Degradation of AlGaN during high-temperature annealing monitored

by ultraviolet Raman scattering

M. Kuball, F. Demangeot, J. Frandon, M. A. Renucci, H. Sands et al.

Citation: Appl. Phys. Lett. 74, 549 (1999); doi: 10.1063/1.123141

View online: http://dx.doi.org/10.1063/1.123141
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Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS VOLUME 74, NUMBER 4 25 JANUARY 1999

Degradation of AlGaN during high-temperature annealing monitored

by ultraviolet Raman scattering
M. Kuballa)
H. H. Wills Physics Laboratory, University of Bristol, Bristol BS8 1TL, United Kingdom
F. Demangeot, J. Frandon, and M. A. Renucci
Laboratoire de Physique des Solides de Toulouse, CNRS, Université Paul Sabatier, 31062 Toulouse Cedex,
France
H. Sands and D. N. Batchelder
Department of Physics, University of Leeds, Leeds LS2 9JT, United Kingdom
S. Clur and O. Briot
GES–CNRS, CC074 Université Montpellier II, 34095 Montpellier Cedex 5, France
~Received 1 October 1998; accepted for publication 23 November 1998!
We have illustrated the use of ultraviolet ~UV! Raman scattering to investigate the thermal stability
of AlGaN layers with high-aluminum content. The degradation pathway of Al0.72Ga0.28N was
monitored for high-temperature treatments up to 1200 °C. For annealing temperatures higher than
1150 °C, the Al0.72Ga0.28N film decomposes: a low- and a high-aluminum composition Alx Ga12x N
phase emerge. At 1100 °C, prior to the Al0.72Ga0.28N decomposition, UV Raman scattering detects
the buildup of a large strain in the Al0.72Ga0.28N film. The crystalline quality of Al0.72Ga0.28N is
unaffected up to 1000 °C. © 1999 American Institute of Physics. @S0003-6951~99!00704-4#

III–V nitrides ~GaN, AlGaN, InGaN! have recently at-
tracted great interest for application such as blue light
emitters1 and high-temperature electronic devices.2 High-
temperature treatments are often part of the device process-
ing, e.g., for the activation of Mg acceptors for the p doping
of GaN. The thermal stability of GaN is, therefore, of great
interest.3–5 We have recently illustrated the great potential of
Raman scattering to monitor the thermal degradation of GaN
noninvasively during high-temperature annealing.3 Recent
studies on the ion implantation of GaN for selective doping
have shown that AlN cap layers are necessary to protect
implanted GaN during high-temperature annealing exceeding
1000 °C for the activation of the implanted dopants.6,7 The
thermal stability of the AlN cap layer is crucial; however,
very little is known about the degradation of AlN or, in gen-
eral, AlGaN at high temperatures. In this letter, we employ
ultraviolet ~UV! Raman scattering to determine the degrada-
tion pathway of AlGaN layers with high-aluminum compo-
sition during high-temperature anneals. The degradation of
Al0.72Ga0.28N at temperatures higher than 1150 °C results in
the emergence of Alx Ga12x N phases with a low- and a high-
aluminum composition.
Al0.72Ga0.28N layers, about 2 mm thick, were grown by
organometallic vapor phase epitaxy on ~0001! sapphire sub-
strates at 980 °C, after depositing a 50-nm-thin AlN buffer
layer. Raman spectra were collected from the top surface of
the samples in backscattering Z(X,•)Z̄ geometry, i.e., unpo-
larized detection, using a Renishaw UV Raman microscope
system with the 244 nm line of an intracavity frequency-
doubled Ar1 laser as the excitation source. A 203 objective
with low chromatic distortion was employed to focus and
collect the laser light with a spatial resolution of about 1 mm.
a!
Electronic mail: martin.kuball@bristol.ac.uk
The samples were annealed in nitrogen ambient at tempera-
tures up to 1200 °C in steps of 50–100 °C. A small amount
of oxygen was present during the annealing. To monitor the
thermal degradation of the AlGaN layers during the anneal-
ing sequence, Raman spectra were recorded after each an-
nealing step.
Figure 1 shows Raman spectra of an Al0.72Ga0.28N film
after various 15 min anneals at temperatures up to 1200 °C,
recorded at room temperature in Z(X,•)Z̄ backscattering ge-
ometry. Both the A 1 (LO) and E 2 phonons of wurtzite
AlGaN are allowed in this configuration. The Raman spec-
trum of the sample shows before annealing ~lowest spec-
trum! the A 1 (LO) phonon at 850 cm21, which is resonantly
enhanced due to the UV excitation of 244 nm, as well as
second- and third-order Raman scattering at 1700 and 2550
cm21, respectively. The E 2 phonon of Al0.72Ga0.28N is much
weaker than the A 1 (LO) phonons under those resonant con-
ditions and not visible on the intensity scale of Fig. 1.
The Raman spectrum of the Al0.72Ga0.28N film is unaf-
fected up to annealing temperatures of 1000 °C and is iden-
tical to the data of Ref. 8. Annealing at 1100 °C, however,
results in a broadening of the second-order Raman scattering
signal at 1700 cm21 and increased third-order Raman scat-
tering at 2550 cm21. The A 1 (LO) phonon is shifted after the
1100 °C anneal by about 6 cm21 to higher wave numbers
with respect to the unannealed sample ~inset of Fig. 1!. The
A 1 (LO) phonon intensity and linewidth remains, to a first
approximation, unaffected by the high-temperature treat-
ments. Dramatic changes in the Raman scattering signal oc-
cur after annealing at 1150 °C with new phonon lines emerg-
ing at 750 and 824 cm21, with a shoulder at (885
65) cm21. Additional weak Raman peaks are detectable at
576 and 645 cm21 and are marked by vertical arrows in Fig.
1 ~top spectra!. No signature of the A 1 (LO) phonon of

0003-6951/99/74(4)/549/3/$15.00 549 © 1999 American Institute of Physics

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550 Appl. Phys. Lett., Vol. 74, No. 4, 25 January 1999
FIG. 1. Raman spectra of an Al0.72Ga0.28N layer after 15 min anneals at
various temperatures, recorded at room temperature in backscattering
Z(X,•)Z̄ geometry using an excitation wavelength of 244 nm.
Al0.72Ga0.28N at 850 cm21 is present anymore. Further an-
nealing at 1200 °C results in an increasing intensity of the
824 and 885 cm21 phonon lines, as well as the appearance of
a second-order Raman scattering signal at 1770 cm21.
The changes in the Raman spectrum of Al0.72Ga0.28N
shown in Fig. 1 allow us to determine the degradation path-
way of the Al0.72Ga0.28N film during the annealing sequence.
The Raman spectrum of the unannealed Al0.72Ga0.28N layer
~lowest spectrum in Fig. 1! is dominated by the A 1 (LO)
phonon at 850 cm21. The UV excitation of 244 nm ~5.08 eV!
close to the band gap of Al0.72Ga0.28N @about 5 eV ~Ref. 9!#
results in a resonant enhancement of the A 1 (LO) phonons.
Resonant enhancement effects of LO phonons are well
known for many III–V and II–VI semiconductors10 and have
recently been studied in the case of GaN by Behr et al.11 The
resonant enhancement is also visible in the large second- and
third-order Raman scattering signal at 1700 and 2550 cm21,
respectively. The second-order Raman scattering signal at
1700 cm21, which under off-resonant excitations, i.e., laser
excitation energies far away from, e.g., the band gap, repre-
sents a good approximation for the phonon density of states
is modified under the resonant UV excitation. The two-
phonon spectrum deviates from the density of states in the
sense that a peak appears for phonons with q'0 as seen by
the strong 2A 1 (LO) peak at 1700 cm21.10 The underlying
broad Raman feature, however, still gives an indication for
the phonon density of states of Al0.72Ga0.28N.
The Al0.72Ga0.28N film is stable up to temperature of
1000 °C. The unchanged Raman spectrum in Fig. 1 shows
that the crystalline quality of the Al0.72Ga0.28N film remains
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Kuball et al.
unaffected by the annealing. This result clearly illustrates the
enhanced thermal stability of Al0.72Ga0.28N when compared
to GaN. Previous studies on GaN using Raman scattering
showed changes in the Raman spectrum at temperatures as
low as 800–900 °C.3
The main result of significance in Fig. 1 is the dramatic
change in the Al0.72Ga0.28N Raman spectrum after the
1150 °C anneal, illustrating the severe degradation of the
sample at those temperatures. The Al0.72Ga0.28N A 1 (LO)
phonon at 850 cm21 disappears. The newly emerging pho-
non modes at 824 and (88565) cm21 can be attributed to the
A 1 (LO) phonons of Al0.46Ga0.54N and Al.0.90Ga,0.10N,
when comparing to Raman data reported on Alx Ga12x N
films as a function of aluminum composition:12,13 low- and
high-aluminum content Alx Ga12x N phases emerge. The ap-
parent second-order Raman scattering signal at 1770 cm21
after the 1200 °C anneal contains the second-order Raman
scattering signal from both Al0.46Ga0.54N and
Al.0.90Ga,0.10N. Contributions from the only 50-nm-thin
AlN buffer layer to the Raman spectrum appear to be negli-
gible due to the nonresonant excitation conditions for AlN.8
The laser light penetrates the emerging (Al0.46Ga0.54N,
Al.0.90Ga,0.10N) layer. Sapphire modes are, therefore, vis-
ible at 576, 645, and 750 cm21 after the 1150 °C anneal. A
reduced average (Al0.46Ga0.54N, Al.0.90Ga,0.10N) layer
thickness appears to be responsible. Note that sapphire
modes were not detectable before annealing due to the ab-
sorption of the laser light in the 2-mm-thick Al0.72Ga0.28N
film. Additional contributions to the observed Raman signal
at 576 and 645 cm21 could arise from the E 2 phonons of
Al0.46Ga0.54N and Al.0.90Ga,0.10N, respectively.12,13 The in-
creasing Al0.46Ga0.54N and Al.0.90Ga,0.10N Raman modes
~824 and 885 cm21! during the subsequent heat treatment at
1200 °C ~without any Al0.72Ga0.28N present after the 1150 °C
anneal! seem to suggest a rather complex transition from
Al0.72Ga0.28N to Al0.46Ga0.54N and Al.0.90Ga,0.10N, involv-
ing decomposition products from the Al0.72Ga0.28N layer and
eventually the AlN buffer layer. Further investigations are
necessary to understand in microscopic terms the transition
from Al0.72Ga0.28N into Al0.46Ga0.54N and Al.0.90Ga,0.10N
during the annealing sequence.
Note that a large amount of strain builds up in the
Al0.72Ga0.28N film prior to its decay at 1150 °C. This strain is
reflected in the shift of the A 1 (LO) phonon mode by about 6
cm21 after the 1100 °C anneal ~inset of Fig. 1!. Studies on
biaxially strained GaN layers14 have shown that A 1 (LO)
phonons of GaN shift with 0.8 cm21/GPa, i.e., 7–8 GPa for
6 cm21. No experimental results on the frequency shift of
A 1 (LO) phonons of AlGaN with strain, however, have so far
been reported in the literature to allow us to determine quan-
titatively the present strain. Further contributions to the
A 1 (LO) frequency shift could arise from changes in the free
carrier concentration; however, they appear to be minor.3
Signs for the introduction of microscopic defects can be
found in the broadened second-order Raman scattering spec-
trum around 1700 cm21, i.e., in the changed phonon density
of states.
It is important to realize that although the Al0.72Ga0.28N
film is severely damaged at temperatures of 1150–1200 °C,
the newly emerging AlGaN layer containing Al0.46Ga0.54N
Appl. Phys. Lett., Vol. 74, No. 4, 25 January 1999
FIG. 2. Photoluminescence spectra of an Al0.72Ga0.28N layer after 15 min
anneals close to the degradation temperatures, recorded at room tempera-
ture.
and Al.0.90Ga,0.10N would still form a protective layer dur-
ing high-temperature annealing for any potential layer under-
neath, e.g., an ion-implanted GaN film. The III–V nitride
film protects the sapphire surface in the investigated sample.
Note that surface damage would result in the activation of
forbidden sapphire modes ~e.g., at 770 cm21!, which are, for
example, clearly observable after high-temperature treat-
ments in the case of GaN grown on sapphire.3 It is clearly a
matter of choosing the proper layer thickness for the AlGaN
cap to form a protective layer dependent on annealing tem-
perature and annealing time. Note that high-temperature
treatments during processing, e.g., for the healing of ion-
implanted GaN as reported by Cao et al.,7 use annealing
times as short as 10 s, i.e., rapid thermal annealing ~RTA!.
Annealing during processing is, therefore, much gentler than
the 15 min treatments in this Raman study.
The severe degradation of the Al0.72Ga0.28N film at
1150 °C evidenced in Fig. 1 results also in significant
changes in the photoluminescence spectrum of the sample.
Figure 2 shows photoluminescence spectra, which were re-
corded after annealing at temperatures close to the degrada-
tion temperature. The decomposition of Al0.72Ga0.28N gives
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Kuball et al. 551
rise to a dominant photoluminescence peak at 3.8 eV. In
contrast, only a weaker photoluminescence signal was ob-
served for the as-grown Al0.72Ga0.28N film with a maximum
at 4.3 eV ~not shown in detail!.8 The origin of the photolu-
minescence features is part of ongoing investigations.
In conclusion, we have illustrated the use of ultraviolet
Raman scattering to monitor noninvasively the degradation
of Al0.72Ga0.28N layers during high-temperature annealing up
to 1200 °C. We have determined the degradation pathway of
Al0.72Ga0.28N layers starting at 1100 °C, which includes the
buildup of strain, the introduction of microscopic defects,
and the transformation of Al0.72Ga0.28N into Al0.46Ga0.54N
and Al.0.90Ga,0.10N. The sample quality was unaffected up
to temperatures of 1000–1100 °C. The investigated nitride
film was found to form a protective coating on the sapphire
substrate for temperatures in excess of 1200 °C. The results
illustrate the enhanced thermal stability of AlGaN compared
to GaN.
The authors thank Dr. G. D. Pitt ~Renishaw Transducers
plc! for financial support and for supplying the high-
temperature stage for the experiment.
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