Giant optical splitting in the spin-states assisting a sharp magnetic

switching in GdN thin films

R. Vidyasagar, T. Kita, T. Sakurai, and H. Ohta

Citation: Appl. Phys. Lett. 102, 222408 (2013); doi: 10.1063/1.4809758

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 APPLIED PHYSICS LETTERS 102, 222408 (2013)

Giant optical splitting in the spin-states assisting a sharp magnetic

switching in GdN thin films
R. Vidyasagar,1,a) 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
Center for Support to Research and Education Activities, Kobe University, 1-1 Rokkodai, Kobe 657-8501,
Japan
3
Molecular Photoscience Research Centre and Graduate School of Science, Kobe University, 1-1 Rokkodai,
Kobe 657-8501, Japan

(Received 30 April 2013; accepted 22 May 2013; published online 5 June 2013)
The spin-states splitting and spin ordering in the band structure of GdN thin films have been studied
using optical absorbance spectroscopy and magnetometer. Remarkably, the optical absorbance
measurements indicate a giant splitting in the spin-states near-infrared frequency regime, through
which the spin-up and spin-down states of the GdN films have been evaluated. Both the spin-up and
spin-down states split subsequently wider, which attributes to a combining effect from the nitrogen
vacancies, and the population of electronic states pertaining to the spins associated with 4f states of
Gd3þ ions. While spin-splitting energy enhances, magnetic-hysteresis loops suggest a sharp
magnetic switching feature. V C 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4809758]

Ferromagnetic semiconductor, a single material in which bandgap below its spin ordering temperature (TC), as discussed
both optical and spin polarization are apt to control and manip- previously.10 Experimental realization of these results encour-
ulate by optical means, has received enormous research atten- ages us that this system leads to new routes in designing spin-
tion from the viewpoint of solid state physics, and not only so tronic devices.
but also spread its vanguard on the way of spintronic device In spite of the tremendous potential of GdN thin film for
technologies.1,2 Key elements for such devices would require spintronics, the stoichiometry and type of spin ordering in
semiconducting host material, inside of which the spin-states GdN are the most controversial and contested since more
are precisely controlled by internal parameters. These spin-state than a half century.5,11,12 The non-stoichiometry of GdN is
configurations are extremely sensitive to temperature, structural broadly classified into two parts: the strain-induced structure
distortion, epitaxial strain, the environment of the magnetic by nitrogen vacancies (NVs), and the structure could effec-
atom, etc., and ensuring the spin transition states is far from tively diffused by oxygen due to its high reactivity towards
understanding. Recently, the ferromagnetic semiconductor atmospheric air. Hence, the experimental studies have been
GdN is particularly interesting, since Gd has a half-filled 4f limited by the facts of instability in atmospheric air and diffi-
shell which determines the inter-atomic 4f-5d exchange interac- culty of depositing high quality films. It has been reported
tion of the individual ions; this 4f shell contributing a large net that measurements without magnetic fields are of great value
magnetic moment of l4f ¼ 7.0 lB.3,4 The 4f shell is electrically because the application of magnetic field itself will transform
inert due to its negligible overlap with the conduction band, the nonmagnetic to ferromagnetic.12 Therefore, confirming
and the unoccupied exchange splitting in 4f-5d bands coupled the spin ordering using the spectroscopic measurements
with p states of GdN governs the charge as well as spin trans- without applying magnetic field is a vindication for ferro-
port characteristics. So far, the nature of the spin-states is often magnetic signature. In this letter, we describe an optically
being interpreted by theoretical studies.5,6 Recently, Local Spin induced spin-splitting in the band structure of GdN thin
Density Approximation (LDSA) þ U calculations predicted films. Optical absorbance measurements have been carried
that the average gap of spin-up (1.12 eV) and spin-down out to provide a direct evidence of spin-states splitting in the
(1.58 eV) gap comes to be 1.35 eV in the ferromagnetic state of band structure of GdN without the complication of external
GdN;7 from these calculations, it is understood that the spin- fields. Magnetic-hysteresis (M-H) loops display a sharp mag-
states can split up to 0.46 eV in the band structure of GdN. netic switching with an increase of remanence.
Despite a number of attempts over past decades, none have Double heterostructures of AlN/GdN/AlN were epitax-
been able to experimentally replicate the spin-states splitting in ially grown on c-sapphire (0001) substrates at 500  C using re-
the band structure of GdN. More recently, we purported the first active rf magnetron sputtering technique. Chemically cleaned
experimental evidence of the spin-states split up to 0.14 eV in c-sapphire substrate (10  10 mm2) was mounted onto a sam-
the band structure of 68 nm thin GdN film,8,9 and this splitting ple holder and transferred into the growth chamber. The
value is by a factor of 3 smaller than the predicted value. The growth chamber was evacuated below 2.5  106 Pa, and the
strong magneto-optical effects in GdN thin films are evidenced substrate was out-gassed at 500  C for 2 h. We introduced 6N
by a drastic red-shift (approximately 300 meV) in the optical pure mixed Ar and N2 gases with specific timing and duration
using a mass flow controller, by which the Ar:N2 ratio ¼ 9:6
a)
Author to whom correspondence should be addressed. Electronic mail: sccm is maintained during the reactive growth process; the
[email protected] total sputtering pressure stabilized at 5 Pa. The GdN epilayers

0003-6951/2013/102(22)/222408/4/$30.00 102, 222408-1 C 2013 AIP Publishing LLC

V
222408-2 Vidyasagar et al. Appl. Phys. Lett. 102, 222408 (2013)

with thickness (t) in the range of 45 < t < 90 nm were depos- the band mixing of spin-up and spin down states.13 When the
ited as a sandwich layer between the 100 nm thin AlN buffer thickness of GdN decreases to 75 nm, a narrow deviation has
layer and 100 nm thin AlN capping layer. The typical growth been identified in the Tauc plots, which ascribed to the elec-
rates are 32.3 nm/s for AlN and 2.0 nm/s for GdN, respectively. tronic states spilt into spin-up (E" ¼ 1.28 eV) and spin-down
The oxophilicity feature is curtailed by both the AlN capping (E# ¼ 1.19 eV) band energies, well separated by the spin-states
layer and the ultra-pure depositing conditions. Our earlier stud- splitting energy (DE ¼ E#  E") of 0.11 eV. The direct
ies showed that the X-ray diffraction profiles of GdN films bandgap of 75 nm thin GdN film is 1.335 eV, which is an aver-
showed a preferential [111] orientation of rock-salt structure. age value of E" and E#. When the thickness of GdN decreased
Extended X-ray absorption fine structure analysis reveals that to 60 nm, the average bandgap of E" (1.26 eV) and E#
the structure function for GdN exhibited the nearest-neighbor (1.53 eV) comes out to be 1.395 eV, where the DE is enhanced
site of nitrogen, the second-nearest sites of the next Gd, and to 0.27 eV. Furthermore, when the thickness of GdN is
the third-nearest sites of the next nitrogen; prior to that, no sig- decreased down to 45 nm, the direct bandgap of 1.325 eV is an
nal related to Gd2O3 and metal Gd has been observed in SIMS average value of the E" (1.10 eV) and E# (1.55 eV); in this
profiles.10 A home-built spectrophotometer (Monochromator case, the DE is greatly enhanced to 0.45 eV. Inset in Figure
Model: Ocean Optics USB-2000þ) attached with a helium 1(b) presents the energy-dependent optical absorbance coeffi-
flow cryostat is used to probe the spin-states splitting in the cient for GdN, from which an indirect bandgap at C point has
band structure of thin GdN films. The superconducting quan- been estimated by extrapolating the linear portion of the curve
tum interference device (Quantum design MPMS-XL) is used onto a1/2 ¼ 0. It is important to note that the indirect bandgap
to estimate the TC and spin switching feature of thin GdN of 45 nm thin GdN film is 0.84 eV, which is quite small when
films. compared with remaining films (1.15 eV and 1.19 eV). The
Figure 1(a) shows typical optical absorbance spectra of indirect bandgap shrinking is about 0.35 eV. It has been
GdN films with different thicknesses. These spectral trends reported that nitrogen p band can split up to 0.2 eV;14 the large
were recorded in the near-infrared wavelength range of value of 0.35 eV is attributed to spin-states splitting of the 5d
640–1030 nm at 5 K. Remarkably, the spectral trends indicate bands induced by intra-atomic exchange interaction with the 4f
a giant deviation in the wavelength range of 700–780 nm, and state. Accordingly, it is being quite reasonably assumed that
this large deviation attributed to the spin-states splitting in the 5d bands pushed the N-2p states to lower energies; leading
the band structure of GdN at X symmetry point. The manifes- to decrease in the indirect bandgap.
tation of spin-states splitting introduces a net imbalance In Figure 2(a), we plot the optical direct bandgap against
between spin pointing in different direction, which enable us GdN film thickness; the data showed that GdN layer exhibits
to evaluate both the spin-up and spin-down band states in the the Burstein-Moss shift in the bandgap with the decrease in
band structure of GdN. Notably, the spectral trends consist of thickness; the film deposited at a thickness of 75 nm to
dissimilar line shapes along with giant deviations in the ab- 45 nm showed nearly similar bandgap (1.35 6 0.05 eV). The
sorbance edge. In light of these observations: (i) the reduction Burstein-Moss shift could be ascribed to a combined effect
of broadness in the absorbance edge, (ii) the absorbance edge from the NVs, which donate excess electrons and the popula-
shifts towards shorter wavelength side, and (iii) enhanced tion of Gd-4f electronic states mediated by the hybridization
light absorbance in the wavelength range of 700–780 nm with between the Gd-5d bands and the N-2p states. In our earlier
decrease of GdN thickness. These facets reflect that absorb- studies, the magnitude of NVs has been investigated from
ance spectral lines strongly depend on the electronic coupling the free carrier absorption signal in infrared frequency
effects. regimes, in which we observed that the peak position shifted
By using the optical absorbance spectra, the direct towards the shorter wavelength side; the intensity of the
bandgap of GdN thin films has been evaluated though Tauc peak decreased, while the carrier density increases with the
plots, which is shown in Figure 1(b). The direct bandgap for decrease of GdN thickness.10 It is quite correctly presumed
GdN films at X point obtained by extrapolating the linear por- that the NVs prevailed by an inefficient activation of N2
tion of the curve onto (aht)1/2 ¼ 0. The 90 nm thin GdN film would be lower diffusion rate of nitrogen in the metal lattice.
showed a direct bandgap of 0.98 eV without spin-splitting in More recently, even a small portion of NVs in GdN illus-
the band structure of GdN. This peculiar behavior might be trates the suppression of bandgap from 1.03 eV (Ar:N2
due to the effect of spin-orbit scattering, which originates from ratio ¼ 9:6 sccm) to 0.95 eV (Ar:N2 ratio ¼ 9:3.6 sccm).15

FIG. 1. (a) Typical optical absorbance

spectra of the thin GdN films vary as a
function of thickness exhibiting absorp-
tion edge broadening. (b) Tauc plots for
the thin GdN films, both the spin-up
and spin-down states are spread wider
(see arrows in Figure 1(b)) as the film
thickness decreases; the inset shows the
energy-dependent optical absorbance
coefficient of GdN films, and the linear
portion extended to a1/2 ¼ 0 gives an
indirect bandgap.
222408-3 Vidyasagar et al. Appl. Phys. Lett. 102, 222408 (2013)

FIG. 2. (a) Direct bandgap of GdN thin

films varied as a function of thickness.
(b) Thickness-dependent optical spin-
splitting energy for GdN films, where
68 nm GdN film data of DE have been
taken from our previous report.

We note that the optical bandgaps obtained in the present by the magnetic Gd3þ ions expected to be too small in this
study is relatively larger than the half-metallic bandgap of optical studies. So that, it being plainly stated that the linear
0.6 eV, thus the half-metallic nature is forbidden in GdN.16 increase of DE is attributed to a combining effect from the
We explore the optically induced DE in the band struc- biaxial compressive strain, the strong magnetic anisotropy,
ture of GdN films, which varies as a function of thickness and the population of electronic states pertaining to the spins
(75–45 nm). In Figure 2(b), we find that the magnitude of the associated with 4f electronic states of Gd3þ mediated by p-d
DE increases linearly (linearly fits using linear relation) with hybridization. The earlier theoretical predictions showed that
the decrease of GdN layer thickness. The spin-states splitting the spin-states splitting energy is constant in case of half me-
energy is defined as tallic;18 in the present study, we have clearly seen that the
spin-states splitting energy increased linearly with increase
DE ¼ gð7=2 þ xÞlB B þ Hint ; of bandgap. It is quite correctly considered that the GdN thin
films are semiconducting rather than a half-metallic.
where g is Lande g-factor, lB is Bohr magneton, B is applied The distinctive magnetic switching feature has been
magnetic field, x is referred as defects, and Hint is the internal studied with different GdN layer thickness using the M-H
fields. In the present study, DE is obtained without applying loops. Figure 3(a) shows typical M-H loops of GdN thin films
magnetic field; hence, the effect of B is negligible. We with t ¼ 45, 60, 75, and 90 nm and these measurements were
observed that both the E" and E# electronic states subse- carried out at 4.2 K. From the inset in Fig. 3(a), it is obvious
quently split wider (an indication of spin-splitting in both that the thinner films have a sharp magnetic switching
conduction and the valance band) with decrease of GdN film (square-like M-H loop) with narrow coercive fields (HC).
thickness. By focusing on this subsequent splitting, we Fascinatingly, we observed an enhancement of in-plane re-
explore the x and Hint terms. The wider splitting is explained manent magnetization (Mr) about 30% (3.09 to 4.45 lB/
as follows: reduction in the bandgap of the minority spin Gd3þ) with the decrease of GdN layer thickness. This re-
energy caused by compressive strains; specifically, with an markable enhancement can be understood by the following:
in-plane compressive strain of 3%, where the Fermi level The electronic states are populated by the free carriers gener-
crossing the valance bands.16 In contrast with this compres- ated by the electron trapping at 2p nitrogen vacancy states,
sive strains, the angular dependence resonance field studies and alignment of 4f magnetic moments relies on the coordi-
of thin GdN films showed that the resonance field is maxi- nation of the Gd3þ ions at the interface. The population of
mum along the out-of-plane and minimum along the in- electronic states would strengthen the exchange interaction,
plane, which contemplated to strong demagnetization fields which splits the electronic states into spin-up and spin-down,
associated with the static magnetization; thus, we presume such phonological spin-states splitting has already been dem-
that the thinner GdN film has relatively strong magnetic ani- onstrated in the optical studies. Accordingly, we presume that
sotropy along in-plane.17 Moreover, the interstitial nitrogen the magnetic anisotropy in the internal structure of GdN is inti-
vacancy centers lead to strengthen the p-d hybridization, and mately related with pinning efficiency, in which the spin car-
the population of electron states that carry spin associated riers assist the pinning of the extremely narrow domain walls;
with 4f states of Gd atom. Hint is the internal field produced thus, the sharp magnetic switching feature prevailed in thinner

FIG. 3. (a) In-plane magnetic hysteresis

loops of GdN films varied as a function
of thickness. Measurement was taken at
4.2 K. Top inset: The magnification of
the hysteresis loop. (b) The TC and MS
as a function of GdN film thickness;
these TC values were estimated using
Arrott plots.
222408-4 Vidyasagar et al. Appl. Phys. Lett. 102, 222408 (2013)

GdN films. Contrastingly, the large Mr (4.45 lB/Gd3þ) with a effect from the p states of NVs, the magnetic anisotropy, and
narrow HC (37 Oe) featuring the GdN is a soft ferromagnet. the population of electronic states pertaining to the spins
These values are better than that of the previous reports of associated with 4f of Gd3þ linked p-d hybridization. Upon
GdN.13,19 The saturation magnetization (MS) and TC (esti- enhancement of spin-states splitting energy, the magnetic
mated using Arrott plots) as a function of GdN layer thickness hysteresis loops reveal a sharp magnetic switching with
are plotted in Fig. 3(b). From the M-H loops, it is obvious that increase of remanence. These results vindicate an insepara-
the MS value increased from 6.80 to 7.65 (60.2) lB/Gd3þ with ble correlation between the optical and magnetic properties
the decrease of GdN film thickness range from 90 to 45 nm. that can be amply controlled by the GdN film thickness.
Each NV donates three electrons in the conduction band; we
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7 lB/Gd3þ) can be ascribed to the NVs. The MS for 90 nm thin 2
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