Optical Materials xxx (2014) xxxxxx

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Thickness and structure change of titanium(IV) oxide thin films

synthesized by the solgel spin coating method
Aneta Lewkowicz a,1, Anna Synak a, Beata Grobelna b,, Piotr Bojarski a, Robert Bogdanowicz c,
Jakub Karczewski d, Karol Szczodrowski a, Mirosaw Behrendt a
a
Institute of Experimental Physics of Gdansk, Wita Stwosza 57, 80-952 Gdansk, Poland
b
Faculty of Chemistry, University of Gdansk, Wita Stwosza 63, 80-952 Gdansk, Poland
c
Faculty of Electronics, Telecommunications and Informatics, Gdansk University of Technology, 11/12 Narutowicza Str., 80-233 Gdansk, Poland
d
Faculty of Applied Physics and Mathematics, Gdansk University of Technology, Narutowicza 11/12, 80-952 Gdansk, Poland

a r t i c l e i n f o a b s t r a c t

Article history: Titanium dioxide is a well-known material in nanotechnology, while it provides new opportunities due to
Available online xxxx its interesting properties, for example, as a semiconductor with a quite signicant forbidden band gap
energy of 3.2 eV. In this study, thin lms of titanium dioxide (TiO2) were synthesized in amorphous
Keywords: and crystallographic systems using the solgel process. Atomic Force Microscopy (AFM), Raman spectros-
Titanium dioxide copy and X-ray diffraction (XRD) techniques were applied to obtain structural characteristics of the pre-
Anatase pared lms. We estimated that TiO2 thin lms crystallize in anatase phase between temperatures 380 C
Rutile
and 700 C, and into anataserutile phase at 650 C, while rutile phase exists alone above 800 C. The
Solgel method
changes in porosity of materials in relation to temperature were calculated as well. The refractive index
of titanium dioxide thin lms from ellipsometric measurements is also provided.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Titanium dioxide is one of the most industrially demanded
material, which is used as a photocatalyst for water purications
[1], as a semiconductor for dye-sensitized solar cells [2,3], in thin
lm capacitors [4], in inorganic membranes [5], in panel displays
and in other optical devices [6]. For some applications, it is essen-
tial to obtain TiO2 thin lms with well controlled crystalline struc-
ture, morphology, size and pore distribution. Therefore, studies of
formation mechanisms and the development of new preparation
methods become extremely important [7].
Titanium dioxide thin lms are considered to be very useful
materials in optoelectronic applications, because of their high
optical transmittance in the visible and near infrared regions, good
stability at high temperatures, mechanical abrasion and chemical
durability. TiO2 thin lms can be produced using a variety of tech-
niques like chemical vapor deposition (CVD), ion beam technique,
evaporation, hydrothermal methods, solvothermal synthesis or
solgel methods [79]. On the other hand, the solgel process
Corresponding author. Tel.: +48 (0)58 5235103; fax: +48 (0)58 3413175.
E-mail addresses: aneta.lewkowicz@ug.edu.pl (A. Lewkowicz), beata.grobelna@
ug.edu.pl (B. Grobelna).
1
Tel.: +48 (0)58 5232244.
which is one of the simplest methods offers many advantages such
as controllability, reliability, reproducibility of the material and
therefore can be selected for the preparation of high quality
nano-structured thin lms [10]. Moreover, this process can be per-
formed with a relatively simple experimental setup, it does not re-
quire vacuum and is effective. During this process, the titania
precursor undergoes hydrolysis and condensation reactions lead-
ing to the formation of an interconnected titanium dioxide net-
work. In general, the conditions for preparing TiO2 thin lms
using the solgel process can strongly affect the physical proper-
ties of the lm [11,12]. Therefore, it is vital to systematically study
the structural and optical properties of solgel TiO2 thin lms, tak-
ing into account the preparation conditions.
The main goal of this work was the preparation, the study of the
surface morphology and the optical properties of TiO2 thin lms
deposited on glass with the solgel spin coating technique. As a re-
sult, transparent, nontoxic and chemically stable material was ob-
tained, which may be applied in solar energy conversion or used as
antireective coatings. One of the advantages of this experiment
was also the fact that the thickness of lms could be controlled.
On top of that, our method allows the use of only one step of the
synthesis in order to prepare titanium(IV) oxide thin lms, which
can be used to produce materials with controlled thickness and
composition due to good optical quality and durability of the

http://dx.doi.org/10.1016/j.optmat.2014.02.033
0925-3467/ 2014 Elsevier B.V. All rights reserved.

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2 A. Lewkowicz et al. / Optical Materials xxx (2014) xxxxxx

matrix. Structural and optical evolutions recorded against in- amorphous structure. From this gure it can be concluded that
creases of annealing temperature were investigated with XRD, the layer forms a network structure with comparable size of
AFM, Raman techniques and spectroscopic ellipsometry. 510 lm and the difference in height amounting to single nanome-
ters. In the case of the thin lms which were obtained after anneal-
ing of the material at the temperature of 450 C the formation of
2. Experimental techniques
single grains can be observed (Fig. 1b). Furthermore, an increase
in the concentration of granules in the crack on the surface of
2.1. Materials
the lm was observed. Moreover, these sites are natural centers
of crystallization. However, an increase of the annealing tempera-
All reactants used in this work were of analytical grade. Tita-
ture to 700 C leads to the formation of a homogeneous polycrys-
nium(IV) tetra(2-propanolate), propan-2-ol, poly(ethylene glycol),
talline layer, as can be observed in Fig. 1c. The size of the
Triton X-100 and pentane-2,4-dione were purchased from Sig-
crystallite was estimated from Fig. 3 and it amounts to
maAldrich (Germany). Hydrochloric acid was purchased from
75100 nm. The crystallization at high temperature (900 C)
POCH Company (Gliwice, Poland). Deionized water was obtained
causes the growth of the larger particle grain responsible for the
from Hydrolab system installed in our laboratory.
large increase in roughness (Fig. 1d). On the other hand, the layer
The precursor solution for TiO2 thin lms was obtained using
is still homogeneous and smooth with an average crystallites size
titanium(IV) tetra(2-propanolate), propan-2-ol, Triton X-100 and
of 250 nm.
hydrochloric acid (37%). Detailed procedure on sol preparation
Crystalline TiO2 exists in three phases: rutile (tetragonal), ana-
can be found in our earlier work [9]. Thin lms were distributed
tase (tetragonal) and brookite (orthorhombic). The transformation
over a clean piece of microscopic glass using spin-coating tech-
of amorphous TiO2 to either anatase or rutile and the temperature
nique. The sol was applied on the glass after 90 min following
at which the transformation occurs, depend on many variables,
the addition of water. This specic time was chosen, because spec-
including the method of preparation, the presence metal particles
troscopic and structural properties of hybrid materials strongly de-
or catalysts [13]. Therefore, for optical applications it is necessary
pend on the gelation time. After spin coating, the thin lms were
to control the phases of TiO2, which have different structural and
dried in air conditions for 24 h. Next they were annealed for 3 h
optical properties [14].
at different temperatures of 380, 430, 450, 550, 650, 700, 800
Fig. 2 shows the XRD patterns of the TiO2 thin lms annealed for
and 900 C in air at a speed of 10 per minute.
3 h in air at various temperatures from 380 to 900 C. It can be seen
that the amorphous titanium dioxide can be crystallized with
2.2. Methods
increasing the temperature of the treatment. For the thin lm
being annealed at 380 C we observed the signal at 25.3, which
The topography of the surface and the structure of pores were
can be attributed to the most intense (1 0 1) reection in anatase
analyzed using atomic force microscopy (AFM Nanosurf Easyscan
phase (PDF 00-021-1272). Unfortunately, at this temperature the
2), equipped with AFM dry scanner in the semi-contact mode.
diffraction peak is visible only as an outline. However, annealing
Images were analyzed using Gwyddion 2.30 software.
of the thin lm at 650 C leads to rutile phase to appear (the signal
The presence of crystallized forms of titanium dioxide in the
at 27.1 attributed to the (1 1 0) reection, PDF 01-076-9000). Both
thin lms after heat treatment was examined with X-ray diffrac-
phases coexist also at 700 C, but above this temperature only the
tion method (XRD) using BRUKER D2PHASER equipment employ-
well resolved diffraction peak of the rutile phase can be observed.
ing Cu Ka radiation operated at 30 kV and 10 mA. The XRD
Furthermore, at a temperature of 900 C the outlines of additional
patterns were collected from 20 to 45 2h angle range using scan-
signals of rutile phase at 35.6 and 40.8 can be distinguished. The
ning step of 0.02 and counting time of 0.4 s per step.
intensity of diffraction peaks increases together with the increase
The Raman spectra were obtained with an integrated confocal
of temperature, because of higher amount of titanium dioxide crys-
micro-Raman system with a LabRam Aramis (Horiba Jobin Yvon)
tals. According to Negishi and Takeuchi [15], the anatase-to-rutile
460 mm spectrometer equipped with a confocal microscope. The
phase transformation takes place at a temperature range of 600
excitation source was the diode pumped solid state (DPSS) laser
800 C. However, Kim et al. [16] reported that phase transforma-
emitting green light at 532 nm with 50 mW power.
tion occurred at 1000 C. In our case the phase transformation oc-
Spectroscopic ellipsometry investigations were conducted with
curred at 650700 C. This is connected with the difference in
a phase-modulated ellipsometer Jobin-Yvon UVISEL (HORIBA Jo-
structure and the size of TiO2 thin lms.
bin-Yvon Inc., Edison, USA). The wavelength region under investi-
The parameter which has major inuence on the anatase-to-ru-
gation was sampled over 350850 nm range with a single step
tile phase transformation is the presence of a catalyst. According to
smaller than 0.5 nm. The experiments were carried out at room
Hashimoto et al. [17], using a base catalyst causes rutile peaks to
temperature at the angle of incidence xed at 60. The compensa-
appear at 650 C (diethanolamine was used as a catalyst). How-
tor was set to 45. The incidence angle resulted from Brewsters an-
ever, rutile peaks did not appear at 800 C, when HNO3 was em-
gle of quartz glass substrate. DeltaPsi software (v. 2.4.3) was
ployed in the same amount as diethanolamine. In our work we
employed to determine the spectral distributions of refractive in-
used HCl as a catalyst and rutile peaks appeared at 700 C. The
dex n(k) and the extinction coefcient k(k) of the titanium dioxide
same catalyst was applied by Kim et al. [16] to obtain TiO2 thin
lms. Moreover, the optical band-gap energy Eg was obtained
lms, however, the temperature in which the rutile peaks were ob-
using Taucs plot.
served was higher (1000 C). Another parameter which also plays a
signicant role in the anatase-to-rutile phase transformation is the
3. Results and discussion presence of silver particles. Ivanova et al. [18] obtained the thin
lms of TiO2 doped with silver particles and heated in air atmo-
AFM microscopy provides information about the morphological sphere. In that case the rutile phase appeared at 600 C. However,
and structural changes that have occurred in the studied material the TiO2 thin lms doped with Ag particles, annealed in nitrogen
after its thermal annealing. Surface topography of the thin lms ambient are polycrystalline with XRD lines attributed to anatase
of titanium(IV) oxide was studied using AFM technique. Fig. 1a TiO2 phase and to cubic Ag.
illustrates a layer of TiO2 which was not heated. It is smooth (aver- The Raman spectra of TiO2 thin lms annealed at different tem-
age surface roughness amounts to Sa = 2.8 nm), and has an peratures are shown in Figs. 3 and 4. All the spectra show that

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 A. Lewkowicz et al. / Optical Materials xxx (2014) xxxxxx 3

Fig. 1. AFM image of amorphous TiO2 thin lm: (a) without heat treatment, (b) annealed at 450 C, (c) annealed at 700 C and (d) annealed at 900 C.

Fig. 2. XRD spectra of TiO2 thin lms.

Fig. 3. The Raman spectra of titanium dioxide thin lms (anatase structure).

intensity of these bands increased with temperature. They also
conrm the existence of crystalline titanium dioxide in thin lms.
Fig. 3 presents the characteristic peaks of anatase at: 140 cm1,
194 cm1, 394 cm1, 514 cm1, 634 cm1. The peaks at 634 cm1
and 194 cm1 can be attributed to the anatase Eg mode, and the
peak placed at 394 cm1 is assigned to the B1g mode of the TiO2
anatase phase. However, peak at 514 cm1 is a doublet of A1g and
B1g modes of TiO2 anatase phase [19]. For the TiO2 thin lms an-
nealed at higher temperatures, i.e. 700, 800 and 900 C (Fig. 4)
we observed three characteristic bands at 233 cm1

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4 A. Lewkowicz et al. / Optical Materials xxx (2014) xxxxxx

Fig. 5. Temperature dependence of the optical constants of titanium dioxide thin

lms for n and k at 550 nm and the thickness at different annealing temperatures.

Fig. 4. The Raman spectra of titanium dioxide thin lms (rutile structure).
Gradual shift can be observed in both parameters with increas-
ing annealing temperature, which agrees with the results pre-
sented by Phadke et al. [27] and Mosaddeq-ur-Rahman et al.
[28]. Samples exhibit different optical behaviour at room tempera-
(multi-phonon), 443 cm1 (Eg) and 607 cm1 (A1g) which can be as-
ture (20 C; RT), low temperatures (300600 C; LT) and high tem-
signed to thermodynamically stable rutile phase [13].
peratures (700900 C; HT). For RT and LT the refractive index peak
The results of XRD and Raman spectra are coherent. Both meth-
is placed in UV range. For HT annealing, this peak is shifted to-
ods conrm that the two structural forms of titanium dioxide: ana-
wards longer wavelengths of 370400 nm (3.353.1 eV).
tase and rutile were obtained. Slight difference in temperature of
The effect of temperature is presented also in the variations of
crystalline from XRD pattern and Raman spectra are due to the dif-
energy band gap in Fig. 6. This is attributed to the changes in phase
ference in calibration and the level of background noise distribut-
structure and morphology, as can be seen in the XRD and AFM
ing the signal.
study. Furthermore, the proposed phase structure (amorphous/
Spectroscopic ellipsometry (SE) was employed for the investi-
anatase/rutile) has been marked in Fig. 5. The extinction coefcient
gation of the optical constants and the thickness of the deposited
peaks were placed in UV range below 350 nm. The k values are
TiO2 lms. In this study, tting calculations were based on a
close to 0 for the wavelength down to 380 nm for RT and LT sam-
three-phase optical model (ambient/titanium dioxide/quartz
ples. It originates from the fact that the amorphous and anatase
glass). Regarding deposition of solgel lm in one-step spin coating
TiO2 phases are highly transparent in the VIS wavelength region.
process the titanium dioxide was assumed to be as an isotropic,
HT samples show signicant increase of the extinction coefcient
homogeneous material. The model including roughness outer layer
resulting from the anatase to rutile phase transformation [29].
was also applied, however its use did not decrease tting error sig-
The maximal k value reaches 1.2 at 350 nm for rutile phase com-
nicantly, which proves that deposited TiO2 lms have smooth
pared to 0.15 for anatase form. For HT samples the k values de-
surfaces. This conclusion is in accordance with AFM results pre-
crease close to zero over 600 nm showing lower lm
sented in Fig. 1ad.
transmittance and optical usefulness as well.
The dispersion was simulated by the TaucLorentz oscillator
Gartner et al. [30] proposed following Eq. (1) for calculating
(TL) model [20], consistent with the KramerKronig formula
optical density shift in polycrystalline lms, which results from
resulting in good tting in a wide range of wavelengths. The pro-
porosity change P:
posed dispersion model for amorphous and polycrystalline TiO2
has been used in [21,22]. TL model is also broadly used for descrip-
tion of TiO2 dispersion of the optical properties of sputtered lms
[23] or deposited by spray pyrolysis [24]. This model is a combina-
tion of the Tauc joint density of states and the quantum mechanical
Lorentz oscillator model. TL model ts to the dielectric functions of
amorphous class of materials, which exhibits a peculiarity due to
the presence of two separated contributions of inter-band
electronic transition related to anatase and rutile form. The appro-
priate parameters of TL model were applied for the analyzed layer
considering different lm structure, which was derived from AFM
and XRD results.
The dispersion of quartz glass was taken from optical dispersion
database [25]. The optical model employed was tted to the exper-
imental data by non-linear LevenbergMarquardt regression [26]
using mean-square error minimization. The tting procedure gives
accurate values of lm thicknesses as well as variation of the
refractive index and extinction coefcient versus wavelength.
Moreover, TL model gives also accurate tting close to the band
gap. Spectral variations of n(k) and k(k) of samples on various Fig. 6. The optical band gap of solgel TiO2 thin lms annealed ant various
annealing temperature are presented in Fig. 5. temperatures for 3 h.

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 A. Lewkowicz et al. / Optical Materials xxx (2014) xxxxxx
 
n2  1
P 1 2  100 % 1
nd  1
The lm porosity is calculated using the refractive index
nd = 2.52 of dense, pore-free anatase phase [30] related to the
refractive indices of the analyzed porous TiO2 samples extracted
from SE at 550 nm. Table 1 summarizes the results of spectroscopic
ellipsometry of TiO2 samples versus annealing temperature. From
RT to 380 C, the refractive index at 550 nm shifts gradually from
1.66 up to 2.04 and the thickness from 550 nm to 172 nm. In liter-
ature, Gartner et al. [30] reported n = 2.051 at 546 nm for annealing
temperature T = 300 C, which is in perfect agreement with our
results.
The lm density increases, which is accompanied by a decrease
in pore volume (see the porosity in values in Table 1). One should
also be aware of the possible effects of residual water and organic
residue on the characteristics of the thin lms obtained. The pres-
ence of such residue in the lms annealed at lower temperatures,
especially for short time could exhibit certain inuence on some
properties of thin lms, like their thickness or porosity. However,
for the material annealed at temperature higher than 400 C the
thickness and the porosity of TiO2 thin lms decreases because of
the elimination of water and organic residue.
Moreover, for the thin lms prepared in RT and annealed in
380 C no signicant changes of the Raman spectra and XRD pat-
terns were observed. The changes start from 380 C in Raman shift
and XRD patterns. This is correlated with a transition phase from
amorphous to polycrystalline anatase phase at LT. In the HT range
700900 C the refractive index increases signicantly from 2.05
observed in LT up to 2.36 and 2.58, respectively. This results from
phase transition from anatase to rutile form (700 C), which has
higher refractive index compared to anatase. This is conrmed also
by k value shift presented in Fig. 5. The extinction coefcient at
550 nm increases from nearly zero in RT and LT up to 0.9  101
at 700 C to 1.4  101 at 800 0C. In comparison, Phadke et al.
[27] reported n of 2.2 at 550 nm for TiO2 lm deposited using tita-
nium isopropoxide sol subsequently annealed at 500 C. Moreover,
Mosaddeq-ur-Rahman et al. reported a sharp increase in n from 2.2
at 600 C up to 2.55 at annealing temperature of 800 C (both given
at 550 nm) [28]. These authors achieved slightly higher values than
those reported in other works. The higher refractive index of aque-
ous solgel TiO2 lms presented above could be explained by their
susceptibility to crystallization and a decrease of effective porosity
[30].
The optical absorption coefcient a of TiO2 thin lms was esti-
mated from extinction coefcient k values. The optical band gap
Egopt was determined from the absorption coefcient a by using
Tauc plot [31]. The estimated values of optical band-gap Egopt are
presented in Fig. 6. From Taucs plot analysis of annealed solgel
samples it was observed that band-to-band indirect transitions
are more probable than the direct transitions (not discussed here).
For the samples prepared at RT the band gap of ca. 3.1 eV was
determined. The reasonable increase of band gap up to 3.35 eV
was achieved for the TiO2 lms annealed at temperature range of
Table 1
The refractive index (n) at 550 nm and porosity (P) of TiO2 samples for different
annealing temperatures.
T (C) Thickness (nm) Refractive index (n@550 nm) Porosity, P (%)
20 550 1.66 67.19
380 172 2.04 40.91
430 164 2.08 37.83
700 103 2.36 14.59
800 98 2.54 a [13] F.D. Hardcastle, J. Arkansas Acad. Sci. 65 (2011) 4348.
900 87 2.58 a [14] D.J. Won, C.H. Wang, H.K. Jang, D.J. Choi, Appl. Phys. A 73 (2001) 595600.
a
Rutile form; calculation was performed for anatase phase.
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5
400700 C. Such a band gap has been reported for anatase phase
in solgel [32] and sputtered lms [23]. The transition from ana-
tase to rutile phase at HT observed in XRD and SE results in a sharp
drop of band gap down to ca. 3.15 eV. It is worth of noting that esti-
mated rutile band gap is also in agreement with the values re-
ported by Mechiakh et al. (for annealing temperature of 1000 C)
[12]. Correlation between microstructure and optical properties
of nano-crystalline TiO2 thin lms prepared by solgel dip coating
and Ivanova et al. (sputtered lms) [18]. However, in our study the
anatase-to-rutile transition takes place at 800 C.
4. Conclusion
Highly porous and nanocrystalline titanium(IV) oxide thin lms
have been successfully obtained through the solgel process and
annealed at different temperatures in the presence of air. The re-
sults of XRD and Raman Spectra are coherent and both show that
the TiO2 thin lms without annealing are amorphous, but their
structure shifts through the anatase (380 C) to rutile (700 C)
phases. It is clear that, due to amorphous nature of titanium diox-
ide obtained using the solgel method, the step of heat-treatment
is required.
With increasing the annealing temperature from 20 to 900 C,
the refractive index of TiO2 thin lms increased from 1.66 to 2.58
(at 552 nm) and the porosity of the TiO2 thin lms decreased from
67% to less than 15% because of shrinkage and densication of the
lms. Additionally, we observed the changes in thickness from
550 nm for the lm without thermal treatment, to 87 nm, when
the lm was annealed at 900 C. However, the extinction coef-
cient at 550 nm increases from nearly zero in RT and LT up to
0.9  101 at 700 C to 1.4  101 at 800 C.
These results suggest that we successfully obtained optical
materials in a form of thin lms, possessing the desired structural
and optical properties.
Acknowledgments
This research has been supported by the grant NCN 2011/03/B/
ST5/03094 (P. Bojarski, A. Synak, B. Grobelna) and International
Ph.D. Project Physics of Future Quantum-Based Information Tech-
nologies (MPD/2009-3/4) nanced by Foundation for Polish Sci-
ence (A. Lewkowicz).
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Please cite this article in press as: A. Lewkowicz et al., Opt. Mater. (2014), http://dx.doi.org/10.1016/j.optmat.2014.02.033