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Raman spectra of aluminu m oxide, Al2O3, have been a subject of Al2 O3 in order to characterize its ¯ uorescence back-
interest over the last two decades. The origin of the ¯ uorescence ground.
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 EXPERIMENTAL
impurities, or hydroxy groups on the surface of Al2O3. In this paper,
Raman spectra of Al2O3 are reported that were acquired with dif- Materials. g -Aluminum oxide was purchased from
feren t excitation frequencies as well as differen t spectrom eters and commercial sources (Merck) and was used without fur-
differ ent temper atures. It is shown that, whereas at an excitation ther puri® cation. An atomic absorption measurement
frequency of 1064 nm a strong ¯ uorescence background is observed, showed its iron content to be about 300 ppm. Heat-treated
a sample of Al2O3 heated at 12508 C when excited with a 632.8-nm
frequency exhibits strong and remarkable ¯ uorescence ® ne struc-
Al2 O3 was obtained by heating g -aluminum oxide for 2
ture. It is concluded that the origin of the ¯ uorescen ce background h at 1250 8 C in an electric furnace.
in the Raman spectra of Al2O3 is iron, and Fe impur ity, and the Instrumentation. Raman spectra were recorded with
intensity of this ¯ uorescen ce depends upon the structure of Al2O3 the use of three different excitation frequencies and three
and the excitation frequen cy used. kinds of instruments, as follows:
Index Headings: Aluminum oxide; Raman spectroscopy; Fluores- 1. A Renishaw Raman microprobe Model 1000 equipped
cence.
with a charge-compled device (CCD) detector. Exci-
tation at 632.8 nm was obtained from a HeNe laser,
Spectra Physics Model 127.
INTRODUCTION 2. A Perkin± Elmer FT-Raman System 2000 equipped
with a GaInAs detector. Excitation at 1064 nm was
Aluminum oxide, Al2 O3, sometimes referred to as alu- obtained from a Nd:YAG laser, I.E. Optomech Model
mina, is a very important mineral with wide applications 385.
as a catalyst support,1 as a ceramic material,2 and as a 3. A Cary Model 82 equipped with a P.M. R943-02 pho-
dielectric in electrolytic capacitors.3 tomultipler. Excitation at 514.5 nm was obtained from
Al2O3 has several different phases. The modi® cations a Coherent Radiation Ar1 laser.
of Al2 O3 and the nature of the phases depend upon the
method and the temperature of production. With boehm- RESULTS AND DISCUSSION
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- Figure 1 shows Raman spectra of g -aluminum oxide
tained; and above 1100 8 C, the a -phase is obtained. Al- (g -Al2O3) with excitation wavelengths of (a) 1064, (b)
though with different starting materials the nature of 514.5, and (c) 632.8 nm, respectively. Figure 2 shows
phases at different temperatures is different, above 1100 Raman spectra of a -aluminum oxide (heated at 1250 8 C),
8 CÐ with any starting materialÐ only the a -phase is ob- at excitation frequencies of (a) 1064, (b) 514.5, and (c)
tained. The naturally occurring forms of Al2 O3 Ð namely, 632.8 nm, respectively. These spectra have been recorded
corundum, emery, sapphire, and rubyÐ are more or less under the following conditions: For 632.8-nm excitation:
pure forms of a -Al2 O3. 8 mW power of a HeNe laser, 10 scans, and the resolution
The ® rst Raman spectrum of corundum was reported of the spectrometer estimated to be 4 cm2 1 . For 1064-nm
by Krishnan,4 who identi® ed seven allowed vibrations. In excitation: 50 mW power of a Nd:YAG laser, 5 scans,
1967 Porto and Krishnan5 described the Raman spectrum and resolution of either 4 or 8 cm2 1 . For 514.5-nm ex-
of a single crystal of corundum. In their Raman spectrum, citation: 400 mW of an Ar1 laser, 5 scans, and resolution
Porto and Krishnan reported seven Raman bands at 378, of about 4 cm2 1.
418, 432, 451, 578, 645, and 751 cm2 1 . Since then, sev- It can be seen from Fig. 1 that, apart from a broad,
eral additional reports have appeared in the literature on weak band at about 1300 cm2 1 in Raman spectrum c,
the Raman spectrum of Al2O3 , all of which show a ¯ u- which was recorded with 632.8-nm excitation, all spectra
orescence background and deal with the origin of this show a typical ¯ uorescence background. However, it can
background.6± 12 be seen from Fig. 2 that, although at 1064-nm excitation
The origin of the ¯ uorescence background in all these a strong and at 514.5-nm a rather weak ¯ uorescence
reports has been a subject of debate.6± 12 We therefore un- background (spectra a and b) are observed, in Raman
dertook a careful investigation of the Raman spectra of spectrum c, which was recorded with excitation at 632.8
nm, a well-resolved spectrum with ® ne structure is ob-
Received 29 May 1996; accepted 5 December 1996. tained. In this spectrum the bands are located at 622, 856,
* Permanent address: College of Chemistry, Isfahan University of Tech- 1000, 1153, 1356, 1400, 1660, 1792, and 2034 cm2 1.
nology, Isfahan, IR, Iran. None of these bands appear at the anti-Stokes side of the
0003-7028 / 97 / 5106-0817$2.00 / 0
Volume 51, Number 6, 1997 q 1997 Society for Applied Spectroscopy 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 .