Materials Science and Engineering B 129 (2006) 180–185

Organo-silica–titania nanocomposite elaborated by sol–gel

processing with tunable optical properties
J. Franc a,∗ , D. Blanc a , A. Zerroukhi b , Y. Chalamet b , A. Last c , N. Destouches a
aLaboratoire Traitement du Signal et Instrumentation, CNRS-UMR 5516, Université Jean Monnet, 10 rue Barrouin,
42100 Saint-Etienne, 18 rue Benoı̂t Lauras, F-42000 Saint-Etienne, France
b Laboratoire de Rhéologie des Matières Plastiques, UMR CNRS 5156, 23 rue Paul Michelon, F-42023 Saint-Etienne Cedex 2, France
c Research Center Karlsruhe, Institute for Microstructure Technology, P.O. Box 3640, 76021 Karlsruhe, Germany

Received 6 December 2005; received in revised form 12 January 2006; accepted 18 January 2006

Abstract
Organically modified silica–titania thin films were elaborated by a sol–gel process and UV assisted photopolymerisation. Two different chelat-
ing agents, methacrylic acid (MAA) and a ␤-diketone (2-(methacryloyloxy) ethyl acetoacetone (MAEA)) were compared in this work. It was
demonstrated that the choice of the chelating agent is a key parameter to increase the molar ratio Si:Ti and therefore raise the refractive index of
the material. ␤-Diketone has proven to be a good candidate to stabilise the titanium precursor and its effects were compared to those observed
with methacrylic acid. Fourier transform infrared spectroscopy was used to monitor the material formation and modification upon irradiation.
M-lines spectroscopy was used to measure the refractive index of the material that varied between 1.51 and 1.59 depending on the titanium molar
concentration. Optical properties were analysed in view of applications in the field of micro-optics and optical coatings.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Refractive index; Transmission; Organic–inorganic hybrid materials; Sol–gel; Photopolymerisation; Chelating agent

1. Introduction for optical interconnections [6] and hard transparent coatings on

high refractive index polymers for the ophthalmic industry [7].
Organic–inorganic hybrid materials synthesised at room tem- It has been shown that the addition of metal alkoxide to a silica
perature via a sol–gel route are particularly attractive for fab- network had a direct effect on the refractive index of the resulting
ricating micro-optical elements and optical coatings as they material [1,8]. This paper will investigate the use of ␤-diketone
combine some advantages of organic polymers (ease of process- as a chelating agent for titanium isopropoxide (Ti). Its expected
ing, elasticity and organic functionalities) with characteristics ability to control the reactivity of the metal alkoxide in the pres-
of inorganic oxides (hardness, thermal and chemical stability, ence of water should allow to introduce larger Ti concentration
transparency and large range of refractive index) [1]. For some into the silicate matrix [9] and lead to higher values of the refrac-
time, research groups have been exploring the chemistry and tive index. The synthesis of the material and film deposition are
physical properties of hybrid materials based on photopoly- described. An insight into the structure of the material is gained
merisable methacryloxypropyltrimethoxysilane (MAPTMS) to through infrared spectroscopy. Optical properties of the coatings
produce optical thin films that are UV-patternable [2–5]. In this are assessed by UV–vis–NIR spectroscopy and M-lines exper-
context, we were motivated to examine the possibility of expand- iments. Finally, conclusions are drawn with respect to the use
ing the accessible refractive index range of this class of materials, and limitation of the material for optical applications.
while keeping the material UV-curable. Other relevant proper-
ties are the transparency and the possibility to deposit thick films
2. Material elaboration
on various types of substrates including plastics. Foreseen appli-
cations are in the field of monomode and multimode waveguides
The formation of the organo-silica–titania material described
in this paper can be described as a two-step process. The inor-
∗ Corresponding author. Tel.: +33 477915826; fax: +33 477915781. ganic backbone is produced by hydrolysis and polycondensation
E-mail address: janyce.franc@univ-st-etienne.fr (J. Franc). of the alkoxides in the solution and during thin film deposition

0921-5107/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.01.011
 J. Franc et al. / Materials Science and Engineering B 129 (2006) 180–185 181

(sol–gel process). The organic network is formed afterwards by was initiated with 0.75 equivalents of acidified water (0.01 M
UV-induced polymerisation. HCl). Under acidic conditions, silicon atoms are depleted of an
The paper is focused on the role of the chelating agent that is electron, making them more electrophilic and thus more sus-
used as a ligand to control the hydrolysis of the titanium alkox- ceptible to attack from water. The hydrolysis is consequently
ide. The control of the hydrolysis should allow to introduce faster and more complete. At the same time, Ti was complexed
a higher ratio of metal alkoxide in the silicate matrix without with MAEA before being dispersed into the pre-hydrolysed
precipitation or early formation of a gel. Larger titanium con- organosiloxane medium. It was found that a ratio Ti:MAEA
centration should lead to a higher refractive index material. In of 2:1 was sufficient to prevent the formation of a precipitate.
a previous study [5] the use of the widely studied methacrylic Hydrolysis and condensation of the remaining silicon alkoxide
acid (MAA) [2] for complexing titanium alkoxide allowed us to and of the Ti were resumed with additional water (H2 O:alkoxide
reach a Si:Ti ratio of 10:4 and a corresponding refractive index of was equal to 1.5). Photoinitiator in the form of 3 wt% of 1,1-
1.54. Here we will study the advantage of 2-(methacryloyloxy) dimethoxy-1-phenyl acetophenone (Irgacure 651) was added
ethyl acetoacetone (MAEA) with respect to MAA. The use of a to the solution. This photoinitiator was chosen as it has been
␤-diketone for metal alkoxide stabilisation is less frequent and identified as a stable and efficient molecule for comparable
reactions have not been extensively studied. ␤-Diketone contains formulations [10]. The free flowing sol was passed through a
a reactive hydroxyl group that forms a complex with titanium 0.45 ␮m filter and allowed to age for 48 h before deposition.
isopropoxide of a formula Ti-[O-CH-(CH3 )2 ]4 , according to a Thin films were dip-coated [11] on glass substrates or sili-
reaction given in Eq. (1), Section 3.1. This reaction produces con wafers with a constant withdraw speed of 5 cm/min. Further
isopropanol and a modified complexed precursor of titanium condensation due to solvent evaporation during the withdrawing
alkoxide that has the advantage of being more stable in the pres- stage contributes to further transformation from sol to gel. The
ence of water. thickness of the coatings which depends on the viscosity of the
Thanks to its strong complexing effect, it was found that solution and the withdrawing speed was about 5 ␮m. Wet films
a molar ratio Ti:MAEA of 2:1 was sufficient to stabilise the were cured using a mercury lamp mounted with an aluminium
titanium alkoxide. This quantity was four times lower than the reflecting mirror. Although the full spectrum of the mercury
necessary amount of MAA and has the advantage to facilitate lamp was used, the 313 nm emission peak was probably the
the hydrolyse step. Furthermore, the Si:Ti ratio can now reach most active. The power density measured at the sample surface
the value of 10:15. could be varied between 100 and 900 mW/cm2 and the temper-
The hybrid organo-silica–titania composite was prepared ature resulting from the infrared radiation from the lamp varied
from combinations of: (a) 3-methacryloyloxypropyltrimethoxy- accordingly between 25 and 80 ◦ C measured on the backside of
silane (98% purity), (b) titanium isopropoxide (97%), the substrate. The effect of the thermal assisted UV treatment
(c) 2-(methacryloyloxy) ethyl acetoacetone (95%) and (c ) on the material structure is studied in the next section.
methacrylic acid (99%) purchased from Aldrich Ltd. and shown
in Fig. 1. 3. Organic and inorganic networks formation
Photoinitiator IRGACURE 651 was acquired from CIBA.
Precursors were used as received, without any purification pro- Photoinduced structural changes in the hybrid material were
cedure. Silica–titania composite sols were prepared according to monitored through infrared spectroscopy. More specifically,
the following method previously developed by Blanc et al. [5]: the titanium complexation mechanism, the development of the
the molar ratios of precursors Si:Ti:MAEA were varied from organic network during thermally assisted UV curing and the
10:1:0.5 to 10:15:7.5 to modulate the optical response of the correlated changes in the inorganic backbone were assessed
material. Partial hydrolysis and polycondensation of MAPTMS with this technique. Infrared spectra were recorded with a

Fig. 1. Chemical precursor formulae: (a) MAPTMS, (b) Ti, (c) MAEA and (c ) MAA.
182 J. Franc et al. / Materials Science and Engineering B 129 (2006) 180–185

FTIR Spectrophotometer Perkin-Elmer “Spectrum One” in the 1720 cm−1 , that does not change with time, corresponds to the
range 4000–400 cm−1 . A set of 5 ␮m thick films with various C O bonds that are not complexed with Ti. The absorption peaks
Si:Ti:MAEA molar ratios were deposited on double side pol- at 1616 and 1529 cm−1 indicate the formation of the chelating
ished silicon wafers. complex. They correspond, respectively, to ␯(CO) vibration (car-
bon 1 in Eq. (1)) and ␯(CC) vibration (carbons 2 and 3 in Eq. (1))
3.1. Complexation of Ti with MAEA of the chelating ring [12]. The noticeable increase of the intensity
of these peaks is a signature of the complexing reaction. Bands
Most metal alkoxides are very reactive to water because of at 1127 and 995 cm−1 whose intensity increases with time may
the presence of electronegative alkoxy groups [12] that make be assigned to C O stretching and C H out-of-plane vibrations
possible a nucleophilic attack. As described in the synthesis bonds in the neighbourhood of Ti atom that are being formed
procedure, titanium isopropoxide needs to be complexed before during the complexation reaction [13].
being added to the silane precursor in order to form a soluble
polymeric solution that will be stable with respect to hydrolysis 3.2. Photoinduced organic network formation
reactions. Amongst the possible ligands, MAEA is a diketone
capable of keto-enol tautomerism [9]. The equilibrium between The polymerisation of the polymethacrylate chains linked to
a ketone and its enol form is described in Eq. (1). As the exper- the silicium atoms leads to the formation of an organic network
imental evidence of complexation of Ti with MAEA is not very through covalent bonding [10,14]. Fig. 3 shows that polymeri-
documented in the literature, a specific study was devoted to sation results in a decrease in the intensity of the C C bands
the mechanism involved in the reaction. MAEA was added drop at 1634 cm−1 and CH C band at 816 cm−1 . Even if the peak
wise to Ti and stirred for a few seconds at room temperature is originate from the methacrylate unsaturation C C, the peak
before being deposited on a silicon wafer. is subject to gradually decrease under UV treatment as the
stretching vibration C C at 1634 cm−1 [8,14,15]. However as
the 1634 cm−1 band overlaps with the 1616 cm−1 peak from
Ti complexation that does not participate to the polymerisation
reactions, this band will not provide a true estimation of the
C C consumption [8]. Indeed, the band at 1616 cm−1 , associ-
ated with the chelating ring does not change in intensity after
10 min proving the high stability of the titanium complex into
the molecule [12]. Therefore, the 816 cm−1 band was used to
monitor the photopolymerisation. Fig. 4 shows the evolution of
the CH C band with irradiation time and the nearly complete
disappearance of the CH C double bonds after 10 min of irra-
diation at 600 mW/cm2 .
To quantify the C C to C C conversion ratio, the C O band
at 1716 cm−1 was chosen as a reference because of its high
(1) intensity and its constant area upon irradiation [8]. As noted
by several authors, the carbonyl vibration position was shifted
Spontaneous reaction of MAEA with Ti was monitored by to 1728 cm−1 subsequently to UV irradiation because C O is
recording the absorption spectra (Fig. 2) of the Ti:MAEA sam- no longer conjugated with a vinyl constituent [10,3]. Fig. 5 is
ples between 5 and 60 min after deposition. It was verified that a zoom on the C O band of a sample of composition 10:4:2
the absorption spectrum was stable after 60 min. The peak at recorded at different irradiation times with a power density of

Fig. 3. FT-IR spectra of composition 10:4:2 before and after UV irradiation

Fig. 2. FT-IR spectra of Ti complexation after 5 and 60 min. (30 min at 600 mW/cm2 ).
 J. Franc et al. / Materials Science and Engineering B 129 (2006) 180–185 183

Fig. 4. Variation of intensity of ␯(CH C) at 816 cm−1 upon irradiation

(600 mW/cm2 ). Fig. 6. Influence of titanium content on photopolymerisation kinetics.

600 mW/cm2 . The maximum shift was observed after 5 min of power densities, the polymerisation mechanism was faster at
irradiation. higher power density.
The conversion ratio C% of the double to single C C bond
was defined as the ratio of the residual amount of C C at a given 3.3. Structural changes in the inorganic network
time, over the amount of C C before irradiation according to the
formula [10]: Inorganic network modifications related to photoinduced

 polymerisation were primarily observed in the range of
At A0 ref 1250–800 cm−1 . Fig. 7 compares the absorption spectra of a
C% = 100 × 1 − ·
At ref A0 10:4:2 composition before and after UV curing (600 mW/cm2 )
in the 1300–800 cm−1 range. The decrease in intensity
where At and A0 are the area under the peak at 816 cm−1 for of Si O CH3 stretching vibration of methoxy groups at
an exposition time t and t = 0 s, respectively, and A0 ref and At ref 1167 cm−1 is directly related to Si O Si or Si O Ti formation
are the area under the reference peak C O. Fig. 6 shows the [3]. Indeed, an increase of the asymmetric Si O Si stretching
kinetics of the conversion ratio for compositions 10:4:2, 10:10:5 is observed in the broad and intense absorption peak with a
and 10:12:6, when samples were irradiated with a power density maximum at 1084 cm−1 [8,14]. The decrease of Si OH peak
of 600 mW/cm2 . The error on the calculated areas is estimated at 932 cm−1 indicates a consumption of hydroxyl groups upon
to be of the order of 5% due to the choice of the minima position irradiation. These significant changes during radical polymeri-
particularly for the small peaks. The conversion ratio reaches sation, confirm that UV irradiation leads to the decomposition
60% after 1 min of irradiation and is nearly saturated at around of the Si O CH3 and Si OH bonds and further densification
90% after 10 min for every composition. The effect of the power of the inorganic Si O Si and Si O Ti network.
density was also investigated for a 10:12:6 composition at two Ti related bands were studied by comparing the absorption
different power densities (130 and 600 mW/cm2 ). Although a spectra of two compositions 10:4:2 and 10:12:6 (Fig. 8). As
maximum conversion ratio of around 90% was obtained for both said previously, bands at 1616 and 1534 cm−1 were assigned to

Fig. 5. Shift of ␯(C O) vibration from 1716 to 1728 cm−1 upon irradiation Fig. 7. FT-IR spectra of composition 10:4:2 showing the structural changes
(600 mW/cm2 ). before and after polymerisation (30 min at 600 mW/cm2 ).
184 J. Franc et al. / Materials Science and Engineering B 129 (2006) 180–185

Fig. 9. UV–vis–NIR spectra of hybrid thin films with various titania contents
Fig. 8. FT-IR spectra of two molar compositions 10:4:2 and 10:12:6 after 30 min
chelating agents with quartz as reference.
of UV irradiation.

the C O and C C vibration due to Ti complexation. Bands at tra of films prepared from sols with the same titanium contents
980 and 910 cm−1 were attributed to Si O Ti stretching and (Si:Ti = 10:4) but different chelating agents. Transmission val-
the latter was overlapped by residual Si OH stretching vibra- ues are those of the films only (a quartz substrate was taken as a
tion at 932 cm−1 . It is important to note that bands at 1167 and reference when acquiring the spectra and the ratio of transmit-
1280 cm−1 attributed, respectively, to Si O CH3 and organic tance was calculated) [16].
part were still present in the sample with high titanium content The chelating agent had a clear influence on the spectra mea-
[16]. Despite the efficient organic polymerisation (C% ∼ 90) in sured with the 10:4 compositions, as a higher absorption was
this sample, it can be concluded that condensation reactions lead- observed in the MAEA containing material.
ing to Si O Si or Si O Ti formation were limited by the high Furthermore, the Ti content strongly affected the position of
density of the structural network. Indeed, the density increased the absorption edge, as seen also in Fig. 9. For higher Ti con-
considerably and prevented the hydrolyse of all the remaining centrations the absorption edge was shifted towards the longer
partial bonds that were trapped in the heart of the material. This wavelengths. Transmission value of 90% was reached at 385 nm
assumption will be used in the next section to explain the satu- for 10:1:MAEA, 430 nm for 10:4:MAEA and 10:4:MAA, and
rated value of the refractive index measured in samples with a 470 nm for 10:12:MAEA. This shift that was attributed to
high titanium concentration. absorption of the Ti–MAEA complex [18], was confirmed by the
In conclusion, complexation with MAEA permits to increase yellow coloration of the films as the Ti concentration increased.
the Ti content in the organically modified silicate. Although However, visual observation showed that, whatever the com-
FTIR spectra are more complicated than these measured with position, the films were transparent and did not scatter light.
MAA, due in particular to the overlap of the C C band at By looking at the spectra more precisely, one can observe
1634 cm−1 , it was still possible to quantify the C C to C C oscillations whose period increases with the wavelength. These
conversion ratio using the 816 cm−1 absorption peak. The max- oscillations are the result of the multiple beams interference
imum conversion rate of 90% was similar to the one obtained phenomenon that occurs in the presence of a thin layer on a
with MAA [2]. The titanium complexation was stable under UV substrate [19].
irradiation as evidenced by the bands at 1616 and 1529 cm−1 The refractive indices were measured with the prism coupler
that were still present in the cured sample. Furthermore, for high method [20] at a wavelength of 632.8 nm. Films of 4 ␮m thick-
titanium concentrations, the large bands at 1167 and 1280 cm−1 ness were cured for 20 min with the mercury lamp at a power
indicate that the condensation of the inorganic network was not density of 600 mW/cm2 to achieve a complete polymerisation.
complete probably due to structural network’s density. Competi- In the prism coupler set-up a laser beam (He–Ne) is coupled by
tion between organic and inorganic network formation has been a prism into the thin coating. Strong coupling is achieved when
pointed out by other authors [17]. the phase velocity of the incident wave in the prism equals the
phase velocity of one of the characteristic modes of propagation
4. Optical properties in the film. Fig. 10 shows the values obtained for different com-
positions Si:Ti with both chelating agents, MAA and MAEA.
The transmission spectrum and the refractive index of the For ratios lower than 10:4, the change of chelating agent does not
polymerised material was studied in the UV, visible and near induce any significant effect and proves that only the Ti quantity
IR ranges. Transmission measurements were performed with a influences the index value. An increase of the refractive index
spectrophotometer Perkin-Elmer Lambda 900. Five microme- almost proportional to the Ti concentration was observed with
ters thick films were dip-coated on quartz substrates and illu- MAEA, up to a maximum value of 1.59 obtained for a ratio of
minated for 30 min with a 600 mW/cm2 power density to reach 10:10:5. For 10:12:6, the refractive index remains constant. We
the maximum degree of polymerisation. Fig. 9 shows the spec- assume that this saturation is caused by the steric hindrance of
 J. Franc et al. / Materials Science and Engineering B 129 (2006) 180–185 185

content increased, might be restrictive for some applications.

Overall, due to their tunable properties, hybrid materials and
related technologies are promising candidates for low cost fab-
rication of micro-optical elements.

Acknowledgments

One of the authors would like to thank the Region Rhône-

Alpes for financial support. This work was carried out in the
framework of the Network of Excellence on Micro-Optics
(NEMO) supported by the European Commission through the
FP6 Program (FP6/2003/IST/2/contract no. 003887).

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