Study on spin-splitting phenomena in the band structure of GdN

R. Vidyasagar, S. Kitayama, H. Yoshitomi, T. Kita, T. Sakurai et al.

Citation: Appl. Phys. Lett. 100, 232410 (2012); doi: 10.1063/1.4727903

View online: http://dx.doi.org/10.1063/1.4727903
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 APPLIED PHYSICS LETTERS 100, 232410 (2012)

Study on spin-splitting phenomena in the band structure of GdN

R. Vidyasagar,1,a) S. Kitayama,1 H. Yoshitomi,1 T. Kita,1 T. Sakurai,2 and H. Ohta3
1
Department of Electrical and Electronic Engineering, Graduate School of Engineering, Kobe University,
1-1 Rokkodai, Kobe 657-8501, Japan
2
Centre for Support to Research and Education Activities, Kobe University, 1-1 Rokkodai, Kobe 657-8501,
Japan
3
Molecular Photoscience Research Center and Graduate School of Science, Kobe University, 1-1 Rokkodai,
Kobe 657-8501, Japan

(Received 18 April 2012; accepted 21 May 2012; published online 8 June 2012)
An exceptional kind of spin splitting in the band structure of AlN/GdN/AlN double heterostructures
has been studied by employing temperature-dependent spectroscopy. This spin splitting can be
attributed to both the band-gap shrink and the difference between minority and majority band
energies in GdN below the Curie point; these results have been established by evaluating the optical
band gaps at the X-point. The temperature-dependent magnetization measurements that provide
direct evidence of the magnetic ordering below 32 K and it is described by long-range spin
C 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4727903]
correlation in GdN. V

Optical and magnetic interactions present in ferromag-
netic semiconductors are dealt with the quantum behaviour
of spins and itinerant carriers, which have recently emerged
as outstanding platform to develop spintronic devices and
for quantum computation originating from solid-state
physics.1–4 For instance, theoretical and experimental studies
have shown that partially filled 4f orbitals in rare-earth
nitride compounds possess magnetic and electronic proper-
ties simultaneously. GdN is known as one of the promising
intrinsic ferromagnetic semiconductors in which Gd has both
partially filled 4f and 5d orbitals.5 The quantum spin effects
could be accessed via the partially filled 4f and 5d orbital
electron properties of the GdN semiconductor. Notably, ear-
lier reports on GdN have stated controversial views on its
electronic and magnetic properties and commented on the
formidable challenges that remain with respect to the physi-
cal characteristics and oxophilicity.6–9 In contrast, our earlier
reports described the AlN/GdN/AlN double heterostructures
grown by reactive radio-frequency (rf) sputtering under
ultra-pure conditions. These reports show that the GdN has a
preferential orientation (111) for the rock-salt structure upon
the c-axis-oriented AlN with the wurtzite structure, which is
established by high-resolution x-ray diffraction and its pole
diagrams. The magnetization measurements indicated that a
Curie temperature (Tc) of 30 K was achieved with an oxygen
content of less than 1020 cm3.10 In addition, an understand-
ing of the physical properties of these materials requires ex-
ploration of their low-temperature properties. Because these
materials typically exhibits near metallic to insulating phase
transitions and non-magnetic to magnetic phase transitions,
the physics of the quantum phase transitions play an impor-
tant role in determining their low-temperature properties. To
understand the exact band structure and ferromagnetic prop-
erty, temperature-dependent optical and magnetic measure-
ments on a highly stoichiometric cubic structure of GdN are
required. In this Letter, we map the variations in the minority
a)
Author to whom correspondence should be addressed. Electronic mail:
drsagar@sapphire.kobe-u.ac.jp.
and majority spin band energies using temperature-
dependent optical spectroscopy. Magnetization measure-
ments have also been performed to evaluate the Curie point
for the GdN thin film. We have used reactive rf sputtering
performed under molecular beam epitaxial quality at a base
pressure of 2.5  106 Pa to obtain stoichiometric AlN/GdN/
AlN heterostructures.
Double heterostructures of AlN/GdN/AlN were epitax-
ially grown on a c-sapphire (0001) substrate using reactive rf
magnetron sputtering. The c-sapphire substrate (10  10
mm2) was cleaned with acetone, methanol, and deionised
(DI) water in an ultrasonic bath to remove residual organic
contamination on the surface. The substrate is subsequently
etched with HF to remove native surface oxides. Then, the
substrate was again cleaned with DI water. After the chemi-
cal cleaning process, the substrate was mounted onto a sam-
ple holder, and then transferred into the growth chamber.
The growth chamber is evacuated to a base pressure of
2.5  106 Pa using a turbo molecular pump; the substrate
was outgassed at 500  C for 2 h. We used a 6N mixed gas of
Ar and N2 for the reactive growth, and the total sputtering
pressure was 5 Pa. Initially, a thin (100 nm) AlN-buffer
layer has grown on the c-sapphire substrate at 500  C to
make the surface smooth. The growth of the 68 nm thin GdN
layer commenced on the AlN buffer layer with a growth rate
of 22 nm/min. The GdN layer was capped with AlN
(100 nm). The oxophilicity is curtailed by both the AlN
capping layer and the ultra-pure depositing conditions. Inter-
estingly, secondary ion mass spectroscopic (SIMS) analysis
on the epitaxial structure of the AlN/GdN/AlN heterostruc-
tures confirmed that the oxygen content is less than
1.0  1019 cm3 (not shown here). The heterostructures have
further been characterized by a home-built temperature-de-
pendent spectrophotometer using a monochromator (Ocean
Optics USB-2000þ) to understand the spin splitting in the
band structure GdN. The magnetization measurements have
been performed by a magnetometer using a superconducting
quantum interference device (Quantum design MPMS-XL)
to confirm the ferromagnetic ordering in GdN.

0003-6951/2012/100(23)/232410/4/$30.00 100, 232410-1 C 2012 American Institute of Physics

V
232410-2 Vidyasagar et al.
Figure 1(a) shows the typical optical absorbance spectra
in the range of 650–930 nm of a 68 nm GdN thin layer meas-
ured at different temperatures. The inhomogeneous back-
ground of the optical absorbance spectra is negligible
because the background is cancelled by subtracting the trans-
mitted signal passing through a reference sapphire substrate.
From Figure 1(a), it is obvious that the broad absorbance
spectral values reduce as the temperatures reduce from 300
to 100 K and that the values slightly increase as the tempera-
ture reduce from 30 to 5 K. A surprising change has been
identified in the trend of the absorbance spectra region of
710–810 nm, which is attributed to the fact that two optically
induced direct transitions originated from the low-
temperature spectra in the range of 30–5 K. This remarkable
change in the optical absorbance spectra is considered im-
portant and makes it possible to evaluate the two optical
direct (i.e., minority and majority spin) band gaps for the
GdN thin film at the X-point below 30 K using Tauc plots,
which are shown in Figure 1(b). From these plots, the respec-
tive optical band gaps are obtained by extrapolating the lin-
ear portion of the curve onto (ah)2 ¼ 0.11 The changes in
the direct band gaps are presented in the inset of Figure 1(b).
A plot of the temperature-dependent (300–3 K) optical
direct band gaps for the AlN/GdN/AlN double heterostruc-
ture is presented in Figure 2. Magneto-optical effects have
been clearly observed in the AlN/GdN/AlN double hetero-
structure below 30 K. From the plot, it is obvious that the
direct band gap increased (blue shift) as the temperature
FIG. 2. Optical direct band gaps of the 68 nm thin GdN film in the range of
3 K to 300 K. Optical band gaps of the minority and majority spin band ener-
gies are indicated in blue and green colors. Without applying magnetic field,
an exceptional spin splitting below its Curie point have been prevailed.
Appl. Phys. Lett. 100, 232410 (2012)
FIG. 1. (a) Temperature dependent opti-
cal absorbance spectra for AlN/GdN/
AlN heterostructure. (b) Tauc plots for
AlN/GdN/AlN heterostructure. The inset
is the magnification part of the optical
band gaps for the minority and majority
energies were presented. The spin split-
ting has been clearly visualized below
30 K.
decreased from 300 to 35 K. Such a trend is referred to as
semiconducting nature. Furthermore, the optical direct band
gap (red shift) drastically reduced as the temperature
decreased from 35 to 3 K. The typical red shift in the optical
gaps of the GdN film is presumed to be due to ferromagnetic
ordering by the exchange interaction between the nearest
neighbouring (J1) and next neighbouring (J2) magnetic states
in the cubic GdN lattice. Earlier theoretical reports based on
the mean field theory showed an anti-ferromagnetic ordering
between the N p and Gd d magnetic moments leading to an
interaction between the nearest neighbouring Gd atoms that
were ordered ferromagnetically through a d-f exchange cou-
pling.12,13 In this case, the investigators merely obtained a Tc
value of 10 K, which is comparatively lower than the experi-
mental value of 70 K. More recently, Sharma et al. reported
that the multi-band modified RKKY theory associated with a
realistic band structure of 5d conduction bands as an input
for the single-particle energies and the d-f exchange coupling
depended on the carrier concentration and the Curie tempera-
ture.14 These results differ considerably to the present exper-
imental findings. Hence, the expected possibilities regarding
the difference in Tc value has been addressed in the later
section.
Apart from the red shift, these heterostructures exhibited
both the minority and majority spin band splitting in the
band structure at the X-point of the GdN epitaxial thin film
in the temperature range of 35–3 K. In the minority spin
band, the reduction in the direct band gap from 35 K to 3 K
is substantial (85 meV), and the majority spin band energy is
greatly reduced (176 meV). According to the earlier reports
based on LSDA þ U calculations, the splitting energy differ-
ence could be attributed to the difference between minority
and majority spin band energies.15 Prior to that, both major-
ity and minority spin band gaps have a considerably larger
value than the half-metallic band gap of 0.6 eV; thus, the
half-metallic nature in the GdN has completely been aban-
doned. The shrink in the optical band gap (red shift) pertain-
ing to the spin disorder scattering by thermodynamic
fluctuations of the magnetic spins is anomalously reduced,
when the magnetic moments are parallel aligned. The spin
splitting energy difference gradually decreases (blue shift)
from 35 to 55 K and finally vanishes. This slight difference
pertaining to randomly oriented spins (marginal increase in
magnetic moments) leads to the paramagnetic behaviour.
The splitting energy difference (DE) and the magnetization
(M) as function of temperature are shown in inset of Figure 2.
From the inset of Figure 2, it is obvious that both the spin
232410-3 Vidyasagar et al.
splitting band difference and magnetization data have
showed similar trends, which confirm that at a finite magnet-
ization the conduction band and valance bands of GdN have
splits due to spin ordering. The combination of both red
shifts in the optical band gap and spin-splitting energies in
GdN are important opto-magnetic features originating from
GdN intrinsic ferromagnetic semiconductor, and such phe-
nomenon has not been identified in the diluted magnetic
semiconductors until now.
Figure 3(a) shows the temperature-dependent magnet-
ization (M-T) plots of AlN/GdN/AlN heterostructure for the
68 nm thin GdN and the external field along the plane of
1–100 mT. From the temperature-dependent magnetization,
it can be seen that there are two phase transitions attributed
to the short and long-range orders in the temperature range
of 62–3 K. When the temperature decreases from 62 to 32 K,
the development of short-range spin-spin correlations is
identified, and these correlations become stable at lower tem-
peratures. This behaviour certainly indicates the presence of
a paramagnetic phase. The magnetization depends on the
scattering of the charge carriers due to the interaction with
localized moments (Multiband Kondo Lattice Model), which
we clearly observed in the region of 62–30 K (II-paramag-
netic). This result supplements our previous findings that the
magnetic moment is gradually increased with temperature
range of 32–60 K.16 The magnetization drastically increases
in the temperature range of 32–5 K (I-Ferromagnetic). This
rapid increase in magnetization is attributed to the alignment
of spins (strength of quenched order is weak) by the long-
range spin-spin correlations, and thus, phase transition
occurs from the paramagnetic to the ferromagnetic state. Fer-
romagnetic materials that are cooled below a critical temper-
ature, Tc, exhibit long-range ordering of their magnetic
moments, as the strength of the thermal fluctuations becomes
Appl. Phys. Lett. 100, 232410 (2012)
less than that of the magnetic moment interactions. When
the temperature approaches zero, the saturation magnetic
moment per Gd atom is estimated to be 6.8 6 0.2 lB/Gd3þ at
B ¼ 100 mT. This value is in good agreement with the
expected 7.0 lB/Gd3þ for a half-filled 4f shell. From these
data, it is difficult to find the exact Curie point for the GdN
epitaxial thin film because the magnetic moment (M) values
simultaneously depend on the temperature (K) and the mag-
netic field intensity (B).
One of the standard experimental methods for determin-
ing the Curie temperature is the use of Arrott plots, in which
the square of the magnetization M in a field B is plotted as a
function of B/M at different temperatures, as shown in
Figure 3(b).17 The intercept (1/v) (v is susceptibility) on the
B/M axis vanishes at 32 K, which indicates that Tc has been
projected as 32 K. This is in good agreement with the data
from the hysteresis loops showing magnetic ordering till
temperatures of up to 30 K. This value is low compared to
those in earlier reports, which showed the highest Tc of GdN
as 69, 68, 65, and 58 K.18–21 It has been reported earlier that
the Tc value is extremely sensitive to the volume variations
(lattice distortion) and to the biaxial compressive strains
caused by uniaxial expansion in the growth direction of GdN
thin layer.19,21 More recent reports demonstrated that the Tc
value increased monotonically at higher sputtering power
and higher N2 partial pressure and confirmed the enhance-
ment in Tc is strongly contemplated to the variations in the
Gd:N ratio in the sputtering plasma (stoichiometric
effects).22–24 If the Gd:N ratio is non-stoichiometric, nitro-
gen vacancies have prevailed in GdN lattice; these nitrogen
vacancies lead to local distortion in the GdN lattice, and the
unit cell surroundings are stretched effectively. This stretch-
ing of the unit cell has caused the increase of the lattice pa-
rameter of GdN, which enables to reduce the Curie
FIG. 3. (a) Temperature dependent
magnetization measured at different
magnetic field intensities from 1 to
100 mT for 68 nm thin GdN. (b) The
Arrott plots (M2 versus B/M) are used to
obtain Tc for 68 nm thin GdN at different
temperatures, and the Tc is projected to
be 32 K. (c)–(d) The magnetic hysteresis
loop for 68 nm thin 68 nm film at 4.2 and
30 K when the external magnetic field is
in parallel with the sample surface. The
observation of hysteresis loop indicates
robust ferromagnetism at 4.2 K and soft
ferromagnetic at 30 K.
232410-4 Vidyasagar et al.
temperature significantly. Following these reports, the lower
Tc value obtained in the present study could be ascribed to
the differences in the Gd:N ratio (stoichiometry), defects
associated by nitrogen vacancies (volume variations), sput-
tering power, and biaxial compressive strains in GdN layer.
The best method for determining the ferromagnetic nature of
a material is to experimentally measure the magnetization-
magnetic field (M-H) hysteresis curves. Figure 3(c) presents
the magnetic-hysteresis loop of the heterostructure measured
at 4.2 K; and the magnification part of the hysteresis loop
measured at 4.2 K and 30 K is shown in inset of Figure 3(c).
The heterostructure exhibits typical magnetic-hysteresis
loops, as well as remanent magnetization, thus indicating the
presence of an ordered magnetic structure at 4.2 K. For
instance, for the heterostructure with the 68 nm thin GdN,
the in-plane orientation was clearly an easier direction
because the remanent magnetization and coercivity are found
to be 3.5 lB/Gd3þ and 47 Oe, respectively, at 4.2 K. The M-
H data for 30 K show that the remanent magnetization and
coercive field values are 0.6 lB/Gd3þ and 40 Oe, respec-
tively, and that the squareness area has greatly been reduced.
Clearly, the remanent magnetization and coercive field con-
siderably increase with a decrease in temperature. Very
small coercive field values observed at 4.2 and 30 K supports
the absence of significant oxygen, which is established by
SIMS measurements in our earlier reports. The saturation
magnetization (6.860.2 lB/Gd3þ) value is in good agree-
ment with the earlier report.20 Interestingly, the saturation
magnetization value of 6.860.2 lB/Gd3þ is close to theoreti-
cal value of 7 lB/Gd3þ; the high saturation magnetization
value is achieved by optimization of GdN depositing condi-
tions specifically at sputtering power of 250 W and N2 partial
pressure (Ar:N2 ¼ 9:6 ccm).24 However, a closer look at the
magnetic features indicates that the GdN epitaxial layer is
ferromagnetic below 32 K. Finally, it can be stated that the
best way to describe the ferromagnetism is at a finite
magnetization that produces a band splitting in the band
structure, thus reducing the carrier energy. The same mag-
netization increases the free energy of the localized spins,
and the free energy decreases as the temperature is lowered.
At the ferromagnetic transition temperature, the two energies
balance, and further reduction of the temperature gives rise
to spontaneous spin splitting and polarization of spins, i.e.,
ferromagnetism. These results have been clearly seen in our
present AlN/GdN/AlN heterostructure. Thus, these films
should be very useful in the development of semiconductor
spintronic and magneto-optical devices.
In conclusion, AlN/GdN/AlN double heterostructures
have been grown on c-sapphire by reactive rf sputtering
under ultra-pure conditions. The temperature-dependent op-
tical absorbance measurements for the heterostructure show
exceptional spin splitting at optical band gaps at the X-point.
The red shift in the optical band gap and the spin splitting
Appl. Phys. Lett. 100, 232410 (2012)
energy difference (DE) in minority and majority bands are
intensively related to carrier scattering and are minimized
when the magnetic moments are parallel aligned. The origin
of ferromagnetism is evidenced by the red shift in the band
gap and spin splitting in the conduction and valance band
and it is established by providing direct evidence of the mag-
netic ordering characterized by in-plane magnetic moments
using Arrott plots in the GdN-based heterostructures. The
saturation magnetic moment value is good agreement with
previous data available on GdN. These measurements pro-
vide a good agreement relative to the co-existent semicon-
ducting and ferromagnetic features and suggest that GdN is
efficient and sensitive enough for the development of low-
temperature spintronic devices.
We express our appreciation for the partial support from
a Grant-in-Aid for Creative Scientific Research (Grant No.
19GS1209) from the Japan Society for the Promotion of
Science.
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