Surface Review and Letters, Vol. 15, No.

5 (2008) 681688
c World Scientic Publishing Company
LOWER TEMPERATURE FORMATION OF ALUMINA
THIN FILMS THROUGH SOLGEL ROUTE
S. RIAZ
,
, S. SHAMAILA

, B. KHAN

and S. NASEEM
,

Centre for Solid State Physics,

Punjab University, Lahore 54590, Pakistan

State Key Laboratory of Magnetism,

Chinese Academy of Sciences, Beijing 100080, China

Department of Chemistry, LCW University,

Lahore, Pakistan

shahzad naseem@yahoo.com
Received 29 February 2008
Bayerite sol is spun onto single crystal Si substrate, after synthesis and optimization, to obtain
lms of thickness 0.2 m. The deposited lms are room temperature dried and then heated
up to a temperature of 350

C in order to obtain Al
2
O
3
. Surface and structural changes, during
heating, are observed with optical microscopy. Scanning electron microscopy (SEM) and X-ray
diraction (XRD) are used for post-treatment analyses/characterization. The as-deposited and
heated samples surfaces are smooth as seen with optical and scanning electron microscope
in case of optimized conditions. XRD patterns show the change from amorphous to crystalline
behavior of these lms when heated under various conditions. The most stable form of aluminum
oxide, i.e. -Al
2
O
3
, is obtained when samples are heated up to a temperature of as low as
350

C. The thin lms are also deposited onto sodalime glass substrates in order to conrm
Al
2
O
3
formation through band gap probing. Photoconduction is used to nd the energy band
gap, which comes out to be 4.7 eV; lower value is correlated to the defect induced states in the
band gap.
Keywords: Alumina; solgel; corrundum; low-temperature.
1. Introduction
Aluminum oxide or alumina is one of the groups of
inorganic chemicals currently produced in very large
volumes.
1
Alumina (Al
2
O
3
) exhibits several attrac-
tive properties such as good corrosion resistance,
high dielectric strength, resistance to the diusion
of impurity, and high chemical and thermal stabil-
ity. These characteristics motivate its use for var-
ious applications, such as electrical,
2
optical,
3
wear
resistant coating for cutting tools,
4
and diusion bar-
rier coating for nonvolatile memories
5
where dense
and closed structures are required, and also as cata-
lyst support where, in contrast, highly porous lms
are required.
6
Several routes such as chemical vapor deposition,
7
electrochemical anodic oxidation,
8
electroless plat-
ing,
9
and spray pyrolysis of metal-organics
10
have
been developed for preparation of nano-materials.
Among these, the solgel method is an emerg-
ing route with high promise for very homogeneous
lms, which can be carried out at relatively low
temperatures.
11,12

Corresponding author.
681
682 S. Riaz et al.
Al
2
O
3
exists in more than 15 distinct crystallo-
graphic phases, and it can undergo a variety of tran-
sitions until the most-stable corundum structure, i.e.
-Al
2
O
3
, forms at high temperature, i.e. 1200

C.
13
However, this temperature is reduced by the intro-
duction of additives such as CuO and Fe
2
O
3
1416
or
-Al
2
O
3
1720
before gelation. Hence, the transforma-
tion is observed at 1050

C.
11
Another alternative is
the modication of the sol formulation,
2125
which
allows conversion to -Al
2
O
3
without additives or
seeding. In this process, the presence of water in the
prepared sol retards the conversion to -Al
2
O
3
,
23
favoring transition via -Al
2
O
3
, which is remarkably
stable.
19
Tsay et al.
24
demonstrated that sols pre-
pared with a reduced amount of water experienced a
direct transformation to -Al
2
O
3
, whereas the water-
containing sol passed through several transition
structures, such as -Al
2
O
3
and -Al
2
O
3
. Indeed, the
measured activation energy of -Al
2
O
3
-Al
2
O
3
transition is 650 kJ/mol, which is in contrast to that
of the induced -Al
2
O
3
-Al
2
O
3
transformation
(360431kJ/mol).
19
Therefore, the key to perform-
ing the -Al
2
O
3
transformation at lower tempera-
tures is to avoid the transition via -Al
2
O
3
.
As solgel precursors, aluminum alkoxides dif-
fer signicantly from other metal-alkoxides in terms
of their chemical reactivity and complex-forming
ability. These dierences dictate the adoption of dif-
ferent strategies for the creation of alumina based
solgel products. The solgel reactions in usual
metal-alkoxides/silica-based system are rather slow
and often require the use of catalysts to acceler-
ate the process. This is explained by the fact that
aluminum alkoxides (e.g., aluminum sec-butoxide)
are very reactive toward nucleophilic reagents like
water.
26
They readily undergo hydrolysis, which
results in a very fast solgel process, as shown in
Fig. 1. Even if the solution of aluminum sec-butoxide
is stirred vigorously, the rates of these reactions
are so high that large agglomerated alumina parti-
cles precipitate out instantaneously when the sol
gel ingredients are mixed together. Such fast pre-
cipitation makes it dicult to reproducibly prepare
alumina-based sol materials.
The hydrolysis activity of aluminum sec-butoxide
can be controlled by chelating it with various -
ketoesters (or R-acetoacetates) through a steric
eect, e.g., ethyl acetoacetate,
28
acetylacetone,
29
which are capable of undergoing ketoenol
Al
OCH(CH
3
)
2
(H
3
C)
2
HCO OCH(CH
3
)
2
+
3H
2
O Al
OH
HO OH
+ 3(CH
3
)
2
CHOH
Aluminum Isopropoxide Aluminum Hydroxide
(a)
Al
OH
HO
OH
+
Al
OH
HO
n
OH
Al
O
HO OH
( O Al
)
n
O Al
O
O
(b)
Al
OCH(CH
3
)CH
2
CH
3
H
3
CH
2
C(H
3
C)HCO OCH(CH
3
)CH
2
CH
3
+ 3H
2
O
Al
OH
HO OH
+ 3CH
3
CH
2
(CH
3
)CHOH
Aluminum sec-butoxide Aluminum Hydroxide
(a)
Al
OH
HO OH
+
Al
OH
HO
n
OH
Al
O
HO OH
( O Al )
n
O Al
O
O
(b)
Fig. 1. Chemical reactions of alumina sols show (a)
hydrolysis and (b) poly-condensation for both Al-
isopropoxide and Al-sec-butoxide (adapted from Ref. 27).
tautomerism. The formation of the stabilized
chelated complex reduces the hydrolysis and conden-
sation rates of aluminum sec-butoxide by decreasing
the number of available alkoxy groups.
Thus, as compared to other metals, alumina is
capable of both ion and ligand exchange.
27
The lig-
and exchange ability of alumina originates from the
presence of Lewis acid sites on the surface, i.e. coor-
dinatively unsaturated Al
3+
, and water molecules or
other easily displaced ligands coordinatively bonded
to the sites, as shown in Fig. 2.
27
Lewis basic ana-
lytes containing polar functional groups such as car-
boxylic, phenolic-OH or amino groups can substitute
for the surface hydroxyl group or coordinated water
molecules and form complexes with the metal ions
of the oxide surface.
30
Therefore, precursors of alu-
mina, such as aluminum sec-butoxide and aluminum
iso-propoxide, are very attractive and are chosen, for
Lower Temperature Formation of Alumina Thin Films Through SolGel Route 683
H
2
O
2(aq)
H
2
O
(l)
+ 1/2 O
2(g)
+ H
O
H
Al
X
O
H
2
O
2(aq)
H
2
O
(l)
O
H
Al
O
OH
Al
O
Strong Bronsted acid site Weak Bronsted Acid Site
Fig. 2. A representation of Lewis acid sites for alumina.
the current work, to prepare alumina lms by the
solgel method that may lead to novel applications.
In this paper, we report on the detailed charac-
terization of solgel based alumina thin lms from
locally synthesized precursors. According to the best
of our knowledge this is the rst alumina report
in which the most stable phase, i.e. corundum, is
achieved at a reaction temperature of 350

C.
2. Experimental Details
2.1. Synthesis of alumina sol
Aluminum foil was rst activated chemically so that
it may become reactive for the next steps. This
pre-activated aluminum foil went through dierent
chemical reactions at various stages to produce the
desired product. Finally, aluminum hydroxide solu-
tion was obtained from two dierent sources sepa-
rately, i.e. aluminum iso-propoxide and aluminum
sec-butoxide by following the hydrolysis and poly-
condensation. The chemical reactions/chains can be
followed through owcharts of Figs. 3(a)3(c).
2.2. Deposition of alumina
thin lms
Silicon (100), 55 mm, substrates were used for thin
lm deposition. An ultrasonic bath for 30 min with
acetone, and 20 min with isopropyl alcohol was given
to the substrates in order to make them free of any
Aluminum Foil
HgCl
2
distilled water
Heatedand aged at room temperature
Activated aluminum foil
washed with distilled water
(a)
Stirring
Refluxing
Activated Al foil Isopropyl Alcohol
Alumnum Iso-propoxide
Adding CCl
4
Vacuum distilation
Stirring
Refluxing
Activated Al foil Absolute sec-butanol
Aluminum sec-butoxide
Adding CCl
4
Vacuum distilation
(b)
AluminumIso-propoxide HNO
3
based solution
Stirring
Refluxed
Sol A(AlOOH)
HNO
3
basedsolution
Aluminumsec-butoxide
Stirring
Refluxed
Sol B(AlOOH)
(c)
Fig. 3. Flowcharts of solgel processes.
contamination and gas residues on the surface after
giving an HF etch. After cleaning, the substrate was
held by vacuum on a homemade spinner (Fig. 4).
Sol (A&B separately) is dropped on surface of the
substrate and spun for half a minute at a speed of
4000 rpm. Thickness of 0.2 m was achieved in this
way. These samples were then dried at room temper-
ature for 20 min. After drying, the samples were sub-
jected to heat treatment at dierent temperatures for
varying times. The whole process can be understood
in a better way diagrammatically as shown in Fig. 5.
2.3. Characterization of alumina
thin lms
Leica DM4000 optical microscope, equipped with a
heating stage, was used to observe the general surface
character and to check the ongoing surface changes
with variation in temperature. The current to the
heating stage was provided by the current controller
system that utilizes Testo 925 digital temperature
684 S. Riaz et al.
Fig. 4. Photographs of the homemade spinner; (a) com-
plete spinner set-up along with a rotary pump and
(b) magnied image of spinner stage.
As-deposited AlOOH
thin film
Characterizations
Wet gel
Heat treatment at different
temperatures
Dried
Aged at room temperature
Spin Coating of Sols (A & B)
Fig. 5. Block diagram of lm deposition.
display. Hitachi S-3400N scanning electron micro-
scope equipped with EDX was used to check the sur-
face and composition of these solgel prepared thin
lms. Alumina thin lms were characterized struc-
turally with the help of Rigaku D/MAX-IIA X-ray
diractometer. For measuring the photoconductivity,
thin lms were prepared on glass substrate. Ohmic
contacts were made on the thin lm of Al
2
O
3
by
evaporating semi-transparent and thick aluminum
lms and then pasting copper wires with conduct-
ing silver epoxy.
Samples were mounted on a test shield model
5104 by Keithley Instruments and Bausch & Lomb
monochromator was used for photoconduction mea-
surements. A 610-C Digital Electrometer was
attached with this assembly in order to measure the
current. The voltage was applied using power supply
model IZS 5165. The photocurrents were normalized
to unit radiant ux incident on the sample at any
wavelength.
3. Results and Discussion
Viscosity of both the sols was checked periodically
and it was found that both sols were very stable for
a long time period as shown by Fig. 6.
The freshly spun transparent sol of aluminum
hydroxide is left to cure at room temperature for
at least 20 min. This room temperature cured sam-
ple is then transferred to metallurgical optical micro-
scope equipped with a heating stage. The sample is
then heated, mostly up to 350

C, while the surface

being micrographed every 15 min. The heat treat-
ment, at the optimum temperature, lasts usually
60 min, which varies from sample to sample. A typ-
ical optical micrograph of the as-deposited sample
(sol A) is shown in Fig. 7. The surface is quite
smooth and featureless but as the reaction tempera-
ture is increased, chained structure appears as shown
in Fig. 8. Appearance of chained structure is indica-
tive of chemical reaction occurring at early stages
of the lm growth. Scanning electron micrograph
Fig. 6. Viscosity vs. time plotted for alumina sols.
Lower Temperature Formation of Alumina Thin Films Through SolGel Route 685
Fig. 7. Optical micrograph of as-deposited thin lm of
sol A (50).
Fig. 8. Optical image of the chained structure of
deposited lm during heat treatment (sol A).
(Fig. 9) shows featureless surfaces at higher magni-
cations for the lm prepared from sol A. However, in
case of sol B lm, there are some voids observed in
the electron micrograph (Fig. 10). These voids show
the poly-condensation of alumina molecules and thus
support the formation of chained network. These
voids have been found to be on the surface alone
rather than through the lm.
Fig. 9. SEM image of optimized Al
2
O
3
thin lm syn-
thesized from sol A.
Fig. 10. SEM image of optimized Al
2
O
3
thin lm syn-
thesized from sol B.
The aluminum based sols A and B, spin coated
onto silicon (100) substrates, were checked for their
crystal structure, phase transformation, and conr-
mation of the nally synthesized product at various
stages. Figure 11 shows XRD patterns of the as-
deposited (room temperature aged) and heated sam-
ples prepared from sol A. It is evident, from the pat-
tern [Fig. 11(a)], that initially the lm exhibits amor-
phous behavior. However, the few emerging peaks
belong to Al(OH)
3
, which are indicative of the for-
mation of Bayerite sol.
31
The aluminum hydroxide
phase is transformed to -alumina
32
after heating
at 350

C for 60 min as shown in Fig. 11(b). Tsay

et al.
24
have demonstrated that sols prepared with a
686 S. Riaz et al.
Fig. 11. XRD patterns of Sol A for (a) as-deposited
Al-hydroxide thin lm and (b) heated at 300

C for
60 min.
reduced amount of water experienced a direct trans-
formation to -Al
2
O
3
, whereas the water-containing
sol passed through several transition structures, such
as -Al
2
O
3
and -Al
2
O
3
. This means that sol A pre-
pared in our case was water-free since a direct tran-
sition to -Al
2
O
3
is observed. This alpha phase of
alumina is more favored in the dielectric applications.
Figure 12 shows the XRD patterns of the
deposited (room temperature aged) and heated sam-
ples of alumina lm prepared from sol B. This pat-
tern (Fig. 12(a)) also shows the amorphous behavior
of the deposited lm along with the presence of alu-
minum hydroxide peaks of varying intensities. It can
be seen from the comparison of Figs. 11(a) and 12(a)
that the peaks of Al(OH)
3
are smaller in case of sol
B. This may be due to the reason that the sol synthe-
sized from Al-sec butoxide based precursor does not
readily react with other constituents of the product
under these conditions. Figure 12(b) shows the XRD
pattern taken after heating of aluminum hydroxide
Fig. 12. XRD patterns of Sol B for (a) as-deposited
Al-hydroxide thin lm and (b) heated at 300

C for
60 min.
(sol B) at 350

C for 60 min. Various peaks of alu-

mina are observed in this gure due to hydrolysis
followed by condensation at this temperature. The
major peak though belongs to -Al
2
O
3
,
32
few peaks
of -Al
2
O
33
3
are also present. This means that sol B
contained some water content as discussed above.
The grain size of these alumina lms was
calculated from the WilliamsonHall plot of the
relation
34,35
:
2
f
cos
K
=
1
D
+
4e
K
sin ,
where 2
f
is in radians, K is the shape factor of the
crystalline particles, is the wavelength, e (= d/d)
is the microstrain, D is the particle size, and is the
Bragg angle.
The extrapolation method for the elimination of
the instrumental broadening of diraction lines has
been used since it does not require a standard sam-
ple. This method is valid for the conventional powder
X-ray diractometer with the BraggBrentano focus-
ing geometry
36,37
that was used in the present case.
The resultant grain size, for both the sols, comes out
to be of the order of 1215 nm.
Lower Temperature Formation of Alumina Thin Films Through SolGel Route 687
Fig. 13. Photoconduction measurements of Al
2
O
3
thin
lm.
The band gap of these Al
2
O
3
lms was deter-
mined by photoconduction measurements. Photo-
conductivity of the sample is plotted in Fig. 13,
which shows the relative photocurrent vs. energy of
the incident photons. The optical band gap (E
g
) of
Al
2
O
3
thin lms was determined from the straight
line intercept at the photon energy axis. For an
applied potential of 0.5 V, the energy band gap is
4.7 eV. At room temperature, the energy band gap
of bulk Al
2
O
3
is 6.2 eV.
38
The discrepancy of about
1.5 eV in the energy band gap of Al
2
O
3
is due to the
fact that we have studied Al
2
O
3
in thin lm form.
In addition, lowering of the band gap value may also
be associated with defect induced states in the band
gap.
39
This idea is supported by the peaks at 3.8 eV
and 4.3 eV in Fig. 13.
4. Conclusions
Alumina sol was spin coated onto silicon sub-
strates after optimization of synthesis of the sol. Al-
isopropoxide based sol (A) and Al-sec-butoxide sol
(B) were optimized for deposition of alumina thin
lms through solgel route. Bayerite [Al(OH)
3
] phase
of both the sols was observed in the room temper-
ature aged samples as conrmed by the XRD pat-
terns. Direct transition of sol A into -Al
2
O
3
was
observed at a temperature of 350

C whereas sol
B exhibited indirect transition to -Al
2
O
3
through
-Al
2
O
3
. Optical and scanning electron micrographs
showed continuous lm surfaces resulting from opti-
mized conditions. The energy band gap value of the
alumina lm was 4.7 eV, which has been attributed
to defect induced states in the band gap.
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