Optical Materials 27 (2005) 14951500

www.elsevier.com/locate/optmat

Coloured organicinorganic coatings on glass

Krzysztof Wojtach a, Katarzyna Cholewa-Kowalska a, Maria aczka
a

a,*

, Z. Olejniczak

AGH-University of Science and Technology, Faculty of Materials Science and Ceramics,

Department of Technology of Glass and Amorphous Coatings, 30-059 Krakow, Poland
b
Institute of Nuclear Physics, 31-342 Krakow, Poland
Available online 10 March 2005

Abstract
Organicinorganic hybrids were obtained by the alcoholate solgel method. The characteristic feature of these materials is that
CnHm groups are connected to silicon atoms by CSi bonds. Such structures are compatible matrices for organic dyes. The gels prepared from pure tetraethoxysilane (TEOS) modied with methyltrimethoxysilane (MTMS) or phenyltriethoxysilane (PhTES) were
subjected to heat treatment in the temperature range 40500 C. Then, they were examined by FTIR spectroscopy. All gels after
heating at 100 C were analysed by 29SiMASNMR. It has been observed that polycondensation proceeds faster in presence of
an organic modier compared to pure TEOS. Moreover, it has been found that copolymers form between the units of TEOS
(Q) and organic modiers (D). Thermal stability of copolymers depends on the modier type but the temperature of 350 C should
not be exceeded. The hybrid materials were coloured by introducing organic absorption dyes to the gel matrix. Hybrid lms were
deposited on glass plates by a dip-coating technique. Optical properties of those lms were examined by measuring light transmission in the range of visual wavelengths (UVvis spectroscopy).
2005 Elsevier B.V. All rights reserved.
Keywords: Coloured lms; Hybrid materials; Solgel method; FTIR spectroscopy; UVvis spectroscopy

1. Introduction
Organicinorganic hybrids are relatively new materials of the Ormosils group (organic modied silicates).
They combine the advantageous properties of both organic and inorganic materials. By proper selection of
an organic modier it is possible to obtain hybrids with
the refractive index changing in a wide range and with a
controlled light transmission in the UV/vis and near IR
range. Such materials in the form of thin lms on appropriate substrates can nd application in optical waveguides for planar integrated circuits [1]. Hybrid gels

Corresponding author.
E-mail addresses: cholewa@uci.agh.edu.pl (K. Cholewa-Kowalska), mlaczka@poczta.fm (M. aczka).
0925-3467/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.optmat.2005.01.016

with proper organic modiers and hydrophobic properties can be used also in the manufacturing of transparent
or translucent window thermal and acoustic insulations
[2,3]. Basic requirements for such applications are: high
transparency of the matrix, abrasion and scratch resistance close to that of glass, very good adhesion to glass
surfaces, stable basic properties, and high stability of
colours (no fading) [4,5]. Low viscosity of the coloured
hybrid sols allows using great variety of coating techniques, the choice being dependent on chemical composition of the sol: dipping, spinning, spraying, brush
painting, roller coating, felt-pen painting, or screen
printing [6,7]. Organicinorganic hybrids are also compatible matrices for intensive organic dyes, laser dyes
and other organic compounds.
The aim of this study was to determine structural
characteristics of the hybrid gels modied with two organic modiers, diering in functional groups: MTMS,

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K. Wojtach et al. / Optical Materials 27 (2005) 14951500

PhTES, and stability of the hybrid structures at elevated

temperatures. The hybrid gels were used as matrices for
the commercial ORASOL-type organic dyes.
2. Experimental
Bulk samples were prepared from tetraethoxysilane
(TEOS) and organic modierseither methyltrimethoxysilane (MTMS) (CH3)Si(CH3O)3, or phenyltriethoxysiOrganic
modifier

TEOS
H2O

Organic
dye
Final
solution

Gels

Coatings
on glass

Fig. 1. Scheme of gels and coatings preparation.

Fig. 2. FTIR spectra of gel after heat treatment at various

temperatures.

Table 1
Characteristic bands appearing in FTIR spectra of the obtained gels and their interpretation [8,9]
TEOS

TEOS + MTMS

TEOS + PhTES

Origin

460

436458

438491

OSiO bend

624626
637698

Oop ring bend

Structural units
O

Si

567572

738740

In phase,
oop 5 adjacent H

800

778802

786795

950

936954

956

m SiOSi
OSiCH3
SiOH

1050

10591085 1135

10681070
11361137

m SiOSi
m SiOSi

1630

3450

3441

Oopout of plane; mstretch; rdeformation.

H
H

SiOSi
SiOSiOCH3
SiOH
Si

Si

CH
r (CH2)

SiCH3
SiCH@CH2

14301432

CH, SiC

Si

1490

Ring

15951606

Ring

12761280
14071412

1630

Si

2978, 3050, 3072

3438

HOH

H2O

CH
OH, H

C H

K. Wojtach et al. / Optical Materials 27 (2005) 14951500

1497

lane (PhTES) C6H5Si(CH3CH2O)3 (Merck, Darmstadt,

Germany). Molar ratios of TEOS to the organic
modiers were 1:1 and 4:1. Phthalocyanine Cu (ORASOL BLUE GN) and chrome complexes (ORASOL
ORANGE RG, ORASOL RED BL) (CIBA Speciality
Chemicals Inc.) were added as dyes to obtain coloured
gels. Gel and coating preparation scheme is given in
Fig. 1. The gels were dried at 40 C and next heated to
the following temperatures: 100, 200, 300, 400 and
500 C.
Microscopic glass plates with proper surface nish
were covered with a suitable solution. The lms were
deposited by means of a dip-coating technique in an apparatus designed for this purpose. The rate of glass-plate
dipping in the solution was determined experimentally.
The coated specimens were dried at ambient temperature
and then at 40 C. The subsequent heat treatment was
carried out at 100 C and at 200 C.
All the bulk samples were examined by FTIR (DIGILAB spectrophotometer) to determine the structure of
gels (Table 1 and Figs. 2 and 3). Bulk gels after heating
at 100 C were also analysed by the 29Si MAS NMR
spectroscopy (magnetic eld of 7.05 T) (Fig. 4).
The lms obtained on glass plates were observed
under a scanning electron microscope (SEM) (Fig. 5),
that allowed rough estimation of their thickness. Surface
roughness was determined according to ISO (DIS H287/
1) using Hammel Tester T500 prolometer (Mommelwerke GmbH, Berlin) (Table 2). Optical characteristics of lms in the UV/vis range were measured using a
UVvis spectrophotometer HP 8453 (Fig. 6). Coloured
lms were additionally tested for chemical resistance in
repeated cycles of washing in tap water, followed by
transmission measurements in the UV/vis range.

3. Results
It was noticed during the gel preparation procedure
that the gelation time depended on the type of organic

Fig. 3. FTIR spectra of gels after heat treatment at various

temperatures.

29

29

Si NMR
4 kHz MAS

Si NMR
4 kHz MAS
TEOS + MTMS

TEOS
TEOS + PhTES

50

-50

-100

ppm TMS
Fig. 4.

29

-150

50

-50

ppm TMS

Si MAS NMR spectra of gels after heat treatment at 100 C.

-100

-150

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K. Wojtach et al. / Optical Materials 27 (2005) 14951500

Fig. 5. SEM image of the Orasol Blue GN dyed lm obtained from the
PhTES-modied TEOS after heat treatment at 100 C.

Table 2
The parameters of surface roughness
Sample

TEOS + MTMS (1:1)

TEOS + MTMS (4:1)

Ra [lm]
Rt [lm]

0.02
0.90

0.02
0.52

Raarithmetic mean of level roughness. Rtmaximum height

between highest peak and lowest valley.

100

100

80

80

60
o

TM_OrBlue_40 C
o
TM_OrBlue_100 C
o
TM_OrBlue_200 C
o
TM_base_100 C

40
20

Transmitance [%]

Transmitance [%]

modier added to the solution. A solution with an addition of MTMS gelled the fastest (2 days) and with an

addition of PhTES gelled the slowest (7 days). Moreover, the viscosity of the TEOS-PhTES sols was higher
compared to the sols obtained with an addition of
MTMS. The gels received at ambient conditions were
fully transparent and had the form of discs, 20 mm in
diameter (almost free of cracks for the molar ratios
4:1). The TEOS + MTMS gel (the molar ratio 1:1)
showed some cracks, whereas the TEOS + PhTES gel
(the molar ratio 1:1) showed numerous cracks. Heating
at 100 C did not change the appearance of the gels,
however, heating at higher temperatures caused some
opacity or even complete loss of transparency. All samples were examined by FTIR spectroscopy (Figs. 2 and
3). Table 1 shows characteristic IR bands and their
interpretation [8,9].
Fig. 4 presents MAS NMR spectra of gels obtained
from TEOS, TEOS + MTMS and TEOS + PhTES after
heating at 100 C. Solutions with an addition of coloured dyes were used for the deposition of thin layers
on glass plates. The quality of layers was examined by
SEM. Fig. 5 presents the SEM photograph of the Orasol
Blue GN dyed lm obtained from PhTES-modied
TEOS after treatment at 100 C. The results were similar
for other samples. All the lms were characterized by
distinct colouring; the most intensive being that of the
TEOS + PhTES hybrid gels. The dierences in the intensity of colouring for the various hybrid matrices were

60
o

TPh_OrBlue_40 C
o
TPh_OrBlue_100 C
o
TPh_OrBlue_200 C
o
TPh_base_100 C

40
20
0

200

400

600

800

200

1000

400

100

100

80

80

60
40

600

800

1000

Wavelength [nm]

TPh_OrOrange_40 C
o
TPh_OrOrange_100 C

20
0

Transmitance [%]

Transmitance [%]

Wavelength [nm]

60
40
o

TPh_OrRed_40 C
o
TPh_OrRed_100 C

20
0

200

400

600

800

Wavelength [nm]

1000

200

400

600

800

1000

Wavelength [nm]

Fig. 6. UVvis spectra of the base lm and the Orasol Blue GN, Orasol Orange RG and Orasol Red BL dyed lms obtained from the MTMS- and
PhTES-modied TEOS after heat treatment at various temperatures (40 C, 100 C, 200 C).

K. Wojtach et al. / Optical Materials 27 (2005) 14951500

due to dierent thickness of the deposited layers. The

TEOS + PhTES lms were the thickest (about 34 lm)
while the TEOS + MTMS ones were thinner (about 2
3 lm). The larger thickness was related to higher viscosity of the sols modied with PhTES. The parameters of
surface roughness are similar for all the samples examined (Table 2). The optical UV/vis characteristics of
the layers after heating at 40, 100 and 200 C are given
in Fig. 5. For the coatings dyed with Orasol Blue GN
maximum heat-treatment temperature was 200 C, while
for the coatings with Orasol Red BL and Orasol Orange
RG it was 100 C.

4. Discussion
4.1. Structure of the hybrids
The structure of the organicinorganic gels was determined basically from FTIR and MAS NMR spectroscopic examinations. In the spectra of the hybrid gels
there appear bands related to the vibrations of both, inorganic and organic, structural units. The most intensive
band, at about 1100 cm 1, is connected to the asymmetric
stretching vibrations of the SiOSi bridges. In the case of
hybrid structures this band becomes clearly split into two
separate bands at about 1060 cm 1 and 1130 cm 1.
Vibrations of the siliconoxygen bridges are also
responsible for the bands at about 800 cm 1 (the symmetric stretching vibrations) and at about 450 cm 1
(the bending vibrations). The band related to vibrations
of the SiOH groups is observed at about 950 cm 1.
Bands connected to vibrations of the organic groups
are usually very sharp and are situated in the ranges of
wavenumbers 14003070 cm 1 and 540740 cm 1. These
are the bands related to vibrations of CH, SiC,
CH@CH2 as well as to the ring structures. So, the FTIR
spectra indicate that both organic and inorganic structural units are present in the obtained gels. The analysis
of the band intensities related to the organic components
as a function of the heating temperature of the gels (100
500 C) indicates that complete decomposition of the organic components takes place at temperatures exceeding
500 C. The organicinorganic hybrid structure is retained up to 400 C. The type of bonds between the inorganic and organic components of the hybrid structure is
an important issue. Chemical properties of the organic
modiers (compounds of the R4 nOSiRn type) suggest
that these compounds should take part in polycondensation with the precursor of the inorganic component, i.e.
Si(OR)4 (TEOS). This reaction should yield copolymers
with the following bonds:
Si

Si

CnHm

1499

According to Gunzler and Gremlich [8] interpretation

the band situated in the range 800770 cm 1 originates
from vibrations of the OSiCH3 group. At 800 cm 1
there appears in the spectrum also a band induced by
bending vibrations of OSiO. In IR spectra of all obtained hybrids distinct, sharp bands at about 770 cm 1
occurs, which become shifted towards higher wave numbers with increasing temperature of heating of the samples (Table 1, Figs. 2, 3). This is and indication that
organic and inorganic components of the hybrids are
connected by chemical bonds.
The presence of copolymers in the obtained organic
inorganic materials is also indicated by the spectra 29Si
MAS NMR (Fig. 4). In these spectra there appear the
peaks originating from the structural TEOS units
(100110 ppm). However, there appear also additional
peaks at 5070 ppm (TEOS + MTMS) and 7090 ppm
(TEOS + PhTES). In agreement with the earlier interpretation given by Brus and Dybal [10] these additional
peaks can be ascribed to copolymers formed from the
organic and inorganic structural units of the hybrid.
4.2. Evaluation of quality of the thin lms and their
optical characteristics
All the hybrid lms were essentially crack-free and
showed very good adhesion to the substrates. Intensive
absorption bands, characteristic of the particular dyes,
were observed in the optical spectra of the lms (Fig.
6). In the case of the TEOS + PhTES hybrid matrix
the absorption band intensities were the highest because
the obtained lms were the thickest. Heating of glass
plates with the deposited lms dyed with Orasol Blue
GN to 200 C did not change the optical characteristics
of the layers. In the case of the coloured lms obtained
with Orasol Red BL and Orasol Orange RG, heat treatment at 200 C induced bleaching of the lms. It was
probably caused by decomposition of the dyes at higher
temperatures. Repeated washing under running water
did not cause any decolourisation of the lms or changes
in the absorption spectra.
The results of this work indicate that the dyes were
rmly incorporated in the hybrid matrix probably being
trapped in some structural voids. The high intensity of
colouring and stability of the hybrid lms demonstrate
the usefulness of the developed method of preparation
and deposition in the manufacturing of coloured glass
and ceramics.

Acknowledgment
This investigation was nancially supported by the
Polish State Committee for Scientic Research, under
Project No.: 11.11.160.113.

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