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Inhomogeneity-induced high temperature ferromagnetism in n-type

ferromagnetic semiconductor (In,Fe)As grown on vicinal GaAs
substrates
To cite this article: Pham Nam Hai et al 2020 Jpn. J. Appl. Phys. 59 063002

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Japanese Journal of Applied Physics 59, 063002 (2020) REGULAR PAPER
https://doi.org/10.35848/1347-4065/ab9401

Inhomogeneity-induced high temperature ferromagnetism in n-type ferromagnetic

semiconductor (In,Fe)As grown on vicinal GaAs substrates
Pham Nam Hai1,2* , Munehiko Yoshida1, Akihide Nagamine1, and Masaaki Tanaka2,3
1
Department of Electrical and Electronic Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro, Tokyo 152-0033, Japan
2
Center for Spintronics Research Network (CSRN), The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
3
Department of Electrical Engineering and Information Systems, The University of Tokyo, 7-3-1 Hongo, Bunkyo, Tokyo 113-8656, Japan
*
E-mail: luosz@jlu.edu.cn
Received April 13, 2020; revised May 7, 2020; accepted May 17, 2020; published online June 2, 2020

We systematically investigate the electrical and magnetic properties of n-type ferromagnetic semiconductor (In,Fe)As thin films grown on vicinal
GaAs(001) substrates with different lattice-relaxation layers and Fe-doping techniques. We show that spinodal decomposition and ferromagnetism
can be enhanced in the (In,Fe)As thin films grown on InAs lattice-relaxation layers under the nucleation growth mode, while they are suppressed in
those grown on the GaSb/AlSb/AlAs (from top to bottom) lattice-relaxation layers under the step-flow growth mode. We demonstrate that room-
temperature ferromagnetism and good electrical properties can be obtained at the same time by using the Fe-delta-doping technique in
combination with the step-flow growth mode. © 2020 The Japan Society of Applied Physics

field Zener model for n-type FMSs,18) high temperature

1. Introduction
Ferromagnetic semiconductors (FMSs) are important spin-
tronic materials inheriting properties of both semiconductors
and ferromagnets. One of the most important topics in FMS
research is to fabricate high quality FMSs with high-
temperature intrinsic ferromagnetism. The most intensively
studied FMS is (Ga, Mn)As,1,2) but its maximum Curie
temperature is limited to 200 K.3) Recently, we have grown
and studied the properties of Fe-doped narrow-gap FMSs,
such as n-type (In,Fe)As,4–6) p-type (Ga,Fe)Sb,7–9) n-type (In,
Fe)Sb,10–12) and insulating (Al,Fe)Sb.13) Among them, (In,
Fe)As is unique because it is an electron-induced n-type FMS
with relatively high electron mobility and quantum coher-
ency. In (In,Fe)As, Fe atoms replace partially In atoms in the
cation (group-III) sites and are in the isoelectronic Fe3+ state.
Thus, the Fe atoms play the role of local magnetic moments,
while free electron carriers are supplied independently by co-
doped donors such as Si or Be double donors. (In,Fe)As shows
a Curie temperature TC of up to several tens of Kelvin at an
electron density n as low as 6 × 1018 cm−3. It is found that
electron carriers reside in the conduction band with small
electron effective mass (0.03 –0.17m0, where m0 is the
free electron mass),6) high electron mobility (up to
1000 cm V−1 s−1), and consequently long quantum coherence
length of the electron wavefunctions. In fact, we observed
quantum size effects in (In,Fe)As quantum wells as thick as
40 nm, and showed that the ferromagnetism in those quantum
wells can be explained by the overlapping of the electron
wavefunctions and the Fe ions.14–16) Furthermore, we demon-
strated “wavefunction engineering of ferromagnetism” in (In,
Fe)As quantum wells by changing the overlapping of the
wavefunctions and the Fe ions without large change of the
electron density.16) This method can be applied to low-power
and high-speed electrical control of ferromagnetism. We also
observed large spontaneous spin splitting in the conduction
band of (In,Fe)As by using tunneling spectroscopy in Esaki
diode structures.17) These results firmly confirmed the intrinsic
ferromagnetism in (In,Fe)As.
Although we obtained TC up to several tens of K at
n ∼ 1018 cm−3 in (In,Fe)As, which is two orders of magni-
tude higher than the TC ∼ 100 mK predicted by the mean-
063002-1
ferromagnetism in (In,Fe)As has not been realized. Because
TC is proportional to xn1/3 in the mean-field Zener model,
where x is the Fe concentration, increasing either x or n will
help enhance ferromagnetism.19,20) The former method
(increasing x) has been employed successfully in p-type
(Ga,Fe)Sb and n-type (In,Fe)Sb to achieve high-temperature
ferromagnetism. In both (Ga,Fe)Sb and (In,Fe)Sb, we can
dope a surprisingly large amount of Fe while maintaining the
zinc-blende crystal structure.9,11,12) We found that TC of
(Ga,Fe)Sb monotonously increases with x, and reaches room
temperature (300 K) when x is higher than 23%.9) Similarly,
TC of (In,Fe)Sb can reach 385 K at x = 35%.12) Thus, it is
reasonable to expect intrinsic room-temperature ferromag-
netism in (In,Fe)As if high enough Fe can be doped in the
InAs matrix without Fe cluster precipitation.
In (In,Fe)As, however, it is difficult to dope a large amount
of Fe (x > 10%) without destroying the zinc-blende crystal
structure. Furthermore, heavy doping of Be double donors in
(In,Fe)As can increase n up to a maximum value of only
1.8 × 1019 cm−3.4) Therefore, realization of TC higher than
100 K in (In,Fe)As by homogeneous Fe doping is still a
challenge. On the other hand, it is possible to increase the
local Fe concentration by utilizing the spinodal decomposi-
tion phenomenon21–23) or Fe-delta-doping technique while
maintaining the zinc-blende crystal structure. (The term
“spinodal decomposition” is widely used to indicate phase
decomposition in FMSs. This is misleading because phase
decomposition is not always spinodal;22) it can be either
binodal or spinodal depending on the polarity of ∂F/∂x,
where F is the free energy function of the FMS and x is the
concentration of magnetic impurities. However, for historical
reasons, we will use the term “spinodal decomposition”
throughout this paper to indicate phase decomposition.)
The spinodal decomposition results in local ferromagnetic
domains with higher Fe concentrations. Recently, Sakamoto
et al. has used X-ray magnetic circular dichroism (MCD) to
investigate the magnetization process in (In,Fe)As:Be.24)
They found the existence of nanoscale ferromagnetic do-
mains at temperatures much higher than the macroscopic
TC. The magnetic moment per ferromagnetic domain is
200–300 μB (corresponding to 40–60 Fe atoms), and the
© 2020 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 59, 063002 (2020) P. N. Hai et al.

density of ferromagnetic domains is nearly the same as the Be

impurities. The existence of nanoscale ferromagnetic do-
mains is the manifestation of spatial fluctuations of Fe
concentration at the nanoscale due to spinodal decomposition
in (In,Fe)As:Be.25) In fact, we have confirmed spinodal
decomposition in (In,Fe)As by investigating the local Fe
concentration in nano-scale areas using the three-dimensional
atom probe, which will be presented elsewhere. Such local
ferromagnetic domains can have local ferromagnetism with
TC much higher than the macroscopic TC of the matrix.
However, because the ferromagnetic domains are distributed
randomly, they are magnetically independent of each other
and become superparamagnetic at high temperatures. If we
can control the positions of such nano-scale domains so that
they are spatially and magnetically connected, high-tempera-
ture macroscopic ferromagnetism can be realized in
(In,Fe)As. Note that the spinodal decomposition has also
been utilized in (Ga,Mn)As to fabricate zinc-blende MnAs
nanoparticles with Curie temperature up to 360 K.26,27)
In this paper, we attempt to control the spinodal decom-
position process in (In,Fe)As by growing (In,Fe)As thin films
on vicinal GaAs(001) substrates to realize high-temperature
ferromagnetism. The vicinal GaAs substrates are miscut from
the (001) surface toward the [110] direction, and have atomic
steps along the [1̄10] direction on their surface. There are two
possible growth modes of (In,Fe)As on vicinal GaAs(001)
substrates. One is the well-known step-flow growth mode, in
which incident atoms (both In and Fe) migrate on the surface
toward the step edges and stick to them, rather than nucleate
on the surface. In this mode, the steps travel laterally on the Fig. 1. (Color online) (a) and (b) Schematic cross-sectional structure of
surface as the growth proceeds. Because the position of the type-A and type-B (In,Fe)As samples, respectively. The thickness of the
steps is continuously changing with time, spinodal decom- AlAs, AlSb, and GaSb buffer layers of type-B samples are 10 nm, 30 nm,
position is suppressed, and the Fe atom distribution becomes and 70 nm, respectively. (c)–(f) RHEED patterns taken along the [1̄10]
azimuth after the MBE growth of (c) the InAs layer in sample A2, (d) the
more homogeneous [see Fig. 1(h)]. The other is the nuclea- AlSb layer in sample B3, (e) the (In0.947,Fe0.053)As layer of sample A2, and
tion growth mode, in which incident atoms nucleate on the (f) the (In0.947, Fe0.053)As layer in sample B3. (g) and (h) Idealized schematic
surface. Because the steps do not move on the surface, their three-dimensional structure of type-A and type-B samples, respectively.
positions are unchanged, and they can provide fixed nuclea- Here, the top InAs cap is omitted for clarity.
tion sites for spinodal decomposition of Fe because of
attractive interaction between Fe atoms. Therefore, we can
expect that laterally unmoving steps enhance spinodal Table I. List of (In,Fe)As samples and the corresponding off-angle of
decomposition at their positions, resulting in more inhomo- vicinal GaAs(001) substrates, lattice-relaxation layers (from top to bottom),
and Curie temperature (TC).
geneous distribution of Fe; higher Fe concentration is
expected at the steps, while lower Fe concentration is Off-angle Lattice-relaxa- TC (K) TC (K)
expected at the terrace areas between steps [see Fig. 1(g)]. Sample (degree) tion layers (terrace) (step)
Thus, we can expect two types of (In,Fe)As grown on vicinal A1 0 [=GaAs InAs 10
GaAs(001) substrates; (i) the more homogeneous (In,Fe)As (001) just-cut]
grown under the step-flow mode, and (ii) the more inhomo- A2 2 20 >300
geneous (In,Fe)As grown under the nucleation mode. By A3 6 30 >300
A4 10 10 >300
investigating their electrical and magnetic properties, we can
A5 19.5 [=GaAs <10 >300
evaluate the roles of spinodal decomposition in (In,Fe)As, (114)A]
and establish methods for obtaining inhomogeneity-induced B1 0 [=GaAs GaSb/AlSb/ <10
high-temperature ferromagnetism in (In,Fe)As. (001) just-cut] AlAs
B2 2 <10
2. Experiments B3 6 <10
B4 10 <10
The studied (In,Fe)As layers were grown by low-temperature B5 19.5 [=GaAs <10
molecular beam epitaxy (LT-MBE) on various vicinal GaAs (114)A]
(001) substrates with off-angles of 2°, 6°, 10°, and 19.5° C 2 150
[GaAs(114)A] toward the [110] direction, as summarized in D 2 305

063002-2 © 2020 The Japan Society of Applied Physics

Jpn. J. Appl. Phys. 59, 063002 (2020)
Table I. For comparison, we also grew reference (In,Fe)As
layers on a GaAs(001) just-cut substrate. To reduce the very
large lattice mismatch between (In,Fe)As (lattice
constant ∼6.06 Å) and GaAs (lattice constant ∼ 5.65 Å),
lattice-relaxation layers are inserted between the GaAs
substrates and the (In,Fe)As layers. We have grown four
types of 20 nm thick (In,Fe)As thin films with various type of
lattice-relaxation layers and Fe doping techniques. Type A
are (In,Fe)As thin films grown on InAs lattice-relaxation
layers, while type B are those grown on a stack of GaSb/
AlSb/AlAs (from top to bottom layers) lattice-relaxation
layers. As shown below, the InAs lattice-relaxation layers
promote nucleation growth mode, while the GaSb/AlSb/AlAs
lattice-relaxation layers promote the step-flow mode. The Fe
concentration x in the (In1−x,Fex)As layers of type A and B
are 5.3%. Type C and type D are those grown by an Fe-delta-
doping technique on the GaSb/AlSb/AlAs lattice-relaxation
layers (More details of the growth procedure will be
described later). During the MBE growth, reflection high-
energy electron diffraction (RHEED) was used to observe the
crystallinity and surface morphology of the samples. After
the thin-film growth, electrical properties, magneto-transport
properties, and magneto-optical properties of those (In,Fe)As
thin films were investigated using various methods such as
MCD spectroscopy and anomalous Hall effect (AHE). The
crystal structure of one sample (A2) was investigated by
scanning transmission electron microscopy (STEM).
3. Results
3.1. Samples A1–A5 and B1–B5
3.1.1. Crystal growth. Figures 1(a) and 1(b) show the
schematic cross-sectional structure of samples A1–A5 (type A)
and samples B1–B5 (type B), respectively. The growth
procedure of these samples is as follows. First, we grew a
50 nm thick GaAs buffer layer at a substrate temperature (TS)
of 580 °C. After that, we grew a 10 nm thick InAs lattice-
relaxation layer at TS = 500 °C for type A, or a stack of 10 nm
thick AlAs (TS = 500 °C), 30 nm thick AlSb (TS = 470 °C),
and 70 nm thick GaSb (TS = 470 °C) lattice-relaxation layers
for type B, respectively. These lattice-relaxation layers reduce
the lattice mismatch between (In,Fe)As and GaAs. After
cooling the samples to 236 °C, we started growing a 20 nm
thick (In0.947,Fe0.053)As layer, doped with double-donor Be
atoms of 1 × 1019 cm−3. Finally, we grew a 3 nm InAs cap
layer.
Figures 1(c)–1(d) show the RHEED patterns taken along
the [1̄10] azimuth of the InAs lattice-relaxation layer of
sample A2 (2°-off substrate) and the AlSb lattice-relaxation
layer of sample B3 (6°-off substrate), respectively. We see
clear difference between these layers. The InAs layer was
grown at a high temperature of 500 °C, allowing fast surface
migration of In atoms and formation of lattice-relaxed InAs
layer with a relatively flat surface, as evidenced by the
streaky patterns in Fig. 1(c). In this case, however, the steps
on the surface of the vicinal GaAs substrate were buried, and
no step-flow growth of (In,Fe)As on the InAs lattice-
relaxation layer can be expected. Nevertheless, we expect
that the steps on the GaAs substrate can leave traces as defect
sites or local strains at the GaAs/InAs interface, which can
remain up to the InAs surface. In spinodal decomposition,
such local defects or strains are known to be nucleation sites
063002-3
P. N. Hai et al.
and can trigger the spinodal decomposition in the top
(In,Fe)As thin films. In contrast, the AlSb layer (and the
following GaSb layer, not shown here) can preserve the steps
structures of the vicinal GaAs substrate even after lattice
relaxation between them has occurred, as clearly seen by their
inclined streaky RHEED patterns in Fig. 1(d). Figures 1(e)
and 1(f) show the RHEED patterns of the (In,Fe)As layer of
sample A2 and sample B3, respectively. The surface of the
(In,Fe)As layer of sample A2, which was grown on the InAs
lattice-relaxation layer, is slightly rough [see Fig. 1(e)],
which is due to the influence of defects or local strains
inherited from the steps on the GaAs substrate. In contrast,
the surface of the (In,Fe)As layer of sample B3 is smooth
with clear inclined streaky RHEED patterns [see Fig. 1(f)],
indicating the step-flow mode of (In,Fe)As even at low
temperature in this sample.
From the RHEED observations mentioned above, we can
expect that samples A2–A5 have stronger spinodal decom-
position and more inhomogeneous distribution of Fe, while
samples B2–B5 have more homogenous distribution of Fe,
compared with the reference sample A1 grown on a
GaAs(001) just-cut substrate under the usual condition. The
idealized schematic three-dimensional (3D) sample structure
and the expected distribution of Fe are depicted in Figs. 1(g)
and 1(h) for samples A2–A5 and B2–B5, respectively. [Note
that in Figs. 1(g) and 1(h), the height of the steps is one
monolayer (ML), and is magnified for better illustration. The
InAs cap layer is omitted.] In samples A2–A5, one can
expect areas with relatively high Fe concentration induced by
defects or local strains inherited from the steps on the GaAs
substrate, and terrace areas in between with relatively low Fe
concentration. In contrast, in samples B2–B5, we expect that
the Fe concentration is more homogenous thanks to the step-
flow mode.
Figure 2 shows a representative STEM lattice image of
sample A2 projected along the [1̄10] azimuth. The STEM
image indicates that the crystal structure of the (In,Fe)As
layer is zinc-blende with some dislocations, but there is no
precipitation of body-centered-cubic or face-centered-cubic
Fe nanoclusters or other types of crystal structure. This
Fig. 2. Cross-sectional scanning transmission electron microscopy
(STEM) lattice image of sample A2, consisting of 3 nm thick InAs cap/20
nm thick (In0.947,Fe0.053)As/10 nm thick InAs lattice-relaxation buffer layer,
grown on a 2°-off GaAs(001) substrate. Note that the 3 nm thick InAs cap
and about 2 nm thick (In,Fe)As were oxidized.
© 2020 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 59, 063002 (2020) P. N. Hai et al.

(a) have higher resistivity. At low temperatures, all type-A

(b)
Fig. 3. (Color online) (a) and (b) Temperature dependence of the resistivity of
type-A and type-B (In,Fe)As samples, respectively. The insets of (a) and (b)
show the electron mobility at 10 K and 300 K versus off-angle of the substrates.
indicates that any high-temperature ferromagnetism observed
in this sample should due to the locally high Fe-concentration
areas of zinc-blende crystal structure, and not due to
precipitated Fe nanoclusters.
3.1.2. Electrical, magneto-optical, and magneto-
transport properties. Figures 3(a) and 3(b) show the
temperature dependence of the resistivity of samples
A1–A5 and B1–B5, respectively. At room temperature,
sample A1, which was grown on a GaAs(001) just-cut
substrate, has the lowest resistivity, while samples A2–A5
samples show insulating behavior, although they are degener-
ated semiconductors with n > 3 × 1018 cm−3 at room tempera-
ture. This indicates that these type-A samples have considerable
scattering centers that cause metal–insulator transition (MIT) at
low temperatures. Interestingly, we observed a trend that the
higher the off-angle is, the more rapidly the resistivity increases
with decreasing temperature, indicating that stronger MIT
occurs. This shows a clear correlation between the off-angle
and the density of scattering centers, supporting our suggestion
that steps on the surface of GaAs create defects or local strains
in the InAs lattice-relaxation layers, which in turn affect the
growth of the top (In,Fe)As layers. The off-angle-dependence of
the electron mobility μ at 300 and 10 K [inset in Fig. 3(a)] also
supports our argument; μ decreases with increasing the off-
angle and lowering temperature. In contrast, the resistivity of
type-B samples shows metallic behavior in a wide range of
temperature, indicating that these samples have good crystal
quality (except for sample B5 which is weakly insulating).
Furthermore, we found that samples B2–B5 have improved μ at
low temperature compared with that of sample B1, as shown in
the inset of Fig. 3(b). This indicates that the step-flow growth
mode of (In,Fe)As layers on top of GaSb/AlSb/AlAs lattice-
relaxation layers helped improve the crystal quality.
Next, we investigate the relationships between the growth
mode of (In,Fe)As and their magnetic properties. First, in
order to prove the intrinsic ferromagnetism of the (In,Fe)As
thin films, we investigate the magneto-optical properties of
the (In,Fe)As thin films using MCD spectroscopy in a
reflection setup. Here, the reflection MCD intensity is
90 (Rs+ - Rs-) 1 dR
expressed as p 2R
∝ R dE
DE, where Rs+ and Rs- are
the reflectance for the incident right (s+) and left (s-) circular
polarized light, respectively, R is the total reflectance, E is the

(a) (c) (e)

(b) (d) (f)

Fig. 4. (Color online) (a) and (b) MCD spectra at 5 K of type-A and type-B (In,Fe)As samples, respectively, under an external magnetic field of 1 T applied
perpendicular to the film plane. Black arrows indicate the optical critical point energies of InAs. (c) and (d) Normalized MCD spectra at 0.2, 0.5, and 1 T of
samples A2 and B3, respectively. (e) and (f) MCD intensity-magnetic field hysteresis at various temperatures of sample A3 and B3, respectively, measured at
the photon energy of E1. The insets of (e) and (f) show the MCD hysteresis at 300 K.

063002-4 © 2020 The Japan Society of Applied Physics

Jpn. J. Appl. Phys. 59, 063002 (2020)
photon energy, and DE is the spin-splitting energy (Zeeman
dR
splitting energy) of a FMS. The MCD spectrum reflects dE ,
which is unique for the FMS in question. The MCD spectrum of
an intrinsic FMS would show strongly enhanced extrema at the
optical critical point energies of the host semiconductors. On the
other hand, if a semiconductor sample contains second-phase
metallic magnetic precipitates, the MCD spectrum would show
a broad background and no particular features related to the host
semiconductor, because the host semiconductor would remain
non-magnetic in this case. Therefore, MCD is a powerful tool to
distinguish whether the magnetization in the samples comes
from the intrinsic FMS phase or metallic second-phase pre-
cipitations. At the same time, the MCD intensity is also
proportional to DE, allowing us to obtain the magnetization
hysteresis of the measured material as a function of the external
magnetic field H. These are the great advantages of MCD over
more conventional techniques, such as superconducting
quantum interference devices, which cannot distinguish the
origin of the observed magnetization.28) Figures 4(a) and 4(b)
show the MCD spectra of samples A1–A5 and B1–B5,
respectively, at 5 K and under a magnetic field of 1 T applied
perpendicular to the film plane. The MCD spectra of both type-
A and type-B samples show strong extrema at the optical critical
point energies E1 (2.61 eV), E1 + D1 (2.88 eV), and E0
(4.39 eV) of InAs.29) These results indicate that (In,Fe)As thin
films grown on vicinal substrates preserve the zinc-blende band
structures, consistent with the STEM observation in Fig. 2.
There is, however, difference in the magnetic field response of
the MCD spectra between type-A and type-B samples.
Figures 4(c) and 4(d) show the normalized MCD spectra by
their intensity at E1 of sample A2 and B3, measured with
applied magnetic fields of 0.2, 0.5, and 1 T. The normalized
MCD spectra of sample B3 shows nearly perfect overlapping on
a single spectrum in the whole photon energy range, indicating
that the MCD spectra come from a single-phase ferromagnetism
of the entire (In,Fe)As film. In contrast, the normalized MCD
spectra of sample A3 show clear difference in the photon energy
range between 3.2 and 4.2 eV, indicating that there are different
phases in this sample. These magnetic responses of the MCD
spectra are consistent with our expectation for the inhomoge-
neous (homogeneous) distribution of Fe in type-A (type-B)
samples, respectively, as shown in Figs. 1(g) and 1(h).
Next, we analyze the magnetic field dependence of the MCD
intensity (MCD − H characteristics). Figures 4(e) and 4(f) show
the representative MCD − H characteristics at different tem-
peratures of sample A3 and B3, respectively, measured at the
optical critical point energy E1. One can see that both samples
show weak hysteresis at low temperatures, indicating the
existence of a low TC ferromagnetic phase. Other samples
show similar MCD − H characteristics. TC of all the samples
was estimated by the Arrott plots (MCD2 − H/MCD) and was
listed in the 4th column of Table I. One can see that samples
B1–B5 have very low TC (<10 K), while samples A1–A5 have
slightly higher TC that do not exceed 30 K. However, there is a
high-TC phase up to room-temperature in sample A3, as shown
by the magnified hysteresis loop at 300 K [see inset of
Fig. 4(e)]. In contrast, there is no such high-TC phase in sample
B3 [see inset of Fig. 4(f)].
In order to clarify the origin of the high-TC phase, we
systematically investigate the MCD − H characteristics of sam-
ples A1–A5 at 300 K, which are shown in Figs. 5(a)–5(e). For
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P. N. Hai et al.
sample A1 [grown on a GaAs(001) just-cut substrate], there is no
hysteresis. However, for samples A2–A5 [grown on vicinal
GaAs(001) substrates], clear hysteresis was observed.
Furthermore, the hysteresis becomes stronger with increasing
the off-angle and the step density. To further confirm the high-
temperature ferromagnetic phase in type-A samples, we mea-
sured the AHE of samples A1–A5 at 300 K. Figures 5(f)–5(j)
show the anomalous Hall resistance (AHR) of samples A1–A5,
normalized by their value at 0.5 T. We observed the same
hysteresis curves of AHR as those of MCD as a function of the
off-angle. For comparison, we show in Figs. 5(k)−5(o) the
MCD − H characteristics of samples B1–B5 at 300 K, which
show no hysteresis. These suggest that the different growth
mode between samples A2–A5 and B2–B5 results in the high-
temperature ferromagnetic phase in samples A2–A5, while such
phase is absent in samples B2–B5.
The co-existence of the high-TC and low-TC phase in
samples A2–A5 and the very low-TC phase in samples B2–
B5 are consistent with spinodal decomposition tailored by the
lattice-relaxation layers and the growth mode of (In,Fe)As, as
illustrated in Figs. 1(g) and 1(h). In samples A2–A5, the
spinodal decomposition is likely enhanced by the existence
of defects or local strains inherited from the atomic steps on
the vicinal GaAs substrates, resulting in local ferromagnetic
domains with high Fe concentrations and high TC. Since
these step-induced high-TC ferromagnetic domains are spa-
tially connected along the steps, they manifest themselves as
the macroscopic high-TC phase. On the other hand, the
terrace areas between those domains have lower Fe concen-
tration, and appear as the low-TC phase. In samples B2–B5
where the growth proceeds by the step-flow growth mode,
the spinodal decomposition is suppressed because the step
position is changing with time. Thus, the Fe atoms are
distributed more randomly, and the TC becomes very low.
These magnetic responses are consistent with the normalized
MCD spectra shown in Figs. 4(c) and 4(d), and conclusions
from the previous XMCD study of (In, Fe)As.24)
3.2. Samples C and D
3.2.1. Crystal growth. In the previous section, we have
shown that room-temperature ferromagnetism can be obtained
by utilizing step-induced spinodal decomposition for (In,Fe)As
grown on the InAs lattice-relaxation layers in type-A samples.
However, those type-A samples have many crystal defects and
relatively poor electrical properties. In this section, we
demonstrate an Fe-delta-doping technique in combination
with the step-flow growth mode on the GaSb/AlSb/AlAs
buffers to achieve high-TC ferromagnetism as well as good
electrical properties. The delta-doping technique enables
doping locally high concentration of magnetic atoms in a
semiconductor while maintaining its crystal structure, and it
was used to obtain high TC up to 250 K in
(Ga,Mn)As.30) Figures 6(a) and 6(b) show the structure of
two new samples C and D, respectively. First, we grew GaSb/
AlSb/AlAs lattice-relaxation layers on 2°-off vicinal GaAs
substrates, in the same way as sample B2. After cooling the
samples to 236 °C, we first grew 4 MLs of Be-doped InAs
(referred to as InAs:Be). For sample C, we used the Fe-delta-
doping technique to grow 1 ML of Be-doped FeAs (referred to
as FeAs:Be), i.e. 1 ML of tetrahedral Fe–As bonding, and
2 MLs of InAs:Be, and repeated this growth process for 22
cycles. For sample D, we grew 0.5 ML of FeAs:Be followed
© 2020 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 59, 063002 (2020)
(a) (b) (c)
(f) (g) (h)
(k) (l) (m)
Fig. 5. (Color online) (a)–(e) Magnetic field dependence of the MCD intensity at room temperature for type-A samples, measured at the photon energy of E1.
(f)–(j) Magnetic field dependence of AHR at room temperature for type-A samples. (k)–(o) Magnetic field dependence of the MCD intensity at room
temperature for type-B samples. The sign of MCD data are reversed (−MCD) for better comparison with AHR data.
Fig. 6. (Color online) (a) and (b) Schematic cross-sectional structure of
samples C and D, respectively. The thickness of the AlAs, AlSb, GaSb
lattice-relaxation layers are the same as those of type-B samples. (c) and
(d) Idealized schematic three-dimensional structure of samples C and D,
respectively.
by 0.5 ML of InAs:Be, and repeated this for 66 cycles. The
total Fe-delta-doped (In,Fe)As layer thickness is 66 MLs
(=20 nm) for both samples C and D. Finally, we grew a
3 nm thick InAs cap layer. Figures 6(c) and 6(d) show the
idealized schematic structure of sample C and D, respectively.
In sample C, 1 ML of FeAs:Be is separated by 2 ML of InAs.
In sample D, each 0.5 ML FeAs:Be is connected vertically,
forming a planar FeAs/InAs superlattice, which is an analogy
to the AlAs/GaAs semiconductor planar superlattice grown on
vicinal GaAs substrates.31)
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P. N. Hai et al.
(d) (e)
(i) (j)
(n) (o)
3.2.2. High-temperature ferromagnetism. Figures 7(a)
and 7(b) show the MCD spectra of samples C and D,
respectively, at 5 K and under a magnetic field of 1 T applied
perpendicular to the film plane. We confirmed the spectral
features of the zinc-blende crystal structure, which are similar
to those of (In,Fe)As grown under usual conditions in our
previous studies. The MCD intensity is as strong as about
100 mdeg at E1. This huge MCD intensity corresponds to an
internal magnetic field of 100 T acting on the InAs host,32)
which cannot be explained by any stray fields from Fe
metallic precipitations acting on non-magnetic InAs, but by
the s,p–d exchange interactions between the Fe localized
d-electrons and InAs. We conclude that the Fe-delta-doped
(In,Fe)As layers in samples C and D also preserve the zinc-
blende band structure.
Figures 7(c) and 7(d) show the MCD − H hysteresis at
various temperatures of samples C and D, respectively,
measured at the photon energy E1. Figures 7(e) and 7(f)
show the Arrott plot of samples C and D, respectively. TC of
sample C is 150 K, while that of sample D is 305 K. The
electron concentration (n) and mobility (μ) are estimated to
be n = 1.35 × 1018 cm−3 and μ = 60 cm2 V−1 s−1 for sample
C, and n = 1.2 × 1019 cm−3 and μ = 122 cm2 V−1 s−1 for
sample D at room temperature. The sample D has better
crystal quality than sample C, and its resistivity is one order
of magnitude smaller than that of type-A and type-B samples.
The ratio of TC between samples D and C (2.03) agrees well
with the ratio of n1/3 between them (2.07), which is consistent
with the “electron-induced” ferromagnetism observed in our
previous studies for (In,Fe)As. Thus, by using the Fe-delta-
doping technique in combination with the step-flow mode,
we achieved both room-temperature ferromagnetism and
good electrical properties with high electron concentration
and high electron mobility in sample D.
© 2020 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 59, 063002 (2020)
(a) (c) (e)
(b) (d) (f)
Fig. 7. (Color online) (a) and (b) MCD spectrum at 5 K of samples C and D, respectively, under an external magnetic field of 1 T applied perpendicular to
the film plane. Black arrows indicate the optical critical point energies of InAs. (c) and (d) MCD intensity-magnetic field hysteresis at various temperatures of
samples C and D, respectively, measured at the photon energy of E1. (e) and (f) Arrott plots of the MCD intensity of samples C and D, respectively.
(g) Temperature dependence of the resistivity of sample D measured when the current was applied along the [110] and [1̄10 ] direction. (h) Normalized
temperature dependence of the resistivity of sample D by their values at room temperature.
The next question is whether the room-temperature ferro-
magnetism in sample D originates from the Fe-delta-doping
induced inhomogeneity, i.e. the planar FeAs/InAs super-
lattice, whose idealized schematic structure is shown in
Fig. 6(d). During the crystal growth, such a superlattice
may collapse due to interdiffusion of Fe and In atoms
between the Fe-delta-doped FeAs domains and the InAs
domains. In the ultimate case, the FeAs and InAs domains
may fuse together to form an (In,Fe)As alloy with the
nominal Fe concentration of 50%. To find whether the planar
FeAs/InAs superlattice in sample D survives such interdiffu-
sion, we measured the resistivity of sample D when the
current is applied along the [110] and [1̄10] direction. If
interdiffusion of Fe and In atoms was completed, there would
be no difference between the resistivity r[110] and r[110
¯ ] for
the current flows along the [110] and [1̄10] direction. On the
hand, if interdiffusion of Fe and In is not completed, we can
expect some difference between them. Using the serial
(parallel) resistor model for the FeAs/InAs superlattice
when the current follows along the [110] ([1̄10]) direction,
r FeAs + r InAs 2r FeAs Dr InAs
we obtain r[110] = 2
and r[110
¯ ]= r FeAs + r InAs
, where
r FeAs and r InAs are the resistivity of the FeAs and InAs
domains. From these formulas, we expect r[110] > r[110
¯ ] for
r FeAs ≠ r InAs. Figures 7(g) shows the temperature depen-
dence of the resistivity of sample D measured when the
current was applied along the [110] and [1̄10] direction, while
Fig. 7(h) shows those normalized by the values at room
temperature. One can see that r[110] is not only larger than
r[110
¯ ] but also increases more rapidly than r[110 ¯ ] with
decreasing temperature, indicating the existence of FeAs/
InAs domains with different electrical characteristics. Thus,
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P. N. Hai et al.
(g)
(h)
we conclude that Fe-delta-doping induced inhomogeneity in
sample D survives and is the origin of the observed room-
temperature ferromagnetism. Finally, we note that high-TC
ferromagnetism is only observed in Fe-delta-doped
(In,Fe)As thin films grown on vicinal GaAs substrates with
the step-flow mode. In Fe-delta-doped (In,Fe)As reference
samples grown on GaAs(001) just-cut substrates, TC was
only several tens of K.
4. Discussion
Under the assumption of the mean-field Zener model, electron-
induced ferromagnetism at temperatures higher than 1 K in n-
type FMSs would not be possible.18) In previous works,
however, we have already demonstrated electron-induced
ferromagnetism up to several tens of K in bulk-like n-type
(In,Fe)As with Fe concentrations less than 10%.4) In this work,
we have further demonstrated ferromagnetism up to room-
temperature in (In,Fe)As thin films with ferromagnetic do-
mains having locally high Fe concentrations. Even higher TC
can be obtained by increasing the electron concentration n.
Note that the maximum n obtained so far in (In,Fe)As is
1.8 × 1019 cm−3, which is much lower than the maximum hole
density (∼1021 cm−3) in (Ga,Mn)As. Thus, there is still more
room for increasing n and TC. High n may be realized by
doping group-VI elements, such as Te or Se, as donors in
(In,Fe)As. From the data of samples C and D, we predict that
the ultimate TC of such (In,Fe)As films would be given by
TC = 305 K × (n/1.2 × 1019 cm−3)1/3. That means, very high
TC of 618 K can be obtained at n = 1 × 1020 cm−3.
5. Conclusion
In conclusion, we have shown that it is possible to realize
high temperature ferromagnetism in (In,Fe)As thin films
© 2020 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 59, 063002 (2020)
grown on vicinal GaAs(001) substrates by utilizing either
spinodal decomposition or Fe-delta-doping techniques.
In particular, we demonstrated that spinodal decomposition
and the corresponding high-temperature ferromagnetism in
(In,Fe)As thin films can be enhanced by growing (In,Fe)As
on the InAs lattice-relaxation layers under the nucleation
growth mode, or suppressed by growing them on the GaSb/
AlSb/AlAs lattice-relaxation layers under the step-flow
mode. We further demonstrated that room-temperature ferro-
magnetism and good electrical properties can be obtained at
the same time by using the Fe-delta-doping technique in
combination with the step-flow mode. Our techniques can
also be applied to other FMSs to obtain high-temperature
ferromagnetism, which is necessary for semiconductor-based
spintronic devices operating at room temperature.
Acknowledgments
This work is supported by the CREST program (No.
JPMJCR1777) of the Japan Science and Technology
Agency (JST), and the Spintronics Research Network of
Japan (Spin-RNJ). P. N. H. acknowledges support from the
Kato Foundation for Promotion of Science, Iketani Science
and Technology Foundation, and Toray Science Foundation.
ORCID iDs
Pham Nam Hai https://orcid.org/0000-0001-6685-4912
Masaaki Tanaka https://orcid.org/0000-0003-3599-663X
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