Front. Mater. Sci.

2012, 6(4): 366–370

DOI 10.1007/s11706-012-0180-6

COMMUNICATION

Annealing effect on structural and magnetic properties

of Tb and Cr co-implanted AlGaN

Chun-Hai YIN, Chao LIU (✉), Dong-Yan TAO, and Yi-Ping ZENG
Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors,
Chinese Academy of Sciences, Beijing 100083, China

© Higher Education Press and Springer-Verlag Berlin Heidelberg 2012

ABSTRACT: Unintentionally doped AlGaN layers, which were co-implanted with 400
keV Tb+ ions and 200 keV Cr+ ions at doses of 1.5
1015 cm–2, have been rapid thermally
annealed at 800°C and 900°C for 5 min in flowing N2. Compared with Tb implanted AlGaN
sample, the Tb and Cr co-implanted sample reveals a larger magnetic signal. In this work,
the annealing effect on the structural and magnetic properties of Tb and Cr co-implanted
AlGaN thin films have been studied. XRD and Raman scattering results indicate that no
second phase presents in the thin films and most of the implantation induced defects can
be removed by post-implantation annealing. Superconducting quantum interference
device (SQUID) measurements show clear room temperature ferromagnetic behavior and
an increase in the saturation magnetization as a result of annealing. The saturation
magnetization of the 900°C annealed sample is about 15 times higher than that of the
800°C annealed sample.

KEYWORDS: diluted magnetic semiconductor (DMS), room temperature ferromagne-

tism, ion implantation, III-nitride thin film

Nitride based diluted magnetic semiconductors (DMSs)
have attracted great attention for their potential applications
in spintronic devices [1]. DMSs based on III-nitrides can be
fabricated by incorporating either rare-earth elements (RE)
or transition metals (TM) into the semiconductors. Room
temperature (RT) ferromagnetism has been observed in
various magnetic elements doped nitrides [2–6]. Among
RE doped nitrides, the magnetic properties of Tb doped
nitrides have been the least investigated. It has only been
reported that GaN:Tb exhibit a predominant paramagnetic
character [7]. The first-principles calculations carried out
by Sato and Katayama-Yoshida show that Cr-doped GaN
has the most stable ferromagnetic states [8]. RT ferromag-
netism has been confirmed in Cr-doped GaN, AlN and
Received September 17, 2012; accepted October 16, 2012
E-mail: cliu@semi.ac.cn
AlGaN films [9–10]. By co-doping RE and TM into
nitrides, it is expected that their 4f and 3d electrons would
take part in the magnetic interaction with atoms of the
matrix. So far, no research concerning RE and TM co-
implanted nitrides has been reported. In this communica-
tion, we report about the annealing effect on structural and
magnetic properties of Tb and Cr co-implanted AlGaN thin
films and the enhancement of ferromagnetism upon Cr co-
implantation. Possible origin of ferromagnetism in AlGaN:
(Tb + Cr) is also briefly discussed.
Unintentionally doped AlxGa1 – xN (x & 0.5) thin films
with the thickness of 1 μm were grown via metal-organic
chemical-vapor deposition (MOCVD). Before the growth
of AlGaN layer, AlN buffer layer (1 μm) had been
deposited on the c-plane of sapphire substrate (as-grown
sample). Ion implantation was performed with a LC-4 ion
implanter at 400°C. The ion beams were oriented 7° off
 Chun-Hai YIN et al. Annealing effect on structural and magnetic properties of Tb and Cr co-implanted AlGaN
perpendicular to the surface of the sample to avoid
channeling. In order to make the Tb3+ and Cr3+ implanta-
tion profiles overlap spatially, the energies of the Tb+ and
Cr+ ions were 400 and 200 keV, respectively. Both of the
doses were 1.5
1015 cm–2 (as-implanted sample). For
reference, AlGaN samples implanted with only Tb+ ions
were prepared by double energy ion implantation. The
energies of the Tb+ ions were 500 and 250 keV, with the
doses of 3.0
1015 and 1.5
1015 cm–2, respectively. The
distribution range of the ions is about 200 nm, based on
SRIM 2008 simulation [11]. Post-implantation annealing
was performed at 800°C and 900°C for 5 min under a
flowing N2 ambient in a rapid thermal processor (annealed
sample).
The structural property and crystal quality of the samples
were investigated by X-ray diffraction (XRD) using X' Pert
Pro MPD and Bede D1, respectively. The Raman
measurements were carried out in a microscopic confocal
Raman spectrometer (Renishaw RM2000) at RT using the
514.5 nm line of Ar+ laser as an excitation source.
Magnetization measurements were carried out using a
Quantum Design superconducting quantum interference
device (SQUID) magnetometer (MPMS XL-7) at 300 K.
The magnetic field swept between – 8000 and 8000 Oe,
which was applied parallel to the sample surface.
Figure 1(a) shows XRD spectra from AlGaN:(Tb + Cr)
after implantation and after annealing at 900°C. In both of
spectra, the diffraction peaks correspond to the expected
AlGaN and AlN (0002) and (0004) lines and the (0006)
line of sapphire substrate. The peaks labeled a and b are the
lines of AlGaN and AlN (0002) caused by Cu Kβ radiation,
respectively. No peak corresponding to second phases is
Fig. 1 (a) XRD spectra of the as-implanted and 900°C annealed samples of AlGaN:(Tb + Cr). The inset shows the X-ray rocking curves
of AlGaN (0002) peak of the above mentioned samples. (b) XRD ω-2θ scans of as-grown, as-implanted and annealed samples.
367
observed within the detection limit of XRD. The inset of
Fig. 1(a) shows X-ray rocking curves of the above
mentioned samples. The full width at half maximum
(FWHM) of the as-implanted and 900°C annealed samples
are 500.7 and 359.7 arcsec, respectively. After annealing
process, the intensity of the diffraction peak doubles. This
indicates that the post-implantation annealing is helpful to
recover the crystal quality of the thin films.
Figure 1(b) compares XRD ω-2θ scans of the as-grown,
as-implanted and annealed samples at AlGaN and AlN
(0002) peak. After implantation there is a broad feature in
the low angle region which indicates the expansion of the
AlGaN lattice due to the incorporation of Tb and Cr ions.
Since both of the radii of Tb3+ (0.092 nm) and Cr3+ (0.063
nm) are larger than that of Ga3+ (0.062 nm). The
interstitials can also cause the expansion of lattice. After
annealing the broad feature is partially recovered, which
means most of the Tb ions substitute the lattice sites. It is
clear that the peak position shifts slightly to lower angle.
We attribute this feature to the superposition of the
diffraction from the implanted region and the unaffected
region. The shape of the spectrum is dominated by the
implanted region which has a higher intensity. Similar
structural properties have also been observed in AlGaN:Tb
samples, which are not shown here.
Figure 2 shows the Raman spectra obtained at RT by
backscattering geometry. For the as-grown sample, the
peaks of the E2(low) (248 cm–1), E2(high) (658 cm–1) and
A1(LO) (888 cm–1) modes of AlN, and two sapphire signals
(418 and 750 cm–1) can be observed. The E2(high) (594
cm–1) and A1(LO) (830 cm–1) modes of AlGaN can also be
clearly seen, but the E2(low) mode (160 cm–1) of AlGaN is
368 Front. Mater. Sci. 2012, 6(4): 366–370

300 K for the 900°C annealed samples of AlGaN:Tb and

AlGaN:(Tb + Cr). The ferromagnetic signal for the Tb and
Cr co-implanted sample is stronger than that of the Tb
implanted one. The effective magnetic moment per atom
can be calculated as peff = Ms/N, where N is the
concentration of magnetic ions [2]. For AlGaN:(Tb + Cr)
samples, N is the sum of NTb and NCr. The effective
magnetic moment increased from 1.43 to 4.17 μB/atom by
the Cr incorporation. Magnetic parameters such as
saturation magnetization (Ms), remanent magnetization
(Mr) and coercive force (Hc) are listed in Table 1.
Until now, no established mechanism can explain the
ferromagnetism in nitride based DMS. It has been

Fig. 2 Raman spectra of the as-grown, as-implanted and

annealed samples of AlGaN:(Tb + Cr).

weak. After implantation, the E2(low) mode of AlGaN

arises, and all the three phonon modes of AlGaN show a
broad feature. After annealing, the intensities of the AlGaN
phonon modes increased, and the broad feature is partially
recovered. This indicates that the damages of the crystal
lattice induced by implantation have been partially
removed by annealing temperature of 800°C and 900°C.
It has been reported that the E2(low) and A1(LO) phonon
energies can quantitatively determine the Al content of
AlxGa1 – xN alloys [12], which are shown as follows:

E2 ðlowÞ=cm – 1 ¼ 142:8 þ 43:5x – 14:5xð1 – xÞ (1)

Fig. 3 Hysteresis loops for annealed samples of AlGaN:(Tb +
Cr) at 300 K. The inset shows an expended region of the magnetic
A1 ðLOÞ=cm – 1 ¼ 734 þ 153x þ 75xð1 – xÞ (2) signals.

The calculated Al content is about 50%, which is

consistent with the growth condition.
Figure 3 shows the hysteresis loops of 800°C and 900°C
annealed samples of AlGaN:(Tb + Cr) with the magnetic
field applied parallel to the sample surface at 300 K. For
each hysteresis plots, the diamagnetic contribution of the
sapphire substrate has been subtracted from the raw data
and the magnetization has been normalized by the volume
of the sample. No ferromagnetic behavior is observed in
the as-implanted sample, while both of the annealed
samples exhibit clear RT ferromagnetism. There is a huge
increase in the saturation magnetization as a result of
annealing. The saturation magnetization (Ms) of the 900°C
annealed sample is about 15 times higher than that of the
800°C annealed one. This indicates that high temperature
Fig. 4 Magnetization curves for 900°C annealed samples of
annealing is essential for obtaining RT ferromagnetism in AlGaN:(Tb + Cr) and AlGaN:Tb at 300 K. The inset shows an
AlGaN:(Tb + Cr). Figure 4 shows magnetization curves at expended region of the magnetic signals.
 Chun-Hai YIN et al. Annealing effect on structural and magnetic properties of Tb and Cr co-implanted AlGaN
Table 1 Magnetic parameters of annealed samples of AlGaN:(Tb + Cr) and AlGaN:Tb
Sample Annealing temperature/°C Ms/(emu$cm–3)
AlGaN:(Tb + Cr) 800 0.39
AlGaN:(Tb + Cr) 900 5.76
AlGaN:Tb 900 2.99
suggested that the colossal magnetic moment in Gd
implanted GaN originates from the long range spin
polarization of Ga and/or N interstitials generated by
implantation [13]. In our experiments, however, the Ms of
900°C annealed sample is 15 times higher than that of
800°C annealed sample, while the former is expected to
contain lower defect concentration than the latter. Thus, we
can exclude defects to be the origin of ferromagnetism in
AlGaN:(Tb + Cr). According to the XRD analysis, no peak
corresponding to the second phase has been observed
within the detection limit. Although small quantities of
second phases can not be completely excluded, second
phases can also be ruled out to be the ferromagnetic origin
in AlGaN:(Tb + Cr), since Cr, CrN, Cr2N, AlxCry and
Gax Cry are not ferromagnetic [14], and the Curie
temperature of TbN [15], TbAl2 [16] and TbGa [17] are
only 44, 105 and 154 K, respectively. Besides, based on the
results of conventional Hall measurement, the samples are
highly resistive, we can also rule out the free-carrier
mediated RKKY (Ruderman-Kittel-Kasuya-Yosida) inter-
action [2]. The formation of bound magnetic polarons
(BMPs) may be the most possible explanation of
ferromagnetism in our samples. A large number of
magnetic ions surround one localized carrier to form a
bound magnetic polaron, and the interactions between
BMPs result in the macroscopic ferromagnetism [18].
In summary, RT ferromagnetic AlGaN:(Tb + Cr) thin
films have been successfully fabricated by ion implanta-
tion. Our study indicates that high temperature annealing
can greatly enhance the ferromagnetic properties of the
films and is essential for the microstructure recovery. The
saturation magnetization of the 900°C annealed sample is
about 15 times higher than that of the 800°C annealed
sample. Compared with Tb implanted AlGaN sample, the
Tb and Cr co-implanted sample reveals a larger saturation
magnetization. The effective magnetic moment increases
from 1.43 to 4.17 μB/atom by the incorporation of Cr. The
formation of BMPs may be the possible origin of
ferromagnetism of the highly resistive AlGaN:(Tb + Cr)
thin films.
Acknowledgements The authors would like to thank Associate Professor
369
Effective magnetic
Mr/(emu$cm–3) Hc/Oe
moment/(μB$atom–1)
0.083 151.81 0.28
0.46 58.80 4.17
0.67 119.93 1.43
Jian-Ming Li and Jia-Dong Xu of Institute of Semiconductors, Chinese
Academy of Sciences, for their assistance with ion implantation experiment.
This work was supported by the National Natural Science Foundation of
China (Grant No. 60876004).
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