Excitation Frequency Dependence and Fluorescence in the
Raman Spectra of Al2O3
A. AMINZADEH*
Centre for Instrumental and Development Chemistry, QUT, Brisbane, Australia
Raman spectra of aluminu m oxide, Al2O3, have been a subject of
interest over the last two decades. The origin of the ¯ uorescence
background in the Raman spectra of Al2O3 is still a subject of dis-
cussion. It has been believed to be due to hydrocarbon, iron ion
impurities, or hydroxy groups on the surface of Al2O3. In this paper,
Raman spectra of Al2O3 are reported that were acquired with dif-
feren t excitation frequencies as well as differen t spectrom eters and
differ ent temper atures. It is shown that, whereas at an excitation
frequency of 1064 nm a strong ¯ uorescence background is observed,
a sample of Al2O3 heated at 12508 C when excited with a 632.8-nm
frequency exhibits strong and remarkable ¯ uorescence ® ne struc-
ture. It is concluded that the origin of the ¯ uorescen ce background
in the Raman spectra of Al2O3 is iron, and Fe impur ity, and the
intensity of this ¯ uorescen ce depends upon the structure of Al2O3
and the excitation frequen cy used.
Index Headings: Aluminum oxide; Raman spectroscopy; Fluores-
cence.
INTRODUCTION
Aluminum oxide, Al2 O3, sometimes referred to as alu-
mina, is a very important mineral with wide applications
as a catalyst support,1 as a ceramic material,2 and as a
dielectric in electrolytic capacitors.3
Al2O3 has several different phases. The modi® cations
of Al2 O3 and the nature of the phases depend upon the
method and the temperature of production. With boehm-
ite as a starting material at 500 to 850 8 C, g -alumina is
formed; from 850 to about 1100 8 C, u -alumina is ob-
tained; and above 1100 8 C, the a -phase is obtained. Al-
though with different starting materials the nature of
phases at different temperatures is different, above 1100
8 CÐ with any starting materialÐ only the a -phase is ob-
tained. The naturally occurring forms of Al2 O3 Ð namely,
corundum, emery, sapphire, and rubyÐ are more or less
pure forms of a -Al2 O3.
The ® rst Raman spectrum of corundum was reported
by Krishnan,4 who identi® ed seven allowed vibrations. In
1967 Porto and Krishnan5 described the Raman spectrum
of a single crystal of corundum. In their Raman spectrum,
Porto and Krishnan reported seven Raman bands at 378,
418, 432, 451, 578, 645, and 751 cm2 1 . Since then, sev-
eral additional reports have appeared in the literature on
the Raman spectrum of Al2O3 , all of which show a ¯ u-
orescence background and deal with the origin of this
background.6± 12
The origin of the ¯ uorescence background in all these
reports has been a subject of debate.6± 12 We therefore un-
dertook a careful investigation of the Raman spectra of
Received 29 May 1996; accepted 5 December 1996.
* Permanent address: College of Chemistry, Isfahan University of Tech-
nology, Isfahan, IR, Iran.
0003-7028 / 97 / 5106-0817$2.00 / 0
Volume 51, Number 6, 1997 q 1997 Society for Applied Spectroscopy
Al2 O3 in order to characterize its ¯ uorescence back-
ground.
EXPERIMENTAL
Materials. g -Aluminum oxide was purchased from
commercial sources (Merck) and was used without fur-
ther puri® cation. An atomic absorption measurement
showed its iron content to be about 300 ppm. Heat-treated
Al2 O3 was obtained by heating g -aluminum oxide for 2
h at 1250 8 C in an electric furnace.
Instrumentation. Raman spectra were recorded with
the use of three different excitation frequencies and three
kinds of instruments, as follows:
1. A Renishaw Raman microprobe Model 1000 equipped
with a charge-compled device (CCD) detector. Exci-
tation at 632.8 nm was obtained from a HeNe laser,
Spectra Physics Model 127.
2. A Perkin± Elmer FT-Raman System 2000 equipped
with a GaInAs detector. Excitation at 1064 nm was
obtained from a Nd:YAG laser, I.E. Optomech Model
385.
3. A Cary Model 82 equipped with a P.M. R943-02 pho-
tomultipler. Excitation at 514.5 nm was obtained from
a Coherent Radiation Ar1 laser.
RESULTS AND DISCUSSION
Figure 1 shows Raman spectra of g -aluminum oxide
(g -Al2O3) with excitation wavelengths of (a) 1064, (b)
514.5, and (c) 632.8 nm, respectively. Figure 2 shows
Raman spectra of a -aluminum oxide (heated at 1250 8 C),
at excitation frequencies of (a) 1064, (b) 514.5, and (c)
632.8 nm, respectively. These spectra have been recorded
under the following conditions: For 632.8-nm excitation:
8 mW power of a HeNe laser, 10 scans, and the resolution
of the spectrometer estimated to be 4 cm2 1 . For 1064-nm
excitation: 50 mW power of a Nd:YAG laser, 5 scans,
and resolution of either 4 or 8 cm2 1 . For 514.5-nm ex-
citation: 400 mW of an Ar1 laser, 5 scans, and resolution
of about 4 cm2 1.
It can be seen from Fig. 1 that, apart from a broad,
weak band at about 1300 cm2 1 in Raman spectrum c,
which was recorded with 632.8-nm excitation, all spectra
show a typical ¯ uorescence background. However, it can
be seen from Fig. 2 that, although at 1064-nm excitation
a strong and at 514.5-nm a rather weak ¯ uorescence
background (spectra a and b) are observed, in Raman
spectrum c, which was recorded with excitation at 632.8
nm, a well-resolved spectrum with ® ne structure is ob-
tained. In this spectrum the bands are located at 622, 856,
1000, 1153, 1356, 1400, 1660, 1792, and 2034 cm2 1.
None of these bands appear at the anti-Stokes side of the
APPLIED SPECTROSCOPY 817
FIG. 1. Raman spectra of g -Al 2O3 with the use of excitation frequen-
cies at (a) 1064, (b) 514.5, and (c) 632.8 nm, in the wavenumber shift
range of 200± 2000 cm2 1 .
Raman spectrum. We therefore designate these bands as
¯ uorescence bands. The only Raman bands which can be
observed in this spectrum might be at 410 and 622 cm2 1 ,
and they are very weak.13
As early as 1945 and 1948, DeMent14 and Kroger,15
respectively, pointed out that pure Al2O3 is neither ¯ uo-
rescent nor phosphorescent. However, a very small por-
tion of chromic oxide (about 10 ppm) will produce ruby
with an intense ¯ uorescence. Egerton et al.6 reported that
the main source of ¯ uorescence background in Al2 O3 is
due to hydrocarbon impurities, with some due to Fe31 . In
a similar interpretation, Jeziorowski and Knozinger ex-
plained the ¯ uorescence background in terms of hydro-
carbon impurities. Fe31 , and excitations from structural
defects.7 Two recent reports of Mortensen et al.9,10 explain
the ¯ uorescence background in the Raman spectra of
Al2O3 in terms of Fe impurity and surface hydroxyl
groups. Another very recent report of Chen et al.12 has
appeared, with the conclusion that the background is due
only to surface hydroxyl groups.
On the basis of our results presented in Figs. 1 and 2,
we propose that the origin of ¯ uorescence in the Raman
spectra of Al2 O3 is due solely to iron impurity and that
its intensity depends upon the structural environment of
the host. In our Raman spectra, three excitation frequen-
ciesÐ namely, 1064, 632.8, and 514.5 nmÐ were used. If
one regards the surface hydroxyl groups as the main or-
igin of ¯ uorescence background in the Raman spectra of
Al2O3, then all three spectra should show a rather similar
background. Moreover, one should also observe Raman
bands due to hydroxyl groups as well. No such bands are
observed in this respect. If one regards hydrocarbon im-
purity as the source of ¯ uorescence background, the Ra-
man spectrum taken with 632.8-nm excitation could be
interpreted only as a rigorous resonace Raman spectrum
originating from an absorption band close to 632.8 nm.
This possibility is rejected since there has been no such
reference either to the nature of this absorption band or
to the concentration of hydrocarbon. Moreover, at tem-
peratures as high as 1250 8 C, no hydrocarbon can exist.
818 Volume 51, Number 6, 1997
FIG. 2. Raman spectra of a -Al2O3 with the use of excitation frequen-
cies at (a) 1064, (b) 514.5, and (c) 632.8 nm, in the wavenumber shift
range of 200± 2000 cm2 1 .
At this temperature, most normal and light hydrocarbons
are burned, and other heavy hydrocarbons are either de-
composed or vaporized.16
There remains our proposal that Fe31 is the source of
¯ uorescence. This conclusion is supported with the fact
that Fe31 has a strong emission band centered at 700 nm
(about 14,300 cm2 1)17 when located in a spinel environ-
ment. As has been pointed out, it is well known that, at
high temperatures, Al2O3 is converted to a -Al2 O3 , which
has a spinel structure. The excitation frequency at 632.8
nm is close to the maxima of the ¯ uorescence band
(14,300 cm2 1), and the position of the two strongest
bands (spectrum c, Fig. 2) at Raman shifts of 1350 and
1400 cm2 1 will, on the absolute wavenumber scale, be
close to the maxima of the emission of the Fe31 ¯ uores-
cence band. In agreement with our ® ndings, Mortenson
et al., using two samples of Al2O3 with 193 ppm and less
than 20 ppm of Fe, report a higher background ¯ uores-
cence with 193-ppm Fe impurity.9
CONCLUSION
We conclude that, in agreement with Mortenson et al.,9
the origin of ¯ uorescence in the Raman spectra of Al2 O3
is due to Fe impurity. We assign the strong bands at spec-
trum c in Fig. 2 to the laser-induced ¯ uorescence bands
of Fe31 , which has replaced the Al31 ion in a spinel struc-
ture.
Finally, we should point out that a recent work on the
Raman spectra of Al2O3 reported by Prassad et al.,18 in
which more than 16 Raman bands have been assigned to
Al2O3 and two Raman bands to NiO as well, might be
wrong and should be revised.
ACKNOWLEDGMENTS
I would like to thank CIDC, Queensland University of Technology,
for the use of Raman equipment. I am grateful to Professor P. Fredericks
for helpful advice and to Dr. L. Rintoul for his excellent technical as-
sistance. I am also grateful to Dr. M. Riley from the University of
Queensland for the use of the Cary Model 82 Raman instrument. Fi-
nally, I would like to thank the Isfahan University of Technology (IR,
Iran) for ® nancial support.
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