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C. The coatings
were characterized by XRD, spectroellipsometry (SE), UV-VIS spectroscopy and AFM methods. The inuence of
substrates, number of coatings and number of thermal treatments on the optical and structural properties of the lms
was established. The thickness of three deposited SiO
2
-ZrO
2
layers is about 496 nm on glass substrates and 413 nm
on the silicon wafer substrate. The lms deposited on glass are more porous than those deposited on silicon. The
properties of optical waveguide prepared from SiO
2
-ZrO
2
layers on silicon substrates will be discussed.
Keywords: solgel method, SiO
2
-ZrO
2
coatings, multilayer deposition, optical waveguide
1. Introduction
SiO
2
-ZrO
2
lms have many applications, as a conse-
quence of their interesting optical and photonics prop-
erties (e.g. waveguides, micro mirrors, transducing lay-
ers for waveguide-based gas sensors, etc.). The sol
gel process offers a versatile method for the prepa-
ration of optical quality lms with controlled refrac-
tive indices and thickness, allowing a nanoscale con-
trol of the lms structure. Although research into the
production of solgel coatings has increased consider-
ably during recent years, less information exist in the
literature about the deposition of lms in the SiO
2
-
ZrO
2
system. Ebener and Winter [1] studied reac-
tions and phase transformations in SiO
2
-ZrO
2
solgel
coated alumina powders. Fan et al. [2] obtained ZrO
2
-
OH H
2
O HNO
3
Conditions of reaction
Precursors
precursors
precursors
precursors pH of the mixture T (
C) t (h)
Si(OC
2
H
5
)
4
19.3 1.85 0.0271 3.5 50 2
Zr(OC
3
H
7
)
4
in N
2
R = C
2
H
5
; R
= C
3
H
7
.
The aimof this paper is the preparation of SiO
2
-ZrO
2
thin lms via an alkoxides-based solgel method, with
simultaneous gelationof bothprecursors. The inuence
of substrate, number of coatings and number of thermal
treatments on the optical and structural properties of the
lms was established.
2. Experimental
2.1. Films Preparation
Tetraethylorthosilicate (Si(OC
2
H
5
)
4
, Merck) was used
as SiO
2
source, zirconium (IV) n-propoxide solution
(Zr(OC
3
H
7
)
4
, 70% solution in n-propanol, Fluka) as
ZrO
2
source, absolute ethyl alcohol and isopropyl al-
cohol (p.a reagent, Reactivul) as solvent, nitric acid
(p.a reagent, Merck), as catalyst and distilled water
for hydrolysis. The composition of the starting solu-
tion, corresponding to molar composition (mol%) of
70SiO
2
-30ZrO
2
and the experimental conditions for
lm preparation are listed in Table 1.
For this binary system, a two steps method for
preparation of the solution was employed. In the rst
step, Si(OC
2
H
5
)
4
was pre-hydrolysed with a sub-
stoichiometric amount of water. In the second step, an
alcoholic solution of Zr(OC
3
H
7
)
4
was added to the par-
tially hydrolyzed and condensed Si(OC
2
H
5
)
4
and the
mixture (pH = 4) was reacted under vigorous stirring
for 2 h at 50
C, with heating
rate of 1
E
2
0
E
2
(1)
where E
d
is the dispersion energy, a measure of the
average strength of the interband optical transitions,
and E
0
is the oscillation energy, which is related to the
optical gap by the empirical formula E
0
=1.5E
g
.
It is well known that the substrate has a signif-
icant inuence upon the growth of a lm and also
upon its optical and microstructural properties [30].
In the following sections, we analyze this inuence in
the case of SiO
2
-ZrO
2
lms in parallel with the inu-
ence of preparation method (dipping and spinning) and
number of deposition cycles.
3.1. The Inuence of the Number of Depositions
The key characteristic in the multilayered lms is the
approximately linear increase in the thickness of the
coatings with the number of deposition cycles, inde-
pendent of the type of substrate (Fig. 1). The refractive
index increases with the number of depositions (partic-
Figure 1. The inuence of the number of layers on the thickness
of lms deposited by dip-coating on glass and SiO
2
/Si substrates.
ularly with glass substrates, Table 2), due to the densi-
cation induced by repeated thermal treatment.
3.2. The Inuence of the Method of Depositions
The single-layer lms deposited by dipping and spin-
ning on the same substrate (SiO
2
/Si) have a higher
thickness when dipping was used (Table 2). Due to the
fact that different applications require different meth-
ods of lmdeposition, information about the properties
of the lms obtained by dip-coating or spinning are of
practical interest.
3.3. The Inuence of the Thermal Treatment
After thermal treatment at 300
C amorphous, con-
tinuous lms, free of organic traces with rather low
170 Crisan et al.
Figure 2. The absorption spectra of single and multilayer fresh and
thermally treated lms (1 h, 300