Journal of Alloys and Compounds 621 (2015) 314–318

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Investigation of blue luminescence in Mg doped AlN films

Xiliang Sun, Juan Xiong ⇑, Weihai Zhang, Lei Liu, Haoshuang Gu ⇑
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Faculty of Physics & Electronic Science, Hubei University, Wuhan 430062, China

a r t i c l e i n f o a b s t r a c t

Article history: The Al1xMgxN thin films were deposited on (1 0 0) silicon substrates by magnetron sputtering. The struc-
Received 16 August 2014 tural and photoluminescence properties of the films with varying Mg concentrations were analyzed by
Received in revised form 27 September 2014 X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS),
Accepted 2 October 2014
Raman spectra and photoluminescence (PL), respectively. The results clearly showed that the Mg atoms
Available online 13 October 2014
successfully incorporated into AlN, while the crystal structure of the films was maintained. The Raman
spectra of Al1xMgxN films reveals the enhancement of A1 (TO) mode, a slightly blue-shift and an
Keywords:
augment in FWHM for E2 (high) phonon mode with increasing Mg content, which can be associated with
Luminescence
AlN thin film
the deterioration of (0 0 2) orientation and the appearance of (1 0 0) orientation. A broad blue band cen-
Mg doping tered at 420 nm and 440 nm was observed in Mg-doped AlN films. It was suggested that the transitions
Sputtering from the shallow donor level not only to the ground state but also to the excited states of the deep level
was responsible for the broad blue emission band. This work indicates the AlN film for the application in
lighting emission devices.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction
III-V nitrides are promising candidates for white light-emitting
diodes (LEDs) and field emission displays (FEDs) owing to their
wide direct band from 0.7 eV (InN) to 6.2 eV (AlN), high thermal
conductivity, excellent chemical and physical stability [1–3].
Among them, AlN thin films have attracted considerable attention
as for thermal dissipation, dielectric layers, and surface and film
bulk acoustic wave devices due to the high piezoelectric response,
high electrical breakdown voltage and very small negative electron
affinity [4,5].
Recently, AlN doped with rare-earth, such as Er, Gd, Tb, Eu, and
Ce, have been intensively asserted the photoluminescence (PL)
properties [6–10]. The absorption and the emission of rare-earth
ions are very efficient in the hosts because of the allowed 4f–5d
broadband transitions. On the other hand, Zn, Si and Mn doped
AlN phosphor or thin film have also been reported, in which the
luminescence is ascribed to the transition of 3d-electrons [11,12].
However, to our knowledge, there is no report about the photo-
luminescence of Mg-doped AlN host. In this paper, we present the
preparation of Mg-doped AlN film by magnetron sputtering with
different doping concentrations. The Raman spectra of Al1xMgxN
films reveals the enhancement of A1 (TO) mod, a slightly blue-shift
⇑ Corresponding authors. Tel.: +86 27 88663497; fax: +86 27 88663390.
E-mail addresses: xiongjuana@163.com (J. Xiong), guhsh@hubu.edu.cn (H. Gu).
and an augment in FWHM for E2 (high) phonon mode with increas-
ing Mg content, which can be associated with the deterioration of
(0 0 2) orientation and the appearance of (1 0 0) orientation. The PL
results show one broad blue band, which is centered at 420 nm and
440 nm. Furthermore, the luminescent mechanism is also
discussed in detail.
2. Experiment
The AlN:Mg films were deposited on Si (0 0 1) substrate in RF magnetron sput-
tering system from Al and Mg purity 99.999% targets by alternatively depositing
AlN and Mg films. A constant partial gas pressure ratio of Ar:N2 = 2:3 with a total
pressure of 0.5 Pa and a RF power of 150 W was applied for depositing AlN film. A
sputtering pressure of pure Ar gas with 0.5 Pa was applied for doping Mg with
the RF power of 60 W. The base pressure in the chamber was below
2.0  104 Pa and the substrate temperature was held on 300 °C. The thickness
of Mg doping and AlN film is about 5–10 nm and 200 nm, respectively, for each
layer. The whole films had a thickness of about 1100 nm. The dopant concentra-
tion of Mg was controlled by varying the sputtering time, which was 20 min for
AlN film and 2–6 s for Mg doping, respectively. Both the beginning and the end of
the layers are AlN films to prevent Mg atoms from permeation to substrate and
oxidation.
The Mg concentration and chemical composition of the Al1xMgxN films was
determined by X-ray photoelectron spectroscopy (XPS, VG Mutilab 2000). The Mg
concentration was varied as 0.8, 1.7, 3.1 to 4.4 at.%. The crystalline structure, surface
and cross-sectional morphology were characterized by X-ray diffraction (XRD, D8
Advance) and field emission scanning electron microscopy (SEM, JSM-7100F). The
photoluminescence spectra of the samples were collected at room temperature
(RT) excited by the 250 nm line of a Xe lamp as the excitation source. Raman spectra
of the samples were performed at RT by a Renishaw InVia spectrometer with a
spectral resolution of 1.0 cm1.

http://dx.doi.org/10.1016/j.jallcom.2014.10.018
0925-8388/Ó 2014 Elsevier B.V. All rights reserved.
 X. Sun et al. / Journal of Alloys and Compounds 621 (2015) 314–318
3. Results and discussions
Fig. 1 shows the XRD patterns of the undoped and Mg-doped
AlN samples with Mg concentrations of 0.8, 1.7, 3.1 and 4.4 at.%.
The concentrations of Mg in the doped samples were determined
by XPS and the XPS results will be discussed in following para-
graph. Strong (0 0 2) peaks were located at 36° for all the samples
in Fig. 1, demonstrating the AlN films possesses a hexagonal wurtz-
ite structure [13]. It can be observed that the (1 0 0) AlN peak
appears as Mg doping content increases to 1.7 at.%. And the inten-
sity of (1 0 0) peak enhances with the Mg concentration increasing
to 4.4 at.%, while the crystal structure is maintained. Indeed, it is
well known that the AlN (0 0 2) plane is the close-packed plane,
whereas, the (1 0 0) plane is the loose-packed plane and the energy
of Al–N bond in (1 0 0) plane is weaker than that of Al–N bond in
(0 0 2) plane [14]. Therefore, Mg atoms with similar atomic radius
to Al are more inclined to substitute the Al sites in (1 0 0) plane.
And the peak shift testifies the substitution of smaller Mg atoms
at Al. positions. It can also be observed that the peak position of
AlN (0 0 2) shifts to smaller angles with the increase of Mg concen-
tration. A similar shift of the (0 0 2) diffraction angle toward lower
angles with increasing doping content is also observed in Cr-,
Cu-doped AlN [15–17]. On the other hand, the intensity of (0 0 2)
peak decreases and the full width at half maximum (FWHM) of
the peak increases. This indicates the deterioration of crystalline
property and it might be attributed to the defects in the samples
induced by Mg ions’ incorporation into the AlN matrix. No peaks
corresponding to any possible secondary phase, such as metallic
Fig. 1. X-ray diffraction patterns of Al1xMgxN samples with varying Mg concen-
trations. x = (a) 0, (b) 0.8, (c) 1.7, (d) 3.1 and (e) 4.4 at.%.
Fig. 2. The cross-sectional morphology of Al0.956Mg0.044N sample.
315
Mg or its oxides and nitrides were observed within the measured
range. Highly parallel columnar crystals with about 1.1 lm thick-
ness are observed in the cross-sectional morphology of the Al0.956-
Mg0.044N sample, as shown in Fig. 2, which demonstrate the
monolayer and homogeneity structure of Mg:AlN films.
The surface morphologies of the Mg-doped AlN samples with
varying Mg concentrations are shown in Fig. 3, respectively. A com-
pact, uniform and nanocrystalline morphology is observed for all
deposited samples. From Fig. 3, it can also be observed that the
grain size of the Mg-doped surface reduced with the increment
of Mg doping concentration from 0.8 to 4.4 at.%. The average grain
size for the Al0.992Mg0.008N sample is around 60–80 nm. The grain
size reduced to around 50 nm, 30 nm, and 20 nm, for the samples
doped with 1.7, 3.1, and 4.4 at.% Mg in the films, respectively.
Chahmat et al. reported that the average crystallite size decreased
with increasing Sn concentration, which suggest a degradation of
crystalline properties [18]. Pan et al. also observed the smaller
grain size in Si-doped AlN films with the increment of Si doping
content, which is attributing to the fact that the heavier Si dopant
would deteriorate the crystal quality of AlN matrix [19]. Based on
the XRD result, we also attribute the decrease of grain size with
increasing Mg concentration to the degradation of crystalline
quality of AlN films.
XPS analysis of the Al1xMgxN thin film was carried out to iden-
tify the chemical binding energy and to confirm the Mg elements
in the Mg:AlN films. We only show the result of Al0.956Mg0.044N
sample in Fig. 4 since the similar spectra of the other samples were
observed by XPS. All the peaks were calibrated according to the
carbon 1s line at corresponding binding energy of 284.6 eV.
Fig. 4(a) shows the survey spectra of Al0.956Mg0.044N film, indicat-
ing the presence of the elements C, O, Al, N and Mg. The C 1s peak
is resulted by the ambient carbon during our measurement. Curve
of Al 2p core level is shown in Fig. 4(b), which is fitted into two
components assigned to Al–N (73.6 eV) and Al–O (74.5 eV) bond-
ing. For the O 1s level, a peak at 531.7 eV for the O2 adsorbed
and traces of chemisorbed O–Al (530.9 eV) bonds can be resolved
(in Fig. 4(c)). Moreover, for N 1s level as shown in Fig. 4(d), only
one peak at 396.4 eV was observed, which is attributed to N–Al
bonding [20]. The core level of Mg 2p located at 50.2 eV can be
observed in Fig. 4(e) and indicates the presence of Mg2+ in the sam-
ple, which demonstrates that Mg were doped successfully into the
AlN [21]. Table 1 summarizes the elemental concentration of the
samples, which includes Al, N, Mg, O, and C for all samples, indicat-
ing the sample is nitrogen-deficient film.
Raman scattering is a useful tool for the characterization of the
structural quality of AlN by analyzing the phonon frequency,
frequency shift and the width of the Raman scattering peak. The
space group of the hexagonal wurtzite AlN belongs to V46v with
all atoms occupying the C3v sites. Six optical phonon modes of
A1 + 2B1 + E1 + 2E2 are predicted at the C point of the Brillouin zone
by group theory. The A1, E1 and two E2 modes are Raman and infra-
red active, while the two B1 modes are Raman silent. And the A1
and E1 modes split into the longitudinal optical (LO) and transverse
optical (TO) branches [22]. Fig. 5(a) depicts the Raman spectra of
the undoped and Mg-doped AlN films with various Mg contents
on Si (1 0 0) substrate at room temperature. The peak at
520 cm1 is originated from the Si substrate [23]. Samples exhibit
two major peaks around 250 cm1, and 655 cm1, which corre-
spond to the E2 (low) mode and the E2 (high) mode of the AlN
[24]. It is noted that the additional A1 (TO) mode (at 610 cm1)
excited in Al1xMgxN films for x P 1.7 at.% is correlated to AlN
(1 0 0) diffraction peak. And the peak intensity was strengthened
with the increasing Mg content. According to the rule of Raman
scattering, the E2 (high) vibrational mode is excited by an electric
field perpendicular to c-axis, while the A1 (TO) mode is excited
by the electric field parallel to the c-axis. Therefore, the E2 (high)
316 X. Sun et al. / Journal of Alloys and Compounds 621 (2015) 314–318

Fig. 3. Surface morphologies of Al1xMgxN samples with varying Mg concentrations. x = (a) 0.8, (b) 1.7, (c) 3.1 and (d) 4.4 at.%.

Fig. 4. XPS spectra of Al0.956Mg0.044N film: (a) survey scan, (b) Al 2p, (c) O 1s, (d) N 1s and (e) Mg 2p core levels, respectively.

mode is allowed and the A1 (TO) mode is forbidden when the direc-
tion of propagation of laser light is parallel to c-axis. However, both
the E2 (high) mode and the A1 (TO) mode will be excited when the
electric field has components parallel and perpendicular to the
c-axis if the grains exhibit other orientation [25]. Therefore,
the enhancement of A1 (TO) mode was observed, which is due to
the appearance and the increasing intensity of (1 0 0) orientation
in the Mg heavier doped samples, which is consistent with the
result of XRD analysis.
In addition, Fig. 5(b) shows the variations in full width at half
maximum (FWHM) of E2 (high) in Al1xMgxN (x = 0–0.044) films
as a function of Mg content. It can be observed that the E2 (high)
mode slightly shifts to lower frequencies and the FWHM is found
to be broadening as the decrease of the (0 0 2) peak. Since the width
of the peak reflects the phonon anharmonic decay, the crystalline
quality, and the presence of defects, it would increase the number
of channels for phonon decay and therefore increase the line width
[26]. In our work, the doped samples are Al-rich characterized by
 X. Sun et al. / Journal of Alloys and Compounds 621 (2015) 314–318 317

Table 1
Atomic concentrations of Al1xMgxN films determined by XPS.

Samples (at.% Mg) Atomic concentrations (at.%)

Mg Al N O C
0 0.0 44.2 39.2 10.4 6.2
0.8 0.8 42.6 39.6 10.5 6.5
1.7 1.7 42.7 39.6 9.6 6.4
3.1 3.1 41.1 39.4 10.1 6.3
4.4 4.4 40.9 38.6 9.8 6.3

Fig. 6. The room temperature photoluminescence spectra of Mg-doped AlN for

varying Mg concentrations. The dashed lines present the blue bands of the
luminescence.

donor–acceptor pair (DAP) transitions with Mg-vacancy complexes

(MgGaVN) as a deep donor and MgGa as an acceptor. They concluded
that nitrogen vacancies (VN) and MgGa are inclined to exist as near-
est-neighbor complex owing to the oppositely charged [29]. Eckey
et al. found a redshift in the DAP emission in highly Mg-doped
c-place GaN with increasing Mg/Ga precursor ratio and attributed
this phenomenon to the high compensation level [30]. Meanwhile,
Mattila et al. suggested that nearly all isolated oxygen would
occupy nitrogen sites in the growth process to keep the thermal
equilibrium, and that ON in AlN is shown to be a deep center. They
also indicated that the possibility for formation of V3Al  3  ON
þ

defect complexes [31].

As a result, considering the similarity between GaN and AlN and
our experiment, the incorporation of O is unavoidable, as con-
firmed by XPS. We can deduce that the blue band in Mg-doped
AlN film can result from the transitions from the shallow donor
level not only to the ground state but also to the excited states of
the deep level. In detail, the shallow donor may also involve VN
and the deep level of V3 þ
Al  3  ON and MgAl–VN defect complexes.
Fig. 5. (a) Raman spectra and (b) concentration dependence of the peak positions
and FWHM of E2 (high) in MgxAl1xN (x = 0–0.044) films on Si (1 0 0) substrate.
4. Conclusion

In conclusion, the Mg-doped AlN films with various Mg concen-

XPS. Hence, more defects exist in doped films than the undoped
AlN, implying the formation of defects may be related to the sub-
stitution of Al and vacancy of N. A similar red-shift of E2 (high)
mode was also observed in the Cu-doped AlN nanorods due to
the Cu substitution of Al in the AlN lattice [27]. Therefore, the
Mg substitution of Al is further demonstrated by the Raman
method and lots of defects existence in the doped samples is
further revealed by the Raman analysis.
Fig. 6 presents the room-temperature photoluminescence (PL)
spectra of undoped and doped samples with different Mg concen-
trations. No emission peak is observed in the spectrum range of
350–500 nm in undoped AlN film. As for the Mg-doped samples,
the PL spectra show a non-band-edge luminescence. A broad blue
band showed two distinct peaks, one centered at 420 nm (denoted
as P1 band) and the other centered at 440 nm (denoted as P2 band)
in Fig. 6. The P1 band shifts to lower energies and gains increasing
relative intensity as the Mg content increases from 0.8 at.% to
4.4 at.%. Moreover, the P2 band exhibits the similar redshift emis-
sion, too. Kim and Harrison reported the shallow donor-related PL
bands above 3.01 eV and the valence band disappeared with
increasing Mg doping level, which indicating the donor levels are
at a deep state from the conduction band [28]. Kim and Song also
observed the two distinct PL band at 2.75 eV and 2.95 eV in
Mg-doped a-plane GaN film, which is attributing to two different
trations were deposited by magnetron sputtering on Si (1 0 0)
substrate. XRD patterns, XPS, Raman and PL spectra were per-
formed to study the photon mode and PL properties in the AlN
films. The Raman spectra of Al1xMgxN films reveals the enhance-
ment of A1 (TO) mod and a slightly blue-shift and an augment in
FWHM for E2 (high) phonon mode with increasing Mg content,
which can be associated with the deterioration of (0 0 2) orienta-
tion and the appearance of (1 0 0) orientation. A broad blue band
showed two distinct peaks, one centered at 420 nm and the other
centered at 440 nm was observed in Mg-doped AlN films. The cen-
ter of the emission band can be attributed to the transitions from
the shallow donor level not only to the ground state but also to
the excited states of the deep level.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (No. 61106070).
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