Journal of Sol-Gel Science and Technology 32, 167172, 2004

c 2004 Kluwer Academic Publishers. Manufactured in The United States.

SolGel SiO
2
-ZrO
2
Coatings for Optical Applications
MARIA CRISAN,

MARIUCA GARTNER, LUMINITA PREDOANA, RARES SCURTU

AND MARIA ZAHARESCU
Institute of Physical Chemistry I.G.Murgulescu, Roumanian Academy, 202 Splaiul Independentei
P.O. Box 12-194, 060021 Bucharest, Roumania
mcrisan@chimz.icf.ro
RALUCA GAVRILA
National Institute for Research and Development in Microtechnologies, P.O. Box 38-160, Bucharest, Roumania
Abstract. SiO
2
-ZrO
2
based nanostructured multilayers lms have been prepared by solgel processing from
metallorganic precursors by low temperature inorganic polymerization reactions. Simultaneous gelation of both
precursors was realized. Homogeneous and transparent lms were obtained at room temperature by dip- and spin-
coating on glass and silicon wafer substrates. Samples with successively deposited layers (13 layers) and successive
thermal treatments have been also studied. Each deposited layer was thermally treated for 1 h at 300

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
-

To whom all correspondence should be addressed.

SiO
2
coatings for wavelength-selective reection l-
ters, using ZrO
2
and SiO
2
sols to deposit multilayered
coatings by a solgel spin-coating technique. Zhang
et al. [3] prepared colloidal-based ZrO
2
highly reec-
tive coatings consisting of alternating layers of quar-
ter wave-thick high and low refractive index compo-
nents on glass substrates, while Canada and Xue [4]
produced optical base sensor SiO
2
-ZrO
2
-organic poly-
mer lms doped with high pK(a) indicators. Most of
these studies have focused on the synthesis of meso-
porous and porous SiO
2
-ZrO
2
mixed oxides by sol
gel methods [516], microporous SiO
2
-ZrO
2
ceramic
membranes [17, 18] for CO
2
separation from exhaust
gases at high temperatures and liquids separation,
silica-zirconia composites (e.g. silica-coated zirconia
microspheres as chromatographic support materials)
[19] and silica-zirconia gels for catalytic applications
[2027].
168 Crisan et al.
Table 1. Composition of starting solution and experimental conditions for binary 70SiO
2
-30ZrO
2
(% mol) lms
preparations.
Molar ratio
ROH+R

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, leading to a homogeneous solgel so-

lution containing both precursors. The hydrolysis re-
action was carried out in a closed system, ushed with
puried nitrogen, via a dropping funnel.
Supported SiO
2
-ZrO
2
lms on glass, silicon wafer
and silicon wafer/SiO
2
substrates were produced by
dip-coating (with a withdrawal speed of 5 cm/min.)
and spin-coating (2000 rpm) using the solutions given
in Table 1. Before deposition, the solutions were aged
for 24 h room temperature. The lms were densied
by thermal treatment for 1 h at 300

C, with heating
rate of 1

C/min, based on the results of DTA/TG anal-

ysis on the un-supported gels. For multi-layered lms,
the same thermal treatment was applied after each
deposition cycle.
2.2. Films Characterization
The optical properties of SiO
2
-ZrO
2
multilayer thin
lms were investigated by spectroscopic ellipsometry
(SE). The measurements were carried out in air, in the
300700 nmwavelength range at an angle of incidence
of 70

. The acquisition interval of the data was 10 nm

and the reading accuracy of the angles of incidence was
0.017

. XRDpatterns were obtained using a TuRM-62

(with HZG-3 equipment) and UV-VIS spectra with a
Shimadzu ISR-24 AA spectrometer. The morphology
and surface roughness of the coatings were investigated
via AFM using contact mode in air, using an apparatus
assembled at the University of Twente.
3. Results and Discussion
Under the conditions used in this work, continuous and
homogeneous lms with a good adherence to the sub-
strates were obtained. XRD results have conrmed the
amorphous character of the as-deposited and thermally
treated (1 h 300

C) lms. Optical properties of the lms

obtained, as determined by SE measurements are pre-
sented in Table 2. In the visible range, all lms are
transparent (k <10
4
).
The experimental ellipsometric spectra were
modeled with the multilayer and multicomponent
Bruggemanns effective medium approximation
(BEMA) model [28]. For the coatings deposited on
glass or silicon substrate, the one-layer model (SiO
2
-
ZrO
2
lm/glass or Si) was used. For the coatings
deposited on SiO
2
/silicon substrate, a two-layers
SolGel SiO
2
-ZrO
2
Coatings for Optical Applications 169
Table 2. The volume fraction of the components and the thickness of the layers obtained from SE measurements on SiO
2
-ZrO
2
lms.
Support Method of deposition NL NTT SiO
2
(%) ZrO
2
(%) Void (Air) (%) d
lm
(

A) n 633 nm E
g
(eV) E
d
(eV)
Glass Dipping 1 0 49.79 24.35 25.86 1338 1.499 6.91 11.91
1 1 54.37 22.87 22.76 1304 1.505 6.75 12.39
2 2 57.80 25.37 16.93 3200 1.552 6.70 13.60
3 3 58.38 25.92 15.70 4958 1.562 6.67 13.84
SiO
2
/Si 1 0 69.33 30.36 0.31 2053 1.661 6.50 16.45
1 1 69.09 30.61 031 1550 1.667 6.47 16.58
2 2 70.67 29.23 0 2460 1.663 6.49 16.49
3 3 69.93 30.07 0 4132 1.669 6.34 16.25
Si Spinning 1 1 70.00 30.00 0 1570
SiO
2
/Si 1 1 69.03 30.97 0 1306
Si 4 4 70.00 30.00 0 5866

NL = number of layers; NTT = number of thermal treatments.

model (SiO
2
-ZrO
2
lm/SiO
2
/Si) was used. The tting
parameters were: the thickness of the layers and the
volume fraction of the components (SiO
2
, ZrO
2
,
air-lled void). From the best t, one obtained the
refractive index (n), the thickness of the layers (d) and
volume fractions of the components (Table 2).
The Wemple-Di Domenico (WDD) model [29] was
usedtot the refractive indexdispersioninthe regionof
transparency (at lowenergy) to obtain the direct optical
bandgap of the SiO
2
-ZrO
2
lm:
n
2
1 =
E
d
E
0

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

C), deposited on glass substrates.

Figure 3. AFMimages of single-layer thermallytreatedlms (glass
substrate, dip-coated) measuredover anarea of 22m. Root-mean-
square roughness (rms), 2.3 nm.
roughness were obtained. According to the DTA/TG
analysis on the corresponding un-supported samples,
all the organic residues were removed below this tem-
perature [31].
3.4. The Inuence of the Substrate
It is very clear that in our study, the dominant inu-
ence upon the structure and optical properties of the
lms is that of the substrate. It is known that the sub-
strate topography inuences the crystallization of the
lm. On a crystalline substrate the lm itself is more
Figure 4. AFM images of single-layer thermally treated lms
(SiO
2
/Si substrate, dip-coating) measured over an area of 2 2 m.
Root-mean-square roughness (rms), 3.4 nm.
Figure 5. AFM images of single-layer thermally treated lms
(SiO
2
/Si substrate, spin-coating) measured over an area of 22 m.
Root-mean-square roughness (rms), 2.8 nm.
liable to crystallize [30]. From the data presented in
Table 2, it is evident that the lms deposited on glass
substrates are more porous than those deposited on
SiO
2
/Si, in which case the substrate appears to in-
duce greater densicaion of the lms. The results ob-
tained are in good agreement with our previous data
[32, 33].
SolGel SiO
2
-ZrO
2
Coatings for Optical Applications 171
Figure 6. AFM images of single-layer thermally treated lms (Si
substrate, spin-coating) measured over an area of 2 2 m. Root-
mean-square roughness (rms), 10.1 nm.
The direct optical gap (E
g
) of the lms, ob-
tained from the WDD model, decreases with the
number of thermal treatments (Table 2) from 6.91
to 6.67 eV for lms on glass substrates, and from
Figure 7. Images of a SiO
2
-ZrO
2
waveguide (width 30 m, thickness 120 nm): (a) optical micrograph, and (b) SEM image.
Figure 8. Images of a SiO
2
-ZrO
2
waveguide (width 60 m, thickness 680 nm): (a) optical micrograph, and (b) SEM image.
6.50 to 6.34 for those on SiO
2
/Si supports. The en-
hancement of the dispersion energy (E
d
) (from 11.91
to 13.84 for the samples deposited on glass and from
16.45 to 16.58 for the samples deposited on SiO
2
/Si)
after thermal treatment shows an increase of structural
order in the matrix of the material, which correlates
with the densication of the lms presented above.
The absorption spectra in the range from 325 to
475 nm of as-deposited and thermally treated lms
on glass substrates exhibited bands at ca. 360 and
ca. 400 nm associated with Zr(IV) species. Their
absorbance increased with thermal treatment due to
densication of the lm, irrespective of the number of
layers deposited [34].
AFM images of single layer, thermally treated lms
deposited by different methods on the different sub-
strates (2 2 m areas), are presented in Figs. 25.
All lms exhibited a uniform (featureless) morphol-
ogy, consistent with the absence of (faceted) crystalline
species observed by XRD. The values of roughness
were in the range 2 to 10 nm, with the lowest value
being observed for coatings deposited on glass sub-
strates via dip-coating (2.3 nm). The SiO
2
/Si substrate
induced in both deposition methods a wave-like aspect
to the lms surface; the origin of this effect remains to
be explained.
172 Crisan et al.
Optical waveguide on silicon substrate were pre-
pared and preliminary results have been presented in
[35]. The solgel layers were used as the waveguide
core or cladding. In the second case, the cladding can
act also as a transducing layer. The bottom waveguide
cladding is a SiO
2
layer, with a thickness and refractive
index of 500 nm and 1.45, respectively. The waveg-
uide core is a solgel layer (SiO
2
-ZrO
2
), with thick-
ness in the range 120800 nm and refractive index be-
tween 1.681.75. The waveguides were obtained by
patterning the solgel layer using a photoresist mask.
The etching was performed in a 2:1 HF:CH
3
-COOH
solution with an etching rate of 6000 nm/min. The
resulting SiO
2
-ZrO
2
waveguides are presented in
Figs. 7 and 8. Future work will be directed towards
optimizing the deposition process to improve the uni-
formity of the layers.
4. Conclusions
Multilayered solgel SiO
2
-ZrO
2
lms deposited by
spin and dip-coating on different substrates were pre-
pared from precursor solutions in which the hydrolysis
and condensation conditions were controlled to pro-
mote uniformgelation of the Si(IV) and Zr(IV) precur-
sors. This work extends the relatively few reports of
the use of solgel processing to produce high-quality
lms in the technologically important SiO
2
-ZrO
2
sys-
tem. The lms produced in our work are homogeneous,
amorphous and at, and exhibit low roughness values.
The inuence of deposition method, substrate type,
number of coatings and number of thermal treatments
on the optical and structural properties of the lms was
established.
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