RESEARCH ARTICLE | NOVEMBER 28 2023

Collinear and noncollinear ferrimagnetic phases in Mn4N

investigated by magneto-optical Kerr spectroscopy 
Jan Zemen 

J. Appl. Phys. 134, 203902 (2023)

https://doi.org/10.1063/5.0170621

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Collinear and noncollinear ferrimagnetic phases in

Mn4N investigated by magneto-optical Kerr
spectroscopy
Cite as: J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
Submitted: 8 August 2023 · Accepted: 25 October 2023 · View Online Export Citation CrossMark
Published Online: 28 November 2023

Jan Zemena)

AFFILIATIONS
Faculty of Electrical Engineering, Czech Technical University in Prague, Technická 2, 160 00 Prague 6, Czech Republic

a)
Author to whom correspondence should be addressed: jan.zemen@cvut.cz

ABSTRACT
Ferrimagnetic antiperovskite Mn4 N has received growing interest due to room-temperature observation of large perpendicular magnetic
anisotropy, low saturation magnetization, and ultrafast response to external magnetic fields. Comprehensive understanding of the underlying
magnetic structure is instrumental in design and fabrication of computer memory and logic devices. Magneto-optical spectroscopy provides
deeper insight into the magnetic and electronic structure than magnetometry. Simulations of a magneto-optical Kerr effect in biaxially

06 December 2023 17:42:02

strained Mn4 N are performed using density functional theory and linear response theory. We consider three ferrimagnetic phases, two col-
linear and one noncollinear, which have been investigated separately by earlier studies. The simulated spectra are compared to measured
magneto-optical data available in recent literature. One of the collinear ferrimagnetic phases is found to be consistent with the measured
spectra. We show that an admixture of the noncollinear phase, which is the ground state of unstrained Mn4 N, further improves the agree-
ment with measured spectra, and at the same time, it could explain the lower than predicted net moment and magnetic anisotropy observed
in thin films on various substrates.

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I. INTRODUCTION We avoid the reliance on common ferrimagnets containing

Traditionally, ferrimagnets have been applied in magneto-
optical recording,1–3 where a laser beam is used to increase the
temperature close to the Curie point so that the magnetization can
be reversed by a small applied magnetic field. However, more
recently, ferrimagnetic materials have attracted much attention for
high-density magnetic random access memories (MRAMs) and
logic devices, which benefit from high perpendicular magnetic
anisotropy (PMA), saturation magnetization much lower than in
typical ferromagnets, and Curie temperature well above room
temperature.4–7
Ferrimagnets usually consist of two magnetic sublattices with
antiferromagnetic coupling between them, which allows for fast
spin dynamics motivating extensive research in antiferromagnetic
spintronics.8–10 The absence of net magnetic moment in antiferro-
magnetic materials allows for closely packed memory arrays but
precludes control of the magnetic domain structure by an external
magnetic field. The small but finite net magnetization of ferrimag-
netic materials alleviates this problem.
rare earth elements11 by turning to metallic antiperovskite
nitrides, some of which have a collinear or noncollinear ferrimag-
netic structure.12–14 Mn-based antiperovskite nitrides are a broad
family of materials hosting a range of phenomena, including
magneto-transport,15–17 magneto-caloric,18–20 or magneto-optical
properties, tunable by chemical composition or lattice strain.21–23
Mn3 GaN, a widely studied member of this family with a triangu-
lar antiferromagnetic ground state, can develop a collinear ferri-
magnetic (FIM) phase under compressive biaxial strain at room
temperature.24 Subsequently, magneto-optical Kerr spectroscopy
has revealed the magnetic structure of Mn3 NiN, a closely related
antiperovskite. The measured data are consistent with the pres-
ence of a collinear FIM phase at room temperature.25
The magnetic structure of antiperovskite Mn4 N has even
further complexity than Mn3 NiN as Ni on the 1a site is replaced
by another Mn with a large magnetic moment as shown in
Figs. 1(a)–1(c). Large PMA reaching 0.1 MJ/m3 and an ultrafast
response to an external field has been observed in Mn4 N

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recently.26–36 In addition, low saturation magnetization,
μ0 Ms
0:1 T, has been demonstrated by numerous studies of
Mn4 N thin films listed in Table I. Therefore, in devices controlled
by spin-transfer torque (STT), such as magnetic tunnel junctions
(MTJs), the critical STT-current density, Jc / αMs tHk (where α is
the damping constant, t is the magnetic layer thickness, and Hk is
the anisotropy field proportional to the PMA energy density, Ku ),
is expected to be small.29,37–39 More favorable material properties
of Mn-based antiperovskite nitrides have been reviewed by Isogami
and Takahashi40 recently.
In order to utilize the potential of Mn4 N for spintronic appli-
cations, such as MTJs or skyrmionic devices,31 it is crucial to attain
a thorough understanding of the microscopic origin of these advan-
tageous properties and to be able to grow thin films with a well
defined magnetic structure on substrates compatible with CMOS
technology.
In experimental studies listed in Table I, Mn4 N has been
deposited since 2014 on a range of substrates, e.g., MgO, SrTiO3
(STO), and LaAlO3 (LAO) with a mismatch of approximately
6%, 0:1%, and þ2%,30 respectively, assuming (001) surfaces
and a lattice constant of cubic Mn4 N equal to 0.3865 nm.41 It has
been observed using x-ray diffraction that the films have
c=a
0:98  0:99, where a and c are the in-plane and out-of-plane
lattice constant, respectively, despite the different magnitude and
sign of a lattice mismatch.
Therefore, experimental studies generally conclude that the
origin of PMA in Mn4 N films is the tetragonal distortion.26,27,30,42
Both Ito et al.28 and Isogami et al.37 found that FIMB has signifi-
cantly lower total energy than FIMA in the range
c=a [ (0:96  1:1), in agreement with our simulations shown in
Fig. 1(d). Both studies suggest that this intrinsic tetragonal phase,
FIMB , explains why c=a [ (0:98  0:99) has been reported in
Mn4 N films epitaxially grown on different substrates regardless of
the film thickness and the lattice mismatch. However, negligible
dependence of PMA on c=a was predicted by Isogami et al.37 in
disagreement with PMA measured by Hirose et al.30 in Mn4 N on
MgO, STO, and LAO. Moreover, very recent x-ray magnetic circu-
lar dichroism (XMCD) measurements of a magnetic structure of
thin Mn4 N films on STO53 reveal the FIMB phase for film thick-
ness t . 5 nm and a noncollinear ferrimagnetic structure for
t ¼ 4 nm. Ito et al.28 and Isogami et al.37 did not consider the
ncFIM phase identified by Fruchart et al.14 as cubic anisotropy was
expected instead of PMA seen in Mn4 N films. This represents a
gap in the available simulations, which hinders interpretation of
new experimental findings.
Therefore, in this study, we compare the collinear (FIMA ,
FIMB ) and noncollinear FIM (ncFIM) phases of strained Mn4 N
based on total energy, magnetocrystalline anisotropies, magnetic
moments, and magneto-optical Kerr effect (MOKE). The

06 December 2023 17:42:02

Ab initio studies of Ref. 28 and 37 investigate two collinear ferri-
magnetic phases with PMA, the so called type A (FIMA ) and type
B (FIMB ) shown in Fig. 1(b) and 1(c), respectively. Both studies
deduce the potential presence of FIMA and FIMB magnetic phases
(both with magnetic space group 123.345, P4/mm0 m0 ) from
neutron diffraction experiments.41 However, Zhang et al.49 and
Gercsi et al.50 point out that there is no experimental evidence for
FIMB in bulk powder samples of Ref. 41, which sees two (as in
FIMA ) rather than three (as in FIMB ) inequivalent Mn sites, in
agreement with a later nuclear magnetic resonance (NMR) study.51
A subsequent diffraction study with polarized neutrons identified a
noncollinear variant of the FIMA phase (two inequivalent Mn sites)
and a triangular ferrimagnetic phase (ncFIM).14 Magnetic
moments of Mn atoms in this “umbrella-like” structure with mag-
netic space group 166.101, R3m0 (cubic) or 12.62, C2’/m0 (biaxially
strained) shown in Fig. 1(a) do not mutually compensate as in
cubic Mn3 NiN or Mn3 GaN due to the extra local magnetic
moment on the 1a site, m1a . The moments in face-center 3c posi-
tions, m3c , are tilted out of the (111) plane (where the Mn atoms
form a kagome lattice) by approximately 20 to have a component
along the [111] axis, antiparallel to m1a . The ncFIM structure was
confirmed computationally by Uhl et al.52 and more recently by
Zhang et al.,49 including the net moment along the [111] axis,
mnet ¼ 1:14 μB .41 The same team also proposed related noncollin-
ear ferrimagnetic phases in the Mn4 N film on MgO46 based on FIG. 1. Comparison of ferrimagnetic structures of Mn4 N considered: (a) ncFIM,
ncFIM and the coplanar triangular antiferromagnetic structure of (b) FIMA , (c) FIMB —unit cells with magnetic moments indicated by arrows and
Mn-based antiperovskite nitrides. chemical identities indicated by labels: Mn on 3c sites in red, Mn on 1a sites in
Here, we focus on experimental data available for thin films. blue, and N in green; and (d) corresponding calculated total energies vs the
c=a ratio assuming fixed ν ¼ 0:33 or fixed a ¼ a0 (as specified in
We are not aware of neutron diffraction studies of thin Mn4 N
parentheses).
films; therefore, we work with FIMA and FIMB studied earlier.28,37

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TABLE I. Comparison of Mn4N films with thickness (t), measured magnetic anisotropy energy (Ku), and saturation magnetization (Ms). The last six rows include data for bulk:
one neutron diffraction data of a powder sample at 77 K and five rows of DFT-simulated data for magnetic phases given in the first column.

Substrate c/a t (nm) Method Ku (MJ/m3) Ms (kA/m)

27
MgO 0.987 35 PLD 0.16 157
MgO26 0.99 26 MBE 0.22 145
MgO42 0.99 100 Sputtering 0.88 110
STO28 0.99 25 MBE 0.1 80
MgO43 0.983 9 MBE 0.18 127
MgO44 0.991 30 MBE 0.075 100
MgO45 … 10 MBE 0.11 118
STO45 … 10 MBE 0.11 105
STO29 … 10 MBE 0.11 71
MgO30 0.993 18 MBE 0.06 63
STO30 0.989 17 MBE 0.126 73
LAO30 0.998 19 MBE 0.045 53
MgO37 0.99 30 Sputtering 0.1 80
MgO46 0.99 28 Sputtering 0.17 156
Glass34 0.993 45 Sputtering 0.022 36
Glass47 0.988 48 Sputtering 0.073 99
MgO/VN36 0.987 28 Sputtering 0.043 85
Bulk41 1.0 … Homog. powder … 178
FIMA37 0.99 … DFT simul. 0.5 6.3
FIMB37 0.99 … DFT simul. 3.8 143
ncFIM48 1.0 … DFT simul. … 194
FIMBa 0.99 … DFT+U simul. 3.78 191
ncFIMa 0.99 … DFT+U simul. 1.81 114

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a
Last two rows show data calculated in this work.

immediate motivation is a recent study of MOKE in 23 nm thick
Mn4 N films sputtered on an MgO substrate, which proposed that a
superposition of different ferrimagnetic phases could exist.54
Moreover, an in-plane component of magnetization has been
detected in an Mn4 N film deposited on MgO by MBE,55 and the
authors explained it in the presence of a FIM phase with magneti-
zation along the [111] axis.
II. COMPUTATIONAL METHODS
We employ noncollinear spin polarized density functional
theory (DFT) combined with linear response theory following the
approach of Ref. 56 and our earlier work.25 We use the projector
augmented wave method as implemented in the VASP code57 with
generalized gradient approximation (GGA) parameterized by
Perdew–Burke–Ernzerhof.58 Our results were obtained using a
500 eV energy cutoff and a 23  23  23 k-mesh (for a unit cell
with 5 atoms) to ensure convergence (in agreement with numerical
settings of Ref. 37). The valence configurations of manganese and
nitrogen are 3d 6 4s1 and 2s2 2p3 , respectively.
As has been done for MOKE spectra of Mn3 NiN25 and earlier
MOKE studies of some collinear antiferromagnets, such as
CuMnAs,59 we modify the intra-atomic Coulomb interaction
within GGA through the rotationally invariant approach to GGA
+U as proposed by Dudarev et al.60 We explore values of U from
0.2 to 2.2 eV on the Mn-3d orbital. (Most data shown here were
simulated using U ¼ 0:7 eV refined in Ref. 25.) This repulsion lifts
the unoccupied manganese 3d-states further away from the Fermi
level, resulting in a blueshift in the optical and magneto-optical
responses, which improves the agreement with the available mea-
sured data.54
MOKE spectra offer a valuable insight into the magnetic and
electronic structure of thin films and reflect the symmetry of the
magnetic structure as detailed in Appendix D. We evaluate the
Kerr rotation, θ(ω), and ellipticity, η(ω), from the complex permit-
tivity tensor, εij (ω), computed using VASP.25,56 In the polar config-
pffiffiffiffiffi
uration, they are related as follows: θ þ iη ¼ εxy =[(ε0  1) ε0 ],
where ε0 ¼ (εxx þ εyy )=2. The films are conductive, 23 nm thick;54
therefore, the light is mostly absorbed within the layer justifying
the use of semi-infinite medium approximation.
III. RESULTS AND DISCUSSION
The unit cells and corresponding total energies as functions of
the c=a ratio are shown in Fig. 1. Available experimental data listed
in Table I provide a range of values of Poisson’s ratio, ν. Therefore,
for each c=a ratio, we calculate the total energy assuming
ν ¼ 0:3346 [labeled by ν in Fig. 1(d)] as well as constant a ¼ a0
[labeled by a0 in Fig. 1(d)], where a0 ¼ 0:389 nm is the equilibrium
lattice parameter of ncFIM (the ground state at c=a ¼ 1) from our

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DFT simulations. This is close to the experimental value

a0 ¼ 0:3865 nm and to an earlier DFT calculation,
a0 ¼ 0:382 nm.49 We note that our conclusion is independent of
this choice: The energy minimum for the FIMA phase obtained at
c=a . 1 is more than 0.2 eV/f.u. higher than the energy minimum
of FIMB at c=a ¼ 0:98, in agreement with earlier DFT studies,28,37
which suggest that the Mn–Mn direct AFM interaction might be
stabilizing the FIMB structure. However, the ground state of the
ncFIM phase (c=a ¼ 1) is another 30 meV/f.u. lower than the
energy minimum of FIMB .
Therefore, it is conceivable that the ncFIM phase, energetically
favorable for c=a [ (0:99  1:0), coexists with the FIMB phase in
films where the lattice mismatch with the substrate does not induce
large tensile biaxial strain, c=a , 0:99. This failure to induce strain
can be due to (a) dislocations in the lattice structure at the inter-
face,27,28 (b) nitrogen deficiency at the interface,37 or (c) relaxation
due to greater film thickness. Areas of the film with less disloca-
tions (better epitaxy) are then more likely to stabilize the tetragonal
FIMB phase by the smaller c=a ratio. The films relevant to our
MOKE study show c=a ¼ 0:989;54 therefore, the ncFIM could
coexist with the FIMB phase.

A. MOKE spectra
Figure 2 presents the main result of the work. It shows Kerr
rotation and Kerr ellipticity as a function of energy, ω [ (1  7) eV.
(Our model does not include the intraband contribution, which

06 December 2023 17:42:02

dominates below 1 eV.) We calculated the spectra for several ratios
c=a [ (0:97  1:03), but the dependence on tetragonal distortion
appears to be much smaller than the differences between the three
FIM phases; therefore, we plot only spectra for c=a ¼ 0:99 and 1.01.
The spectra in this figure include fine features as we use small
Gaussian smearing, σ ¼ 0:01 eV, to treat the partial occupancies in
k-space integration. This approach would correspond to experimen-
tal data measured in a high quality monocrystalline (epitaxial) film
with low density of structural defects at low temperatures.
In order to interpret our spectra based on features of the band
structure, we plot the projected DOS (PDOS) for all three phases in
Fig. 3. We resolve PDOS only for Mn-3d orbitals as the other con-
tributions are small and too far from the Fermi energy to play an
important role in the visible magneto-optical response. Mn1 , Mn2 ,
and Mn3 occupy the 3c sites with Cartesian coordinates (0.0, 0.5,
0.5), (0.5, 0.0, 0.5), and (0.5, 0.5, 0.0), respectively, whereas Mn4
occupies the 1a site with coordinates (0, 0, 0) as shown in Fig. 1.
We note that our PDOS for FIMB phase is in agreement with Fig. 7
(a) of Ref. 37.
Figure 3(a) for FIMA shows PDOS with one dominant transi-
tion indicated by a gray arrow between a peak in occupied states of
Mn13 and a peak in excited states of Mn4 . This transition described
by energy difference, dE
2 eV, corresponds to the sharp peak in
the magneto-optical response at ω
2 eV. Figure 3(b) for FIMB
shows PDOS with two dominant transitions indicated again by
arrows described by dE
2 and 3 eV, which correspond to a dip
and a peak in Kerr rotation, respectively.
Figure 3(c) for ncFIM shows PDOS lacking prominent peaks
around 2 eV below the Fermi level, which are present in the case of
FIMB . The peak in PDOS of FIMA around 0.5 eV above Fermi
FIG. 2. Simulated MOKE spectra: (a) Kerr rotation and (b) Kerr ellipticity; for
c=a ¼ 0:99 (solid lines in both panels) and c=a ¼ 1:01 (dashed lines in both
panels), U = 0.7 eV, and no smoothing.
energy is shifted to 1 eV in ncFIM. Such a band structure results in
the absence of prominent peaks in the magneto-optical response at
photon energies below 4 eV. We conclude that the predicted spec-
tral features can be interpreted qualitatively based on transitions
from Mn-3d orbitals on 3c sites to Mn-3d orbitals on site 1a.
In order to compare our data to MOKE spectra measured by
Sakaguchi et al.,54 we interpolate our curves plotted in Fig. 2 using
the UnivariateSpline function from Python SciPy package with a
smoothing parameter set to 0.003 on a linear grid with 200 points.
In addition, we include analogous MOKE spectra for U ¼ 2:2 eV.
(Please see Appendix B for this spectra without smoothing.)
The smeared spectra for c=a ¼ 0:99 are shown in Fig. 4. Our
Kerr rotation and ellipticity can be compared directly to Figs. 5(a)
and 5(b) of Ref. 54, respectively, where the boron content in Mn4 N
is zero.

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First, we note that the amplitude of the measured spectra is
approximately 0.1 , an order of magnitude larger than in the
related noncollinear Mn-based systems, such as Mn3 NiN25 and
Mn3 Sn.61 The amplitude of the simulated spectra is only a factor of
two larger, indicating high quality of the Mn4 N film.
Second, the measured θ(ω) is positive below 1.5 eV, has a dip
around 2.2 eV, and returns to positive values above 3 eV, where the
studied interval ends. Such a trend is observed only in data simu-
lated for the FIMB phase with a corresponding dip at 2.1 eV
(2.3 eV) for U ¼ 0:7 eV (U ¼ 2:2 eV). The crossing points,
θ(ω) ¼ 0, are at 1.4 and 2.6 eV (1.5 and 3 eV) for U ¼ 0:7 eV
(U ¼ 2:2 eV). We note that there is a shift to lower energies for
U ¼ 0:7 eV and a perfect agreement with experiment for
U ¼ 2:2 eV. A shift of optical and magneto-optical responses to
higher energies is commonly achieved in DFT studied by increasing
FIG. 3. Comparison of projected density of states (PDOS) for FIMA (a), FIMB
(b), and ncFIM (c) phases with c=a ¼ 0:99 and U = 0.7 eV. Gray arrows indi-
cate potentially dominant excitations.
J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
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the Coulomb repulsion on sites with more localized states (here the
Mn-3d states). Therefore, we simulated the spectra for a range of
Hubbard parameters, U, from U ¼ 0:2 to 2:2 eV. The upper
limit is large in comparison with Mn3 NiN25 and CuMnAs59 where
U ¼ 0:7 and U ¼ 1:7 eV were used, respectively. U ¼ 2:2 eV does
not significantly affect the local magnetic moments and MAE
of FIMB as shown in Appendix A, but the properties of ncFIM
become unrealistic, including the prediction of a ferrimagnetic
compensation (zero saturation magnetization), which has never
been observed experimentally. We believe that it is unlikely that the
localization of Mn-3d electrons should be described by very differ-
ent values of U in different magnetic phases.
Alternatively, the crossing point at 2.6 eV for FIMB could be
shifted to higher energy by assuming an admixture of ncFIM,
which is negative throughout the energy interval. Such a superposi-
tion of spectra would also shift the crossing point at 1 eV to lower
06 December 2023 17:42:02
FIG. 4. Simulated MOKE spectra: (a) Kerr rotation and (b) Kerr ellipticity; for
c=a ¼ 0:99, U ¼ 0:7, and U ¼ 2:2 eV, smoothing parameter ¼ 0:003.
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energies in contrast to the experiment. However, our predictions Isogami et al.37 speculate that this discrepancy is due to
are less reliable below 1.5 eV as our model does not include the imperfect chemical ordering of nitrogen, which can lead to nitro-
intraband contributions (the Drude peak). gen deficient impurity phases, such as nano-crystals of pure Mn, or
We check the agreement in the case of Kerr ellipticity, η(ω), the formation of dislocations in the initial growth layer. More gen-
which is Kramers–Kronig-related to θ(ω). Figure 5(b) of Ref. 54 erally, the initial growth layer of the Mn4 N film on the substrate
shows a monotonous decrease of η(ω) to zero around 3 eV. As with a large lattice mismatch is prone to dislocations, which
expected, FIMB is the only phase that shows such a trend in the degrade the PMA due to their weak crystallinity. On the other
simulated spectrum, but the crossing point is shifted to slightly hand, the anisotropy, Ku , of FIMB is not predicted to depend
lower energy. To conclude the comparison with Fig. 4, we caution strongly on biaxial strain;37 therefore, we cannot expect lower PMA
that the smoothing parameter reflects the unknown density of for substrates of a low lattice mismatch with Mn4 N. At the same
structural defects and thermal excitations in the sample—we have time, the shape anisotropy competes with PMA, but it is negligible
to use a large value to obtain the smooth spectra observed experi- due to the low saturation magnetization. We note that experimental
mentally, which turns the exact crossing-point values less reliable. PMA is determined using the crossing point of saturated
In conclusion, the comparison of our MOKE spectra to out-of-plane (easy axis) and in-plane (hard axis) hysteresis curves;
Ref. 54 strongly suggests the presence of FIMB in agreement with a
recent NMR study,53 but it cannot confirm or rule out the presence
of ncFIM. In order to attain a deeper understanding of the nontriv-
ial magnetic structure giving rise to the MOKE spectra presented
above, we proceed by comparing the simulated magneto-crystalline
anisotropy and the saturation magnetization with experimental
values. The film is measured in a magnetic field applied parallel
and antiparallel to the [001] axis (out-of-plane), and the two
spectra are subtracted to eliminate nonlinear magneto-optical
effects.54 The film has to undergo a rotation of magnetic moments
between the two measurements, i.e., overcoming a certain energy
barrier. Sakaguchi et al.54 measured the anisotropy field,
Hk ¼ 1:5 T, which is a typical value in Mn4 N on MgO, but we do

06 December 2023 17:42:02

not know the saturation magnetization. We have to assume that the
anisotropy follows the general trend shown in Table I
(Ku ¼ 0:1 MJ/m3 ) so that the sample could be fully aligned with
the applied field during MOKE measurement.

B. Magnetocrystalline anisotropy
We calculate the total energies of magnetic structures shown
in Figs. 1(a) and 1(c) coherently rotated to align the net magnetic
moment, mnet , with the [001] axis (perp-to-plane), the [110] axis
(in-plane), and the [001] axis. In the case of FIMB , the anisotropy
within the (001) plane is weak (e.g., the difference between energies
for mnet k[110] and mnet k[100] is below 0.03 meV/f.u.
2% of the
predicted PMA); therefore, we choose the rotation to the [110]
axis, which goes through the easy axis of the ncFIM phase,
mnet k[111].
In Fig. 5(a), the total energy is plotted as a function of angle f
between the net magnetization and the [001] axis (perpendicular to
the film). The insets show the orientation of the local moments of
the FIMB phase for net magnetization pointing along [001], [110],
and [001]. This choice is relevant for the polar-MOKE experiment,
where the sample is measured in a magnetic field applied parallel
and antiparallel to the [001] axis.54 The film has to undergo a rota-
tion of magnetic moments driven by the reversal of the perpendic-
ular applied field between the two measurements. Therefore, it has
to overcome the energy barrier of the in-plane orientation, FIG. 5. Comparison of FIMB and ncFIM phases based on (a) total energy and
f ¼ π=2, which is Ku ¼ 1:4 meV per formula unit or 3.78 MJ/m3 (b) magnetization projection, Mz ; angle f describes the switching from magneti-
for the FIMB at c=a ¼ 0:99. This PMA is in perfect agreement with zation along the [001] axis to the opposite direction. Data for c=a ¼ 0:99 and
U ¼ 0:7 eV. The insets show the magnetic structure at significant points along
earlier calculations37 as shown in Table I. However, the value is an the selected switching paths.
order of magnitude larger than experimental PMA
0:1 MJ/m3 .

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therefore, magnetization switching facilitated by domain-wall prop-
agation cannot explain the smaller experimental values either.
However, several films show a small but finite coercive field
even for the in-plane M-H loop which is not consistent with purely
uniaxial anisotropy of FIMB phase34,43,47 and speaks in favor of our
hypothesis of ncFIM and FIMB coexistence. Moreover, the admix-
ture of ncFIM is consistent with the conclusions of Wang et al.55
and Yasuda et al.53 based on measured anomalous Hall effect
(AHE) and XMCD data, respectively.
Therefore, we also study the magnetocrystalline anisotropy of
ncFIM. The energy barrier during the magnetization reversal at
c=a ¼ 0:99 is smaller, Ku ¼ 0:67 eV/f.u. or 1.81 MJ/m3 ; therefore,
an admixture of ncFIM could provide another mechanism explain-
ing the smaller experimental Ku . However, the spin reorientation
mechanism becomes much more complicated in the case of ncFIM.
There are eight variants of this phase with the net magnetization
pointing parallel or antiparallel to the four body-diagonals, in
perfect analogy to Mn3 NiN.17 A large applied field can, in princi-
ple, align the net magnetization with the [001] axis, but the rota-
tion of the moments to the opposite field orientation can go
through different energy minima and energy barriers depending on
the local conditions in the film. We have carried out a DFT study
of the total energy landscape as a function of coherent rotations of
the four local moments.
We considered all rotations that belong to the Pm3m space
group of the cubic perovskite lattice: twofold and fourfold rotations
about the main axes, threefold rotations about the body diagonals,
and twofold rotations about the side diagonals. Details about our
findings will be summarized elsewhere. Here, we show an example
of a rotation between two energy minima (from [111] to [111]),
which incurs the lowest energy barrier, Ku ¼ 0:67 eV/f.u. men-
tioned above. This rotation is a simultaneous rotation by π=2 about
the [010] axis, by π=2 about the [001] axis, and by 2π=3 about
[111] axis. (An intuitive simple rotation of magnetization from
[111] to [111] about the [110] axis would not restore the ground
state magnetic structure.) The dashed–dotted line in Fig. 5 consists
of (i) a simple rotation about the [110] axis from a state with net
moment along [001] to pffiffithe ground state along [111] denoted by
f0 ¼ π=2  arctan (1= (2)) or f0 ¼ 55:4 in the case of c=a ¼ 1
or c=a ¼ 0:99, respectively, (ii) the simultaneous rotation to
another ground state along [111] denoted by π  f0 ), and (iii) a
simple rotation about [110] to a state with net magnetization along
[001]. All four significant states are depicted as insets in Fig. 5(b).
Notably, the structure in the first inset is of the same type (and has
the same direction of magnetization) as the noncollinear structure
proposed for Mn4 N in Fig. 2(d) of Ref. 46.
In summary, Fig. 5 illustrates that a film in the ncFIM phase
with a cubic lattice or with slight tetragonal distortion,
c=a [ (0:99, 1), can be in a multi-domain state even at saturation if
the field is applied perpendicular to the film and the magnetization
reversal can follow different paths for each domain. The anisotropy,
Ku , is smaller than in FIMB but still too large to achieve saturation
when the field typically applied in the experiment (
1 T) is along a
hard axis, such as the [001] axis. For simplicity, in our MOKE sim-
ulation of ncFIM presented in Fig. 2, we assume that the applied
field switches between two single-domain ground states with net
moment along [111] and [111] whose local moments are linked by
J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
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an inversion, in analogy to our earlier work on MOKE in
Mn3 NiN.25 We have to subtract the off-diagonal elements of the
dielectric tensor calculated for these two states in order to eliminate
non-linear magneto-optical effects. In the case of a collinear ferri-
magnet or a ferromagnet, this inversion of all moments can be
achieved by a coherent rotation of all moments around an axis per-
pendicular to all of the moments. Such a process corresponds to
experimental magnetization switching. However, in ncFIM, there is
no axis perpendicular to all four magnetic moments. The coherent
rotation of ncFIM shown in Fig. 5(b) may describe an experimental
switching scenario, but it does not invert all the moments and it
inverts only the x and z-component of the net moment. It is
beyond the scope of this work to establish if the application of the
field perpendicular to the film can achieve the full inversion of
magnetic moments assumed in our theory or if it can be described
by coherent rotations of the noncollinear moments. We caution
that this ambiguity of the magnetization switching process compro-
mises our ability to interpret the measured MOKE spectra.
C. Saturation magnetization
Our hypothesis of an ncFIM admixture in a dominant FIMB
phase has implications also for the observed saturation magnetiza-
tion, Ms (net moment); therefore, we include Fig. 5(b) to show the
out-of-plane magnetization component, Mz . Isogami et al.37
predict Ms ¼ 180 mT for FIMB and observe 110 mT experimen-
tally. They are able to attribute the discrepancy to a dead layer at
06 December 2023 17:42:02
the interface with a substrate, nitrogen deficiency, and top surface
oxidation. Here, we suggest that the lower Ms could be due to the
admixture of ncFIM with Ms ¼ 0:727 μb /f.u. = 143 mT as shown in
Table I, which is smaller than Ms ¼ 1:223 μb /f.u. = 240 mT that we
predict for FIMB .
More details about the dependence of local magnetic
moments on Mn sites and the net moment on the Hubbard param-
eter U for all three phases are presented in Appendix A. Here, we
compare our moments calculated with U ¼ 0:7 eV to local mag-
netic moments deduced by Takei et al.41 based on neutron diffrac-
tion in powder samples. They obtained a net moment,
exp
mnet ¼ m1a þ 3m3c ¼ 1:14 μB /f.u., from magnetometry and
exp
mdiff ¼ m1a  m3c ¼ 4:75 μB /f.u. from the magnetic scattering with
mixed indices. Solving these two equations assuming collinear
order with m1a antiparallel to m3c gives m1a ¼ 3:85 μB /f.u. and
m3c ¼ 0:9 μB /f.u. in disagreement with our results for FIMA .
Takei et al. assume FIMA with a cubic lattice where we get prohibi-
tively high total energy as shown in Fig. 1(d). Later, a polarized
neutron diffraction study by Fruchart et al.14 found a noncollinear
variant of FIMA , possibly the ncFIM phase where we get
mnet ¼ 0:727 μb /f.u. and m1a ¼ 3:65 μB /f.u. (on the Mn4 site),
which is in reasonable agreement with Takei et al. Our value of
m3c ¼ 2:8 μB /f.u. (on sites Mn1 , Mn2 , Mn3 ) is much larger than the
measured 0.9 μB /f.u. We believe that this discrepancy is due to the
assumption of collinearity in Ref. 41. Increasing U leads to a higher
discrepancy in the case of the simulated net moment, which van-
ishes at U ¼ 1:7 eV. Such magnetic compensation has not been
observed in Mn4 N, to our best knowledge; therefore, we prefer to
explain our MOKE spectra by a combination of FIMB and ncFIM
phases rather than FIMB alone with U ¼ 2:2 eV.
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IV. SUMMARY
We simulated the MOKE spectrum of strained Mn4 N using
DFT+U assuming three ferrimagnetic phases investigated by earlier
theoretical studies. We compared our results to polar-MOKE
spectra measured by Sakaguchi et al.54 in Mn4 N films on an MgO
substrate. We found that the key features of the simulated spectra
are consistent with the measured spectrum in the case of the FIMB
phase. The agreement of the simulated Kerr rotation could be
further improved if a fraction of the ncFIM phase was added to the
dominant FIMB phase. At the same time, the admixture of ncFIM
could explain the lower PMA, the lower Ms , and the deviation of
the magnetic easy axis from the film normal, all observed experi-
mentally. We believe that our analysis will motivate further MOKE
studies where the energy interval is wider and the applied field can
be inverted along a chosen path. This could shed more light on the
ncFIM phase preferred at lower tensile strains and enable spin-
tronic devices with sub-nanosecond spin dynamics at room
temperature.

ACKNOWLEDGMENTS
We acknowledge fruitful discussions with Freya Johnson,
Lesley F. Cohen, Martin Veis, Jakub Železný, and Zsolt Gercsi. This
work was supported by the Ministry of Education, Youth and
Sports of the Czech Republic through the e-INFRA CZ (ID:
90254).

AUTHOR DECLARATIONS

06 December 2023 17:42:02

Conflict of Interest
The author has no conflicts to disclose.

Author Contributions
J. Zemen: Conceptualization (equal); Data curation (equal);
Formal analysis (equal); Funding acquisition (equal); Investigation
(equal); Methodology (equal); Validation (equal); Visualization
(equal); Writing – original draft (equal); Writing – review &
editing (equal).

DATA AVAILABILITY
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
APPENDIX A: MAGNETIC MOMENTS
In a ferrimagnetic system, it is useful to list the predicted mag-
netic moments to fully describe the magnetic structure. Moreover,
we use the magnetic moments to check for reasonable values of the
Hubbard parameter U on the Mn-3d orbitals. Figure 6 shows the
dependence of local magnetic moments on Mn sites and the net
moment (saturation magnetization) on U for c=a ¼ 0:99 and all
three phases. The moment of Mn4 on the corner site, m1a , and the
exp
net moment, mnet , measured by Takei et al.41 in a powder sample
are included as a reference (horizontal lines) in all three panels. As
discussed in the main text, there is semiquantitative agreement
with predicted mnet and m1a . (The other predicted local moments
are much larger than the experimental reference most likely due to
FIG. 6. Comparison of local magnetic moments on Mn atoms for (a) FIMA , (b)
FIMB , and (c) ncFIM phases for c=a ¼ 0:99 and a range of parameters U. The
sites are labeled as in Fig. 3. The legend is the same for all three panels. In the
case of collinear phases FIMA and FIMB , the moments are parallel or antiparal-
lel to the z-axis so that we can include signs. In the case of ncFIM, the
moments are noncollinear so that we plot only the magnitude with the exception
of mnet where the negative sign indicates antiparallel alignment to Mn4 .
Experimental moments41 are indicated by dashed–dotted horizontal lines.
the inappropriate assumption of collinear phase FIMA in the exper-
iment.) In case of ncFIM, mnet (m1a ) decreases (increases) with U,
and we find the best overall agreement for U ¼ 0:7 eV, which we
also identified in an earlier MOKE study of Mn3 NiN.25
The best agreement with the measured moments is observed in
case FIMB , which is most likely a coincidence as Takei et al. saw
only two inequivalent magnetic sites (1a and 3c) respecting the
cubic symmetry of the lattice. However, FIMB has three inequivalent
magnetic sites. We note that using our methodology, FIMA and

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FIMB cannot be simulated with a cubic lattice—the moments relax
to ncFIM during the self-consistent DFT cycle or vanish when a
constraint is applied. Therefore, we compare all the moments for
c=a ¼ 0:99, but the tetragonal distortion c=a [ (0:97, 1:1) has only
an insignificant impact on the local moment sizes. As expected
based on the unfavorable total energy, FIMA shows the poorest
exp
agreement with experimental net moment mnet .
APPENDIX B: DEPENDENCE OF MOKE ON U
We calculated MOKE spectra for the FIMB and ncFIM phase
for c=a ¼ 0:99 with a range of Hubbard parameter,
U [ (0:2, 2:2) eV. Figure 7 shows a clear trend how the onsite
repulsion lifts the unoccupied manganese 3d-states further away
from the Fermi level, resulting in a blueshift in the spectra. The
dominant peak around 3 eV moves to higher energies with increas-
ing U. At the same time, for higher U, a minor peak appears in
FIG. 7. Simulated MOKE spectra for the FIMB phase at c=a ¼ 0:99: (a) Kerr
rotation and (b) Kerr ellipticity.
J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
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Kerr rotation around 2.5 eV in disagreement with the measured
spectra, but it is not large enough to appear in the smoothed
spectra that we compare to the experiment.
Figure 8 shows an analogous set of spectral curves for the
ncFIM phase. A less clear blueshift is visible due to the lack of
more pronounced features in the spectrum. Two spectra are
included for an ncFIMz state, which has the net moment aligned
with the [001] axis as shown in Fig. 5. We explained in the main
text that we do not expect the field applied perpendicular to the
film to force the moment of the ncFIM domain into this hard
direction due to the large anisotropy. If the applied field was large
enough to achieve saturation, the Kerr rotation of the ncFIMz state
could not be used to push the crossing-point of the combined
(FIMB +ncFIMz ) from 2.5 to 3 eV as seen in the experiment.
However, the dip at 2.5 eV is broadly in agreement with the mea-
sured spectra. Finally, we note that ncFIM spectra with U ¼ 2:2 eV
06 December 2023 17:42:02
FIG. 8. Simulated MOKE spectra for the ncFIM phase at c=a ¼ 0:99: (a) Kerr
rotation and (b) Kerr ellipticity. ncFIMz labels spectra of a state with the net
moment along the z-axis.
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FIG. 9. Comparison of projected density of states (PDOS) for FIMA (a), FIMB
(b), and ncFIM (c) phases with c=a ¼ 0:99, U ¼ 0:7, and 2.2 eV.
are highly speculative as the net moment is predicted antiparallel to
Mn4 , which is not consistent with experimental results and other
theoretical studies.48
To check the consistency of the dependence of MOKE on U
with the underlying electronic states, we provide a comparison of
the projected DOS for U ¼ 0:7 and 2:2 eV in Fig. 9. The data for
U ¼ 0:7 eV were already presented in Fig. 3. The comparison
reveals the expected general trend when all the occupied Mn-3d
states shift to lower energies and an unoccupied state to higher
energies. The transitions between them that correspond to peaks in
the MOKE spectrum span a wider energy difference, resulting in
the blueshift mentioned earlier.
APPENDIX C: BAND STRUCTURE
To complete the study of the electronic structure of Mn4 , we
present the band structure for FIMA and FIMB with c=a ¼ 0:99
J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
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06 December 2023 17:42:02
FIG. 10. Band structure for FIMA with c=a ¼ 0:99: (a) U ¼ 0:7 and (b) 2:2 eV.
The solid (dashed) lines mark spin-up (spin-down) states in both panels.
and U ¼ 0:7 and 2.2 eV. The spin–orbit coupling that needs to be
included to simulate MOKE is not used here in order to be able to
resolve spin-up and spin-down states. We do not plot the band
structure of ncFIM as the noncollinear magnetic structure does
not allow for comparison to the collinear phases on the same
footing (spin quantization axis along [001]). Figure 10 compares
the band structure for the FIMA . One can observe how the bands
are moving away from the Fermi level with the increased U.
Figure 11 shows the same trend for the FIMB phase.
Unfortunately, we have not been able to find plots of the band
structure for Mn4 N in the literature; therefore, comparison with
this level of detail is not possible.
APPENDIX D: SYMMETRY ANALYSIS
In analogy to our recent study of MOKE spectra in
Mn3 NiN,25 we note that MOKE is an optical counterpart of the
anomalous Hall effect (AHE). Both MOKE and the intrinsic con-
tribution to anomalous Hall conductivity (AHC), σ αβ , originate
(within linear response theory) in an non-vanishing integral of
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TABLE II. Comparison of magnetic space groups and the corresponding anomalous
Hall conductivity tensor (AHC) for each phase assuming tetragonal lattice distortion.

ncFIM FIMA, FIMB

Space group 123, P4/mmm 123, P4/mmm
0 0
Mag. space group 0 12.62, C2 /m 1 123.345,
0 P4/mm0 m1
0

AHC, σαβ 0 σ xy σ xz 0 σ xy 0
@ σ xy 0 σ xz A @ σ xy 0 0 A
σ xz σ xz 0 0 0 0

where ω is the photon energy, and we assume that the z-axis (paral-
lel to the incident beam) is perpendicular to the film.
The presence of MOKE and AHE can be determined by ana-
lyzing the transformation properties of the Berry curvature under
all symmetry operations of a particular magnetic space group. In
Table II, we list the space groups of the three FIM phases of Mn4 N
(subject to tetragonal distortion) obtained by FINDSYM soft-
ware.62,63 The last row of Table II presents the form of the AHC
tensor in a linear response regime obtained using software
Symmetr64 considering both sets of symmetry operations and the
spin–orbit coupling. We note that both collinear FIM phases share
the same form of an AHC tensor with one independent nonzero
element, σ xy , inducing the polar-MOKE.
The AHC tensor of ncFIM has two independent nonzero ele-
ments, σ xy and σ xz ¼ σ yz as in case of strained Mn3 NiN.25 Cubic
Mn4 N would have σ xy ¼ σ xz ¼ σ yz . The listed forms of the AHC

06 December 2023 17:42:02

tensor are determined by the symmetry of the structure rather than
the net magnetization so they would not change (AHE and MOKE
would not vanish) even if the net magnetic moment vanished, i.e.,
if full compensation of the ferrimagnet was achieved, which is
FIG. 11. Band structure for FIMB with c=a ¼ 0:99: (a) U ¼ 0:7 and (b) 2:2 eV. desirable when seeking ultrafast spintronic devices.31,49
The solid (dashed) lines mark spin-up (spin-down) states in both panels.
REFERENCES
1
P. Chaudhari, J. Cuomo, and R. Gambino, “Amorphous metallic films for
Berry curvature Ωnαβ (k) over the Brillouin zone, magneto-optic applications,” Appl. Phys. Lett. 22, 337–339 (1973).
2
R. Carey, D. Newman, and B. Thomas, “Magneto-optic recording,” J. Phys. D:
ð Appl. Phys. 28, 2207 (1995).
dk X
σ αβ ¼ eh 3
2
f [εn (k)  μ]Ωnαβ (k), P. Hansen, C. Clausen, G. Much, M. Rosenkranz, and K. Witter, “Magnetic and
2π 3 n(occ:) magneto-optical properties of rare-earth transition-metal alloys containing Gd,
    (D1) Tb, Fe, Co,” J. Appl. Phys. 66, 756–767 (1989).
X hkmjν α (k)jkni knν β (k)km 4
Ωnαβ (k) ¼ 2I , T. Suemasu, L. Vila, and J. P. Attané, “Present status of rare-earth free ferrimag-
m=n ½εkn  εkm 2 net Mn4 N and future prospects of Mn4 N-based compensated ferrimagnets,”
J. Phys. Soc. Jpn. 90, 081010 (2021).
5
S. K. Kim, G. S. Beach, K.-J. Lee, T. Ono, T. Rasing, and H. Yang,
where f [εn (k)  μ] denotes the Fermi distribution function with “Ferrimagnetic spintronics,” Nat. Mater. 21, 24–34 (2022).
εn (k) and μ being the energy eigenvalues of the occupied (unoccu- 6
H.-A. Zhou, T. Xu, H. Bai, and W. Jiang, “Efficient spintronics with fully com-
pied) Bloch band, n, and the Fermi energy, respectively, and where pensated ferrimagnets,” J. Phys. Soc. Jpn. 90, 081006 (2021).
7
ν α (k) corresponds to the velocity operator in Cartesian coordinates. S. A. Siddiqui, J. Han, J. T. Finley, C. A. Ross, and L. Liu, “Current-induced
The Kerr rotation, θ(ω), and ellipticity, η(ω), in the case of domain wall motion in a compensated ferrimagnet,” Phys. Rev. Lett. 121,
polar-MOKE geometry depend on optical conductivity tensor, 057701 (2018).
8
T. Jungwirth, X. Marti, P. Wadley, and J. Wunderlich, “Antiferromagnetic spin-
σ αβ (ω), as follows:25
tronics,” Nat. Nanotechnol. 11, 231–241 (2016).
9
J. Železnỳ, P. Wadley, K. Olejník, A. Hoffmann, and H. Ohno, “Spin transport
σ xy (ω) and spin torque in antiferromagnetic devices,” Nat. Phys. 14, 220–228 (2018).
θ(ω) þ iη(ω) ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi , (D2) 10
V. Baltz, A. Manchon, M. Tsoi, T. Moriyama, T. Ono, and Y. Tserkovnyak,
σ xx (ω) 1 þ i(4π=ω)σ xx (ω) “Antiferromagnetic spintronics,” Rev. Mod. Phys. 90, 015005 (2018).

J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621 134, 203902-11

Published under an exclusive license by AIP Publishing
 Journal of
Applied Physics
11
S. Tsunashima, “Magneto-optical recording,” J. Phys. D: Appl. Phys. 34, R87 (2001).
12
D. Fruchart, E. Bertaut, J. Sénateur, and R. Fruchart, “Magnetic studies on the
metallic perovskite-type compound Mn 3SnN,” J. Phys. Lett. 38, 21–23 (1977).
13
D. Fruchart and F. Bertaut, “Magnetic studies of the metallic perovskite-type
compounds of manganese,” J. Phys. Soc. Jpn. 44, 781–791 (1978).
14
D. Fruchart, D. Givord, P. Convert, P. l’Heritier, and J. Senateur, “The non-
collinear component in the magnetic structure of Mn4 N,” J. Phys. F: Met. Phys.
9, 2431 (1979).
15
G. Gurung, D.-F. Shao, T. R. Paudel, and E. Y. Tsymbal, “Anomalous Hall
conductivity of noncollinear magnetic antiperovskites,” Phys. Rev. Mater. 3,
044409 (2019).
16
D. Boldrin, I. Samathrakis, J. Zemen, A. Mihai, B. Zou, F. Johnson,
B. D. Esser, D. W. McComb, P. K. Petrov, H. Zhang, and H. Cohen, “Anomalous
Hall effect in noncollinear antiferromagnetic Mn3 NiN thin films,” Phys. Rev.
Mater. 3, 094409 (2019).
17
F. Johnson, J. Kimák, J. Zemen, Z. Šobáň, E. Schmoranzerová, J. Godinho,
P. Němec, S. Beckert, H. Reichlová, D. Boldrin, J. Wunderlich, and L. F. Cohen,
“Identifying the octupole antiferromagnetic domain orientation in Mn3 NiN by scan-
ning anomalous nernst effect microscopy,” Appl. Phys. Lett. 120, 232402 (2022).
18
D. Matsunami, A. Fujita, K. Takenaka, and M. Kano, “Giant barocaloric effect
enhanced by the frustration of the antiferromagnetic phase in Mn3 GaN,” Nat.
Mater. 14, 73–78 (2015).
19
D. Boldrin, E. Mendive-Tapia, J. Zemen, J. B. Staunton, T. Hansen, A. Aznar,
J.-L. Tamarit, M. Barrio, P. Lloveras, J. Kim, X. Moya, and L. F. Cohen,
“Multisite exchange-enhanced barocaloric response in Mn3 NiN,” Phys. Rev. X 8,
041035 (2018).
20
D. Boldrin, E. Mendive-Tapia, J. Zemen, J. B. Staunton, A. M. Gomes,
L. Ghivelder, J. Halpin, A. S. Gibbs, A. Aznar, J.-L. Tamarit et al., “Barocaloric
properties of quaternary Mn3 (Zn, In)N for room-temperature refrigeration
applications,” Phys. Rev. B 104, 134101 (2021).
21
M. Wu, C. Wang, Y. Sun, L. Chu, J. Yan, D. Chen, Q. Huang, and J. W. Lynn,
“Magnetic structure and lattice contraction in Mn3 NiN,” J. Appl. Phys. 114,
123902 (2013).
22
H. K. Singh, I. Samathrakis, N. M. Fortunato, J. Zemen, C. Shen,
O. Gutfleisch, and H. Zhang, “Multifunctional antiperovskites driven by strong
magnetostructural coupling,” npj Comput. Mater. 7, 98 (2021).
23
D. Boldrin, F. Johnson, R. Thompson, A. P. Mihai, B. Zou, J. Zemen,
J. Griffiths, P. Gubeljak, K. L. Ormandy, P. Manuel et al., “The biaxial strain
dependence of magnetic order in spin frustrated Mn3 NiN thin films,” Adv.
Funct. Mater. 29, 1902502 (2019).
24
J. Zemen, E. Mendive-Tapia, Z. Gercsi, R. Banerjee, J. Staunton, and
K. Sandeman, “Frustrated magnetism and caloric effects in Mn-based antiperov-
skite nitrides: Ab initio theory,” Phys. Rev. B 95, 184438 (2017).
25
F. Johnson, J. Zázvorka, L. Beran, D. Boldrin, L. Cohen, J. Zemen, and
M. Veis, “Room-temperature weak collinear ferrimagnet with symmetry-driven
large intrinsic magneto-optic signatures,” Phys. Rev. B 107, 014404 (2023).
26
Y. Yasutomi, K. Ito, T. Sanai, K. Toko, and T. Suemasu, “Perpendicular mag-
netic anisotropy of Mn4 N films on MgO(001) and SrTiO3 (001) substrates,”
J. Appl. Phys. 115, 17A935 (2014).
27
X. Shen, A. Chikamatsu, K. Shigematsu, Y. Hirose, T. Fukumura, and T. Hasegawa,
“Metallic transport and large anomalous Hall effect at room temperature in ferrimag-
netic Mn4 N epitaxial thin film,” Appl. Phys. Lett. 105, 072410 (2014).
28
K. Ito, Y. Yasutomi, K. Kabara, T. Gushi, S. Higashikozono, K. Toko,
M. Tsunoda, and T. Suemasu, “Perpendicular magnetic anisotropy in
Cox Mn4x N (x ¼ 0 and 0.2) epitaxial films and possibility of tetragonal Mn4 N
phase,” AIP Adv. 6, 056201 (2016).
29
T. Gushi, M. Jovičević Klug, J. Pena Garcia, S. Ghosh, J. P. Attane, H. Okuno,
O. Fruchart, J. Vogel, T. Suemasu, S. Pizzini, and L. Vila, “Large current driven
domain wall mobility and gate tuning of coercivity in ferrimagnetic Mn4 N thin
films,” Nano Lett. 19, 8716–8723 (2019).
30
T. Hirose, T. Komori, T. Gushi, A. Anzai, K. Toko, and T. Suemasu, “Strong
correlation between uniaxial magnetic anisotropic constant and in-plane tensile
strain in Mn4 N epitaxial films,” AIP Adv. 10, 025117 (2020).
J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
Published under an exclusive license by AIP Publishing
ARTICLE pubs.aip.org/aip/jap
31
T. Bayaraa, C. Xu, and L. Bellaiche, “Magnetization compensation temperature
and frustration-induced topological defects in ferrimagnetic antiperovskite
Mn4 N,” Phys. Rev. Lett. 127, 217204 (2021).
32
W. Zhou, C. T. Ma, T. Q. Hartnett, P. V. Balachandran, and S. J. Poon,
“Rare-earth-free ferrimagnetic Mn4 N sub-20 nm thin films as potential high-
temperature spintronic material,” AIP Adv. 11, 015334 (2021).
33
S. Isogami, M. Ohtake, Y. Kozuka, and Y. K. Takahashi, “Wide modulation of
coercive fields in Mn4 N ferrimagnetic thin films caused dominantly by disloca-
tion microstructures,” J. Magn. Magn. Mater. 560, 169642 (2022).
34
W. Li, X. Xu, T. Gao, T. Harumoto, Y. Nakamura, and J. Shi, “Enhanced per-
pendicular magnetic anisotropy of ferrimagnetic Mn4 N films deposited on the
glass substrate,” J. Phys. D: Appl. Phys. 55, 275004 (2022).
35
Z. Y. Zhang, J. W. Jiang, X. H. Shi, X. Liu, X. Chen, Z. P. Hou, and W. B. Mi,
“Sign reversal and manipulation of anomalous Hall resistivity in facing-target
sputtered Pt/Mn4 N bilayers,” Rare Metals 42, 591–601 (2023).
36
K. Imamura, M. Ohtake, S. Isogami, M. Futamoto, T. Kawai, F. Kirino, and
N. Inaba, “Introduction of VN underlayer and caplayer for preparation of Mn4 N
(001) single-crystal thin film with perpendicular magnetic anisotropy,” AIP Adv.
13, 025110 (2023).
37
S. Isogami, K. Masuda, and Y. Miura, “Contributions of magnetic structure
and nitrogen to perpendicular magnetocrystalline anisotropy in antiperovskite
Mn4 N,” Phys. Rev. Mater. 4, 014406 (2020).
38
K.-J. Kim, S. K. Kim, Y. Hirata, S.-H. Oh, T. Tono, D.-H. Kim, T. Okuno,
W. S. Ham, S. Kim, G. Go, “Y. Tserkovnyak, “A. Tsukamoto, “T. Moriyama,
“K.-J. Lee, “T. Ono, “Fast domain wall motion in the vicinity of the angular momen-
tum compensation temperature of ferrimagnets,” Nat. Mater. 16, 1187 (2017).
39
L. Caretta, M. Mann, F. Büttner, K. Ueda, B. Pfau, C. M. Günther, P. Hessing,
A. Churikova, C. Klose, M. Schneider et al., “Fast current-driven domain walls
and small skyrmions in a compensated ferrimagnet,” Nat. Nanotechnol. 13,
1154–1160 (2018).
40
06 December 2023 17:42:02
S. Isogami and Y. K. Takahashi, “Antiperovskite magnetic materials with 2p
light elements for future practical applications,” Adv. Electron. Mater. 9,
2200515 (2023).
41
W. Takei, R. Heikes, and G. Shirane, “Magnetic structure of Mn4 N-type com-
pounds,” Phys. Rev. 125, 1893 (1962).
42
K. Kabara and M. Tsunoda, “Perpendicular magnetic anisotropy of Mn4 N films
fabricated by reactive sputtering method,” J. Appl. Phys. 117, 17B512 (2015).
43
A. Foley, J. Corbett, A. Khan, A. L. Richard, D. C. Ingram, A. R. Smith,
L. Zhao, J. C. Gallagher, and F. Yang, “Contribution from Ising domains overlap-
ping out-of-plane to perpendicular magnetic anisotropy in Mn4 N thin films on
MgO(001),” J. Magn. Magn. Mater. 439, 236–244 (2017).
44
A. Anzai, F. Takata, T. Gushi, K. Toko, and T. Suemasu, “Epitaxial growth and
magnetic properties of Fe4x Mnx N thin films grown on MgO(001) substrates by
molecular beam epitaxy,” J. Cryst. Growth 489, 20–23 (2018).
45
T. Gushi, L. Vila, O. Fruchart, A. Marty, S. Pizzini, J. Vogel, F. Takata,
A. Anzai, K. Toko, T. Suemasu, and J. P. Attane, “Millimeter-sized magnetic
domains in perpendicularly magnetized ferrimagnetic Mn4 N thin films grown
on SrTiO3 ,” Jpn. J. Appl. Phys. 57, 120310 (2018).
46
Y. He, S. Lenne, Z. Gercsi, G. Atcheson, J. O’Brien, D. Fruchart, K. Rode, and
J. M. Coey, “Noncollinear ferrimagnetism and anomalous Hall effects in Mn4 N
thin films,” Phys. Rev. B 106, L060409 (2022).
47
W. Li, R. Tanaka, T. Usami, T. Gao, T. Harumoto, Y. Nakamura, and J. Shi,
“Growth of Mn4 N film with enhanced perpendicular magnetization on glass
substrate using MnO seed layer,” Mater. Lett. 311, 131615 (2022).
48
Z. Zhang, Q. Zhang, and W. Mi, “Anomalous Hall effect of facing-target sput-
tered ferrimagnetic Mn4 N epitaxial films with perpendicular magnetic anisot-
ropy,” Chin. Phys. B 31, 047305 (2022).
49
R. Zhang, Y. He, D. Fruchart, J. M. Coey, and Z. Gercsi, “Rare-earth-free non-
collinear metallic ferrimagnets Mn4x Zx N with compensation at room tempera-
ture,” Acta Mater. 234, 118021 (2022).
50
Z. Gercsi, Y. He, and J. D. Coey, “Comment on “magnetization compensation
temperature and frustration-induced topological defects in ferrimagnetic antiper-
ovskite Mn4 N”,” Phys. Rev. Lett. 131, 089701 (2023).
134, 203902-12
 Journal of
Applied Physics
51
H. Abe, M. Matsuura, A. Hirai, J. Haruna, and M. Mekata, “Nuclear magnetic
resonances of Mn55 and N14 in ferrimagnetic intermetallic Mn4 N–anisotropic
and transferred hyperfine fields in intermetallic compound,” J. Phys. Soc. Jpn.
22, 558–572 (1967).
52
M. Uhl, S. F. Matar, and P. Mohn, “Ab initio analysis of magnetic properties
in noncollinearly orderedN,” Phys. Rev. B 55, 2995–3002 (1997).
53
T. Yasuda, K. Amemiya, and T. Suemasu, “Growth of ultrathin Mn4 N epitaxial
films on SrTiO3 (001) and their thickness-dependent magnetic structures,” Appl.
Phys. Lett. 123, 122404 (2023).
54
H. Sakaguchi, S. Isogami, M. Niimi, and T. Ishibashi, “Boron-induced
magneto-optical Kerr spectra and dielectric tensors in ferrimagnetic
(Mn 4 N)B antiperovskite thin films,” J. Phys. D: Appl. Phys. 56, 365002
(2023).
55
G. Wang, S. Wu, P. Hu, and S. Li, “Magnetic properties and evidence of
current-induced perpendicular field in epitaxial ferrimagnetic Mn4 N (002) film
mixed with (111) phase,” J. Appl. Phys. 122, 133905 (2017).
56
W. Feng, G.-Y. Guo, J. Zhou, Y. Yao, and Q. Niu, “Large magneto-optical Kerr
effect in noncollinear antiferromagnets Mn3 X (X ¼ Rh, Ir, Pt),” Phys. Rev. B
92, 144426 (2015).
J. Appl. Phys. 134, 203902 (2023); doi: 10.1063/5.0170621
Published under an exclusive license by AIP Publishing
ARTICLE pubs.aip.org/aip/jap
57
G. Kresse and J. Hafner, “Ab initio molecular dynamics for liquid metals,”
Phys. Rev. B 47, 558 (1993).
58
J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approxima-
tion made simple,” Phys. Rev. Lett. 77, 3865 (1996).
59
M. Veis, J. Minár, G. Steciuk, L. Palatinus, C. Rinaldi, M. Cantoni, D. Kriegner,
K. Tikuišis, J. Hamrle, M. Zahradník et al., “Band structure of CuMnAs probed
by optical and photoemission spectroscopy,” Phys. Rev. B 97, 125109 (2018).
60
S. L. Dudarev, G. A. Botton, S. Y. Savrasov, C. Humphreys, and A. P. Sutton,
“Electron-energy-loss spectra and the structural stability of nickel oxide: An
LSDA+U study,” Phys. Rev. B 57, 1505 (1998).
61
T. Higo, H. Man, D. B. Gopman, L. Wu, T. Koretsune, O. M. van’t Erve,
Y. P. Kabanov, D. Rees, Y. Li, M.-T. Suzuki et al., “Large magneto-optical Kerr
effect and imaging of magnetic octupole domains in an antiferromagnetic
metal,” Nat. Photonics 12, 73–78 (2018).
62
H. T. Stokes and D. M. Hatch, “FINDSYM: Program for identifying the space-
group symmetry of a crystal,” J. Appl. Crystallogr. 38, 237–238 (2005).
63
H. T. Stokes, D. M. Hatch, and B. J. Campbell, see iso.byu.edu for “FINDSYM.”
64
J. Železný, “Linear response symmetry,” available at https://bitbucket.org/
zeleznyj/linear-response-symmetry.
06 December 2023 17:42:02
134, 203902-13