin ordering is the most stable patterns [supplementary material, Fig. S2]. The contrast rep-
configuration for RS CoO (space group: Fm3m), and transi- resents the variation of the lattice parameter over this length
tion metal impurities do not form clusters, with the AFM-II scale. From electron diffraction analysis, two different sets
configuration being retained in doped CoO as well.29 Hence, of patterns are identified and indexed, as shown in Fig. 3.
we have considered all the RS structures under investigation One corresponds to the spinel configuration (IS) and the
with the AFM-II spin configuration. To avoid construction of other to the rock salt (RS) type. Lattice parameters calculated
a large unit cell, the hexagonal unit cell with Bravais lattice by analyzing the selected area diffraction patterns are tabu-
vectors a and b lying on the {111} plane of the rock salt unit lated in Table I. The values closely match with the literature
cell is considered (Fig. 1). The deviation in the ideal c/a ratio values for the IS NCO structure, with an in-plane lattice
of the rock salt structure results in a rhombohedral parameter of 8.083 Å and out-of-plane lattice parameters of
distortion.30 8.178 and 8.173 Å for NCO250 and NCO350, respec-
tively.11,12 The RS phase has a lattice parameter 2a 8.4 Å
III. RESULTS AND DISCUSSION for all three films grown at different temperatures. In com-
Our previous observation of dark diffused contrast in parison, the lattice parameter of the IS phase is a  8.1, 8.2,
NFO and CFO films has been confirmed to be related to and 8.3 Å for films grown at 250, 350, and 550  C,
either A site cation vacancy regions or overlapping antiphase
domains.15,16 Similar dark contrast regions have been
observed in CoO epitaxial thin films and are attributed to Co
vacancy defects.19 However, in the case of NCO, other than
the dark diffused contrast areas (which are on a somewhat
larger length scale), nanoscale wavy alternate dark-bright
contrast is also observed. Strain contrast bright field images
of three NCO thin films grown at different temperatures are
shown in Fig. 2. The images are taken with the diffraction
vector g ¼ h220i and h400i, and both show alternate dark-
bright contrast areas. A wavy ripple-like alternate dark-
bright contrast is visible for NCO250 and NCO350 films. On
the other hand, the observed contrast is rather straight and
parallel to the growth direction of NCO 550 films [Figs. 2(c)
and 2(f)]. A slight difference in density between the two
structural configurations (IS and RS phases, see later discus-
sion regarding experimental confirmation) is responsible for
different scattering amplitudes of the respective volume of
materials that produce the contrast in the TEM-BF images. FIG. 3. (a)–(c) HRTEM images of three different NCO films (NCO250,
NCO350, and NCO550) showing two different coexisting phases, i.e., RS
The ripple periods are around 4–5 nm for NCO250, 5–6 nm
and IS NCO. RS and IS phases are marked with red and yellow boxes,
for NCO350, and 5–7 nm for NCO550 films, as evaluated respectively, and the corresponding indexed FFT diffractograms are shown
from the intensity profiles taken perpendicular to the ripple in the insets.
225301-4 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

TABLE I. Experimental lattice parameters extracted from electron diffrac- Based on relative energy consideration, we also explain later
tion and HRTEM images. why such observation is not expected in the case of NFO and
Lattice parameters
CFO films. The calculated C.E., lattice parameters, and mag-
netic moments of various RS structures and RS structures
Structure from HRTEM image (þ/0.1) (Å) from DP (þ/0.06)(Å) with various types of cation defects are listed in Table II.
RS 250  C 8.4 8.43 The theoretical calculations provide the lattice parameter of
350  C 8.4 8.43 the RS phase to be 4.22 (2a ¼ 8.44) Å, which is larger com-
550  C 8.4 8.43 pared to that of the IS phase (a ¼ 8.15 Å). The lattice param-
IS 250  C 8.1 8.13 eter of the RS NCO structure obtained from the electron
350  C 8.2 8.26 diffraction patterns and HRTEM imaging is found to closely
550  C 8.3 8.35 match with the theoretical lattice parameter of RS NCO with
cation defects. In the RS phase, the anion sub-lattice main-
respectively, as extracted from the electron diffraction pat- tains a pseudo cubic close packed arrangement as in the case
terns. Kindly note that the unit cell of the RS phase is dou- of spinel, with the cations randomly occupying octahedral
bled to help in comparing the lattice parameter and the lattice sites and the tetrahedral sites remaining vacant.
relative stability of various RS structures considered for the Observation of a second set of diffraction spots and the pres-
theoretical calculation with the IS structures. ence of a dominant RS phase near the top surface region in
A close inspection of the HRTEM images (Fig. 4) also the present case, along with the recent report of a high tem-
reveals regions with regular spinel-like geometry (IS) and perature RS phase, motivated us to investigate theoretically
those corresponding to A site cation defect-like (RS) areas. the possibility and stability of such phases in NCO [supple-
Areas with RS and IS phases are marked with red and yellow mentary material, Fig. S4]. Cation defects are additionally
dotted boxes, respectively, and the corresponding FFT dif- created at different concentrations to narrow the stoichiome-
fractograms are displayed in the insets. The patterns are try gap with the IS structure. The C.E. of the RS NCO phase
indexed, and they match with the RS and IS structures [Figs. is higher (5.9429 eV/atom) than that of the IS phase
4(d) and 4(e)]. Evaluation of the local lattice parameter from (5.3443 eV/atom), suggesting that it is a more stable configu-
the HRTEM images yields essentially similar values as those ration. For ideal stoichiometry, namely, the anion to cation
obtained from electron diffraction patterns for both the struc- ratio of the RS phase is NiCo2O3 and that of the IS phase is
tures (Table I). The boundaries between the two different NiCo2O4, which are not the same. The ratio of total anions to
phases are found to be incoherent with the periodic presence total cations per unit cell for these two structures is thus 1
of dislocations with the translation vector along (020) and and 1.33, with densities of 6.552 g/cm3 and 6.033 g/cm3,
(200) directions (supplementary material, Fig. S3). respectively. These suggest that the RS phase of NCO is
Formation of the RS phase is further supported by first prone to have cation defects. Theoretical calculations predict
principles based calculations of cohesive energy (C.E.). an even higher C.E. value of 6.0014 eV/atom for both Ni and

FIG. 4. (a)–(c) Electron diffraction patterns of three different samples showing the coexistence of two different RS and IS phases. Example diffraction spots
associated with two different phases with separation between them (d)–(e).
225301-5 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

TABLE II. Calculated lattice parameters, cohesive energies, magnetic moments, and bandgap values are listed for various structures. Cohesive energy for IS
NCO, CFO, and NFO cases are taken from Refs. 14 and 23.

Bandgap (eV)

Structure Lattice parameter (Å) Cohesive energy (eV/atom) Magnetic moment lB/formula unit Spin-up Spin-down

IS NCO 8.15 5.3443 2 3.9 2.79

IS NCO 25% mixed14 8.14 6.2147 0 3.31 Metallic
RS NCO 8.44 5.9429 0 3.89 3.89
RS NCO Ni vacancy 8.22 6.0014 0 3.48 Metallic
RS NCO Co vacancy 8.28 6.0014 3.6411 Metallic Metallic
RS NCO swapped position 8.42 5.9715 2.0026 3.56 3.25
IS NFO23 8.36 6.6355 2 0.35 0.35
RS NFO 8.34 6.3673 0 2.70 2.00
IS CFO23 8.32 6.6164 2 1.25 1.25
RS CFO 8.42 6.4055 0 1.60 0.80

Co vacancies in the RS structure, with a ¼ 8.22 and 8.28 Å, IS structural configurations. The cohesive energies of RS and
respectively. This implies that with cation defects, the stabil- IS structures of NFO and CFO are also listed in Table II. It
ity of the RS phase further increases as compared to IS can clearly be observed that although the RS structure is
NCO. However, it is not possible to preserve the atomic den- energetically favorable for NCO (C.E. of 6.0014 compared
sity and the stoichiometry of NiCo2O4 in the RS phase. For to 5.3443 eV/atom for IS NCO), it is not so for NFO (C.E. of
the RS phase with cation defects, the density and stoichiome- 6.3673 compared to 6.6355 eV/atom of IS NFO) and CFO
try are thus likely to be in between those of the ideal RS and (C.E. of 6.4055 compared to 6.6164 eV/atom of IS CFO).

FIG. 5. Densities of states (DOS) of (a) NCO RS, (b) NCO RS with swapped Ni and Co positions, (c) NCO RS with VNi, and (d) NCO RS with VCo.
225301-6 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

However, the point to be noted is that theoretically 25% metallic channel is dominated by Co eg and Ni t2g states with
mixed IS NCO is the most stable configuration (C.E., different levels of contributions from all the atoms in the lat-
6.2147 eV/atom), and lattice relaxation likely favors the for- tice. The bottom of the conduction band is dominated by Co
mation of a RS structure with cation defects near the upper eg states for both spin-up and spin-down channels. The fun-
regions of the films, which is the next most stable configura- damental bandgap is 2.79 eV (D ! XÞ for indirect and 3.9 eV
tion in the list. ðX ! XÞ for direct. The bandgap switches from direct to
The close match of lattice parameters of RS with Ni indirect fundamentally as the structure changes from IS
vacancies (8.22 Å) and the substrate MAO (8.083 Å) sug- (nonmagnetic) to a mixed cation (ferrimagnetic).13
gests that its formation is more favorable compared to the In the case of RS NCO, with chemical formula
RS phase without any vacancies (8.44 Å) and with Co vacan- NiCo2O3, all the octahedral sites are filled with cations and
cies (8.28 Å) due to slightly lower in-plane compressive with no cations in the tetrahedral sites of the structure. Both
strain. Our previous report on X-ray measurements of these Co and Ni are in the 2þ valence state and have a high spin
NCO samples did not reveal the presence of the RS phase configuration with magnetic moments of 2.75 lB and 1.82
with VNi because of the similar lattice parameters and lB for Co2þ and Ni2þ atoms, respectively [supplementary
restricted geometry of epitaxial thin films grown on a sub- material, Figs. S5 and S6(a)]. Kindly note that there are two
strate.11 Moreover, the formation of a ripple-like periodic different planes which are equally populated by Ni and Co
pattern of two different phases may likely be due to close lat- ions, with an equal magnitude of magnetic moments individ-
tice parameters and growth conditions and not due to peri- ually, but oriented in opposite directions with respect to each
odic strain induced by the substrate. other. The net magnetization of the structure is zero due to
We next discuss the electronic structure of various RS cancellation of total spin-up and spin-down states. The top of
phases of NCO calculated by density functional theory. The the valence band and the bottom of the conduction band are
densities of states (DOSs) and band structure plots are shown dominated by Co eg and Co t2g states [Fig. 5(a)]. As
in Figs. 5 and 6, respectively, for four different variants of observed from the DOS, the cation 3d and Op orbitals are
the RS structure. In the ideal IS NCO structure, 1=2 of total strongly hybridized. This system is a Mott Hubbard insulator
octahedral and 1=8 of total tetrahedral sites are occupied by with an indirect bandgap of 3.89 eV in both the spin-up and
[Ni2þCo3þ] and Co3þ ions. The top of the valence band of spin-down states [Fig. 6(a)]. In the case of RS NCO, when
spin-up states is dominated by Ni t2g , while the spin down Ni and Co atoms are swapped, it generates two inequivalent

FIG. 6. Band structures of (a) NCO RS, (b) NCO RS with swapped Ni and Co positions, (c) NCO RS with VNi, and (d) NCO RS with VCo. Direct and indirect
bandgaps for these structures are shown for different spin configurations.
225301-7 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

FIG. 7. Nanoscale experimental EMCD spectra of Co and Ni L3,2 edges of (a) Co and (b) Ni in regions with an IS structure and (c) Co and (d) Ni in regions
with a RS structure.

{111} planes [Fig. 1(b)]. The net magnetic moment of plane The various RS NCO structural configurations with mix-
A is larger compared to that of plane B, and this gives rise to ing between cation positions and cation vacancies have com-
a net magnetic moment of 2 lB /f. u. Both the valence and parable stability. However, the properties of the material in
conduction band edges have contributions from both Co eg terms of macroscopic magnetic moment, bandgap, and met-
and Co t2g states [Fig. 5(b)]. The indirect bandgap decreases allicity change significantly (Table II and Figs. 5 and 6). The
from 3.89 to 3.56 eV for the spin-up state, while the spin- magnetic moment is zero for RS NCO and RS NCO with
down state has a direct bandgap of 3.25 eV [Fig. 6(b)]. RS VNi. On the other hand, the magnetic moment is 2 lB /f. u. for
NCO with both VNi and VCo shows lowering of bandgaps in RS NCO with swapped cation positions and increases signifi-
both spin-up and spin-down states [Figs. 5(c) and 5(d)]. Both cantly to 3.64 lB /f. u. for RS NCO with VCo (Table III). The
the structures are of the p-type half-metallic system. For RS comparable stability and different but close lattice parame-
NCO with VNi, the valence and conduction band edges are ters between the structures suggest that these can be stabi-
dominated by Co t2g and Co eg states, respectively, whereas lized depending on the strain state and film growth
for RS NCO with VCo, Co t2g makes up both the valence and conditions. Previous magnetic measurements on NCO250
conduction band edges. and NCO350 samples showed magnetic moments of 1.87

TABLE III. Average magnetic moment per atom obtained from theoretical calculations, and for IS structures, the magnetic moment values are taken from Ref.
14. þ/ indicates the spin-up and spin-down magnetic moments of an atom, respectively.

Magnetic moment (lB /atom)

RS RS Swapped RS VNi RS VCo

IS Ferrimagnetic IS 25% mixed Ferrimagnetic

B site Co 0.03 0 0 (þ/2.75) 2.75 0.97 0.02

B site Ni 1.48 1.5 0 (þ/1.82) 1.80 1.62 3.07
A site Co 2.95 2.8 … … … …
A site Ni … 2 … … … …
O 0.11 … … … 0.47 0.53
Total/f.u 2 2 0 2.00 0 3.64
225301-8 Sharona et al. J. Appl. Phys. 122, 225301 (2017)

lB /f. u. and 1.5 lB /f. u., respectively, which are less than the the ripple pattern, XMCD simulation results, and magnetic
ideal magnetic moment of 2 lB /f. u. This discrepancy was data table.
explained previously based on either mixing of cations and
charge states between A and B sites or that of A site cation ACKNOWLEDGMENTS
defects.13 However, the observation of RS NCO, and possi-
The authors at JNCASR sincerely thank Professor C. N. R.
bly RS NCO with VNi, suggests that the reduction of mag-
Rao for the Advanced Microscopy Facility and ICMS for the
netic moment can also be because of the presence of such
research funding. The work at the University of Alabama
structures in the material.
was supported by a NSF Grant No. ECCS-1509875.
We have additionally carried out electron magnetic chi-
ral dichroism (EMCD) measurements at the nanoscale to
investigate the specific Co and Ni atom dichroic signals from 1
the coexisting two-phase regions with the diffraction condi- C. F. Windisch, G. J. Exarhos, K. F. Ferris, M. H. Engelhard, and D. C.
Stewart, Thin Solid Films 398–399, 45–52 (2001).
tion g ¼ 400. The sum of dichroic signals contains contribu- 2
D. P. Dubal, P. G. Romero, B. R. Sankapal, and R. Holze, Nano Energy
tions from an atom with different magnetic configurations 11, 377–399 (2015).
3
i.e., antiferromagnetic, ferromagnetic, and nonmagnetic due P. Silwal, C. La-o-vorakiat, E. E. M. Chia, D. H. Kim, and D. Talbayev,
to different site occupation in the present samples. However, AIP Adv. 3, 092116 (2013).
4
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17
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SUPPLEMENTARY MATERIAL 29
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See supplementary material for details on NCO with 30
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