Journal of Sol-Gel Science and Technology 24, 147–154, 2002

c 2002 Kluwer Academic Publishers. Manufactured in The Netherlands.

Role of Organic Additives in the Sol-Gel Synthesis

of Porous CaF2 Anti-Reflective Coatings

SHINOBU FUJIHARA,∗ YASUHIRO KADOTA AND TOSHIO KIMURA

Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi,
Kohoku-ku, Yokohama 223-8522, Japan
shinobu@applc.keio.ac.jp

Received December 8, 2000; Accepted November 1, 2001

Abstract. Porous CaF2 anti-reflective coating films were prepared by the sol-gel method. Effects of organic
additives on deposition and optical properties of the films were investigated. Amino alcohols (2-aminoethanol,
2-dimethylaminoethanol, and triethanolamine) and alcohols with larger molecular weights (ethyleneglycol,
2-methoxyethanol, cyclohexanol, and 2-(2-n-butoxyethoxy)ethanol) were chosen as the organic additives. Among
these additives, cyclohexanol was the most effective to control the surface morphology and the optical properties
of the films. By changing the amount of cyclohexanol in the coating solution, it was possible to control the optical
thickness of the CaF2 films. Accordingly, the wavelength giving the maximum transmittance could be changed in
the UV region.

Keywords: CaF2 , thin film, sol-gel, anti-reflective coating

1. Introduction
Fluoride and oxide materials with large band-gap have
been used in ultraviolet (UV) optics. SiO2 glasses
and CaF2 single crystals are the most important ma-
terials as main optical components for UV, deep-
ultraviolet (DUV) and vacuum-ultraviolet (VUV) high-
power lasers [1–5]. Anti-reflective (AR) coatings for
these components are also composed of the UV opti-
cal materials. For a single-layer AR coating, the com-
plete anti-reflection is limited to following conditions;
n 21 = n 0 n 2 and n 1 d = λ/4, where n 0 , n 1 and n 2 are the
refractive index of air, the coating and the compo-
nent, respectively, d the thickness of the film and λ
the wavelength of light [6]. For example, it is neces-
sary to obtain the films with n 1 values less than 1.22
for the SiO2 glass (n 2 = 1.51) and the CaF2 single crys-
tal (n 2 = 1.47) [7] at 248 nm (a wavelength of a KrF
laser).
∗ To whom all correspondence should be addressed.
Since the smallest refractive index is 1.40 (at 248 nm)
of MgF2 among the non-deliquescent, practical inor-
ganic materials, porous films are required to prepare the
single-layer AR coatings. That is, the refractive index
of the films decreases as a porosity increases accord-
ing to the extended Lorentz-Lorenz formula [8]. Porous
coatings are also effective to enhance the laser damage
thresholds [9]. In earlier works, colloidal suspension
methods were adopted to prepare ∼45% porous MgF2
and ∼50% porous CaF2 films [10]. The sol-gel method
is also well known for its possibility to produce various
porous films [11–13]. Recently, the sol-gel processing
of alkaline earth and rare-earth fluoride films has been
developed starting from metal acetates, trifluoroacetic
acid, water and isopropanol [14]. We reported that the
refractive index of sol-gel-derived porous MgF2 thin
films could be controlled by the heat-treatment con-
ditions [15]. In that case, the porosity of the films
changed by the generation of gaseous phases during
the heat treatment of the coating films. Variable pa-
rameters were merely drying and heating temperatures.
148 Fujihara, Kadota and Kimura

Accordingly, the control of the refractive index was
not easy. In this work, we examined effects of or-
ganic additives on the formation and optical proper-
ties of porous CaF2 films through the sol-gel process.
An attempt was made to control the optical thickness,
n 1 d, and morphology of the films by changing the
amount of the additives. It was possible to reduce light
scattering, control the thickness and increase transmit-
tance in the UV region by using cyclohexanol for the
additive.
2. Experimental
2.1. Preparation of Solutions with Various
Organic Additives
0.0025 mol of Ca(CH3 COO)2 ·H2 O was dissolved in
7.5 ml of isopropanol ((CH3 )2 CHOH; IPA), 1.0 ml of
trifluoroacetic acid (CF3 COOH; TFA) and 1.0 ml of
water. 0.1 ml of organic compounds were added to the
solution, which was stirred for 2 h at room tempera-
ture in air. We chose amino alcohols (2-aminoethanol,
2-dimethylaminoethanol, and triethanolamine) and al-
cohols with large molecular weight (ethyleneglycol,
2-methoxyethanol, cyclohexanol, and 2-(2-n-butoxy-
ethoxy)ethanol) as the organic additives. Molecular
weight and boiling point of the additives are listed in
Table 1. All the resultant solutions were clear and ho-
mogeneous, and no phase separation was observed.
2.2. Preparation of Solutions with Cyclohexanol
0.0025 mol of Ca(CH3 COO)2 ·H2 O was dissolved in
7.5 ml of IPA, 1.0 ml of TFA and 1.0 ml of water.
Cyclohexanol was added to the solution. The amount
of cyclohexanol was varied by x in a volume ratio of
cyclohexanol:IPA = x:1 (x = 0, 0.1, 0.2, 0.3, 0.5 and
1.0). The solutions were stirred for 2 h at room temper-
ature (about 30◦ C) in air.
2.3. Deposition of CaF2 Coating Films
A typical procedure for the deposition of CaF2 coat-
ing films was as follows. The solution was spin-coated
on one side of silica glass substrates (1 mm thick) at
2650 rpm. Then the coated substrate was immediately
placed in a furnace and heated at 500◦ C for 10 min fol-
lowed by quenching in air. This procedure was repeated
to increase the number of coating layers.
2.4. Analysis and Measurement
Calcium trifluoroacetate gel powders were obtained
by drying the solutions at 100◦ C for a few
days. Thermogravimetry-differential thermal analysis
(TG-DTA) was conducted with a Mac Science TG-
DTA2020S thermal analyzer in order to measure the
decomposition temperature of the gels. The surface
of the films was observed by field emission scan-
ning electron microscopy (FESEM) with a Hitachi
S-4700 microscope. Optical transmission spectra were
recorded with a Hitachi U-3300 UV-visible spec-
trophotometer. The refractive index, n 1 , and the
thickness, d, of the films were determined by fitting
a calculated transmittance data to the measured ones.
The Sellmeier equation, n 1 (λ) = {A0 + [A1 λ2 /(λ2 −
A2 )]}1/2 , was used for the calculation of the dispersion
of the refractive index, where λ is the wavelength and
A0 , A1 and A2 are the constants. The viscosity of the so-
lutions was measured with a cone and plate viscometer
(E-type, Tokyo Keiki).

Table 1. Chemical formula, molecular weight and boiling point of the organic additives used. Exothermic peak temperatures of the gels
with the additives are also shown.

Molecular Boiling Exothermic peak temperature

Organic additive Chemical formula weight point/◦ C of the gel/◦ C

2-aminoethanol H2 NCH2 CH2 OH 61.08 171.1 327 (strong), 448 (weak)

2-dimethylaminoethanol (CH3 )2 NCH2 CH2 OH 89.14 134 294 (strong), 420 (weak)
triethanolamine N(CH2 CH2 OH)3 137.17 206.7 299 (strong), 420 (weak)
ethyleneglycol HOCH2 CH2 OH 62.07 197.85 357 (strong)
2-methoxyethanol CH3 OCH2 CH2 OH 71.60 124.5 362 (strong)
cyclohexanol C6 H11 OH 100.16 161.1 347 (strong)
2-(2-n-butoxyethoxy)ethanol CH3 (CH2 )3 OCH2 CH2 OCH2 CH2 OH 162.23 230 347 (strong)
 Role of Organic Additives 149

3. Results and Discussion

3.1. Effects of Organic Additives on Deposition and

Optical Properties of CaF2 Coating Films

We showed in our previous work that the forma-

tion of CaF2 from the solution without the additives
was strongly exothermic with a DTA peak around
342◦ C [14]. The CaF2 films could be obtained by heat-
ing the spin-coated films above 300–400◦ C. Typical
TG-DTA curves of the gels containing the organic
additives are shown in Fig. 1, and the DTA exother-
mic peak temperatures are summarized in Table 1.
The most striking difference between the two gels
added with (a) 2-dimethylaminoethanol (DMAE) and
(b) 2-methoxyethanol (ME) is their exothermic behav-
ior. The strong exotherm is observed at 294◦ C with an
abrupt weight loss for the gel with DMAE. In addi-
tion, a broad and weak exothermic peak is observed
at 420◦ C, which is accompanied by a slight weight
loss. On the contrary, only one sharp exothermic peak
is observed at 362◦ C for the gel added with ME. It is
considered that trifluoroacetate ions, CF3 COO− , are
coordinated to Ca2+ ions in the trifluoroacetate gel
and the decomposition of the gel follows a reaction
[14, 15];

Ca(CF3 COO)2 → CaF2 + gaseous phases.

The gaseous phases are composed mainly of

(CF3 CO)2 O, CO, and CO2 [15]. The theoretical weight
loss of this reaction is as large as 70.7%. Therefore, the
peaks at 294 and 362◦ C in Fig. 1(a) and (b), respec-
tively, are due to the formation of CaF2 .
The thermal decomposition behavior of the gels
added with 2-aminoethanol or triethanolamine was
the same as that with DMAE as shown in Table 1.
The second weak exothermic peaks appeared at tem-
peratures higher than 420◦ C. On the other hand, the
gels with ethyleneglycol, cyclohexanol and 2-(2-n-
butoxyethoxy)ethanol had one sharp exothermic peak.
These results can be explained with the molecular struc-
ture and the coordination of the additives in the solu-
tion. In the presence of water, the calcium trifluoroac-
etate is coordinated also by one H2 O molecule [16].
When we compare Fig. 1(a) and (b), weight loss due
to dehydration at temperatures less than 250◦ C is ob-
served only for the gel with ME. The absence of such
dehydration in the gel with DMAE implies occurrence
of the coordination between Ca2+ and amine nitrogen
Figure 1. (a) TG-DTA curves of the dried solution added with
2-dimethylaminoethanol (DMAE). (b) TG-DTA curves of the dried
solution added with 2-methoxyethanol (ME).
instead of water. The decrease in the decomposition
temperature of the gels to form CaF2 would be related to
this coordination. The second peak at 420◦ C in Fig. 1(a)
is attributed to the decomposition or the combustion of
DMAE.
The fluoride films prepared from the solutions with-
out the additives have generally the porous structure be-
cause of the generation of the gaseous phases during the
heat treatments [15]. In addition, the additives can work
as the origin of the pores when they burn during the
heat treatments. Therefore, the thermal decomposition
150 Fujihara, Kadota and Kimura
Figure 2. FESEM photographs of the surface of the CaF2 films obtained from the solutions containing (a) 2-aminoethanol and (b)
2-methoxyethanol.
behavior of the additives largely influences the mor-
phology of the porous films. Figure 2 shows the surface
morphology of the CaF2 thin films with three coating
layers obtained from the solution added with (a) 2-
aminoethanol (AE) and (b) ME. It is clearly seen that
the addition of AE makes the film more porous. This
result is related to the above discussion about the ther-
mal analysis. That is, AE remains in the film during the
formation of CaF2 by the decomposition of the precur-
sor. The heating temperature of 500◦ C is enough high
to decompose AE and successively form pores in the
film. In reality, it is considered that these decomposi-
tion reactions proceed in a short time of 10 min with
each cycle of the heat treatment. The surface morphol-
ogy of the film from the solution with ME is almost the
same as that with no additive [14]. ME does not remain
in the film after the formation of CaF2 , as suggested by
the thermal analysis of the gel.
The transmittance spectra of the silica glass substrate
coated with the CaF2 films from the solutions con-
taining the organic additives are shown in Fig. 3. The
deposition was conducted with one coating layer on
one side of the substrate. All the substrates coated with
the films from the solution containing the amino alco-
hols exhibit lower transmittance than the uncoated sub-
strate especially in the UV region as shown in Fig. 3(a).
Although a little interference is observed, the trans-
mittance monotonically decreases with decreasing the
wavelength. The transmittance at 200 nm is 85.1,
83.6 and 51.0% for the additive of 2-aminoethanol,
2-dimethylaminoethanol, and triethanolamine, respec-
tively. The reduced transmittance is attributed to the
organic residue as well as light scattering by large
pores. The film exhibited brown color in case of the
triethanolamine additive.
The films with the other additives such as ethyleneg-
lycol, 2-methoxyethanol, cyclohexanol and 2-(2-n-
butoxyethoxy)ethanol have the AR effect as shown in
Fig. 3(b). The decrease in the transmittance due to light
scattering is not serious even in the UV region. These
films exhibit large interference. The position of the
interference peaks with the maximum transmittance,
Tmax , corresponds to the wavelength which fulfills
the AR condition, n 1 d = i(λ/4) (i: odd numbers). The
peak position of the minimum transmittance, Tmin ,
are determined by n 1 d = j(λ/4) ( j: even numbers). If
the Tmin values of the coated substrate are lower than
the transmittance of the uncoated substrate, the coating
film has positive inhomogeneity. This means that the
refractive index of the film gradually increases from
the substrate side to the air side [17, 18]. It is seen
that the inhomogeneity is larger in the films with 2-
methoxyethanol and 2-(2-n-butoxyethoxy)ethanol.
In summary of this sub-section, it was revealed that
the organic additives largely influenced the deposition
and the properties of the CaF2 films. The coordination
state and the decomposition behavior of the additives
were the main factors to be taken into account. Among
the additves examined, ethyleneglycol and cyclohex-
anol were suitable for the preparation of the CaF2 AR
coating films.
3.2. Control of Optical Thickness
of AR Coating Films
The most important parameter for the AR coatings
is the optical thickness, n 1 d, as stated above. The
wavelength giving the maximum transmittance can be
changed by controlling n 1 d. However, it was difficult
to control the thickness d by changing the number of

Figure 3. (a) Transmittance spectra of the silica glass substrate
coated with the CaF2 films obtained from the solutions contain-
ing 2-aminoethanol (AE), 2-dimethylaminoethanol (DMAE) or tri-
ethanolamine (TEA). (b) Transmittance spectra of the silica glass
substrate coated with the CaF2 films obtained from the solutions con-
taining cyclohexanol, ethyleneglycol, 2-(2-n-butoxyethoxy)ethanol,
or 2-methoxyethanol (ME).
coating layers because the film inhomogeneity was en-
hanced in the direction perpendicular to the surface
of the substrate [15]. Changing the concentration of
Ca2+ ions in the IPA-TFA-H2 O solution was effective
to control the thickness, but the transmittance in the UV
region was decreased in that case probably due to light
Role of Organic Additives 151
Figure 4. FESEM photographs of the surface of the CaF2 films
obtained from the solutions containing cyclohexanol with the amount
of x = (a) 0.1, (b) 0.5 and (c) 1.0.
scattering. Therefore we attempted to control n 1 d of the
porous CaF2 AR coating films by using cyclohexanol
as the additive to the solution.
Figure 4 shows the surface morphology of the CaF2
thin films of x = 0.1, 0.5, and 1.0 (x: the volume ratio
of cyclohexanol to IPA) obtained by heating at 500◦ C
for 10 min. The coating time was once. Vein-like pores
are seen in all the films. The amount of smaller pores
in a flat part of the films decreases with increasing x.
152 Fujihara, Kadota and Kimura

The surface of the film from the IPA solution (x = 0)

was the same as that of the x = 0.1 film. The addi-
tion of cyclohexanol is obviously effective to reduce
the pores which may cause light scattering. In sol-gel
coatings, the solvents evaporate to some extent just
after spin-coating the solution on the substrate. Since
cyclohexanol has the higher boiling point of 161.1◦ C
than IPA with 82.4◦ C, it remains in the films before the
heat treatment and works well as the additive which
controls the film deposition process.
The transmittance spectra of the substrates coated
with the films of x = 0, 0.1, 0.2, 0.3, 0.5, and 1.0 are
shown in Fig. 5(a) and (b). Interference is observed
for the films of x = 0–0.5. On the contrary, the film
of x = 1.0 exhibits no interference, implying that the
film thickness is very small. The refractive index, n 1 ,
and the thickness, d, of the films determined with
these spectra is listed in Table 2. While n 1 is almost
constant, d decreases with increasing x. As a result,
the optical thickness n 1 d decreases with increasing x.
Accordingly, the wavelength giving Tmax decreases
following the equation, n 1 d = i(λ/4), as seen in
Fig. 5.
With the silica glass substrates, the original beam of
incident light is decreased in intensity approximately
by the reflectance of 4.1% per surface, making a total of
8.2% [6]. The AR coating on one side of the substrate
can reduce this 4.1% reflectance if the complete AR
condition is fulfilled. The degree of the AR effect can be
estimated by finding T defined by T = Tmax − Tsub
(Tsub : the transmittance of the substrate). The relation-
ship between T and the wavelength for the present
CaF2 films are plotted in Fig. 6. In this plot, the highest
transmittance value is given at the wavelength deter-
mined by i = 3 (the films of x = 0.1, 0.2, 0.3, and 0.5) or
i = 1 (x = 1.0) in n 1 d = i(λ/4). With any wavelength,
about 2.0–2.5% of T is obtained. These results Figure 5. (a) Transmittance spectra of the silica glass substrate
coated with the CaF2 films obtained from the solutions containing
Table 2. The refractive index, n 1 , the thickness, d, and the cyclohexanol with the amount of x = 0, 0.1 and 0.2. (b) Transmit-
optical thickness, n 1 d, of the CaF2 films obtained from the tance spectra of the silica glass substrate coated with the CaF2 films
solutions with the content of cyclohexanol, x. obtained from the solutions containing cyclohexanol with the amount
of x = 0.3, 0.5 and 1.0.
Refractive index Thickness Optical thickness
x (n 1 ) (d/nm) (n 1 d)
indicate that the AR effect can be attained at a desired
0 1.31 299 300 wavelength in the UV range by controlling the optical
0.1 1.36 190 258 thickness of the porous CaF2 coatings.
0.2 1.35 175 236 It can be explained why the thickness and hence the
0.3 1.33 135 180 optical thickness of the films decrease with increasing
0.5 1.31 116 152 x as follows. The concentration of the Ca2+ ions, C,
1.0 1.34 64 86
in the solution decreases with increasing x; 0.24, 0.23,
0.21, 0.19, and 0.15 mol/l for x = 0.1, 0.2, 0.3, 0.5 and

Figure 6. A plot of T vs. wavelength for the CaF2 AR coating
films.
1.0, respectively. In contrast, the viscosity, η, of the
solution increases with x; 2.91, 3.23, 3.47, 3.89, 4.33,
and 5.81 cP (1 cP = 10−3 Pa · s) for x = 0, 0.1, 0.2, 0.3,
0.5 and 1.0, respectively. Then the relationship between
η and x is linear as shown in Fig. 7(a) and is expressed
by the following equation,
η = 2.88x + 2.93
When we plot d/C values against η as shown
in Fig. 7(b), the following relationship can be
derived,
d/C = 2.56 × 106 /η
From the Eqs. (1) and (2), the relationship among x, C
and d can be expressed by the equation,
d = 2.56 × 106 C/(2.88x + 2.93)
In general, the coating films become thinner as the
concentration and/or the viscosity of the solution are
lowered in spin coating [19]. Under the present ex-
perimental conditions, the Eq. (3) demonstrates that
the thickness, d, decreases with decreasing the Ca2+
concentration, C, or increasing the amount of cyclo-
hexanol, x, and therefore η. The latter case comes
from poorer wettability of the solutions with the larger
amount of cyclohexanol on the silica glass substrates,
which we observed experimentally. In conclusion, the
optical thickness of the CaF2 films can be controlled by
changing C and/or x and hence the film thickness since
the refractive index of the films was nearly constant.
Role of Organic Additives 153
Figure 7. The relationship (a) between η and x and (b) between
d/C and η.
(1) 4. Conclusions
The role of the organic additives in the fabrication of
the porous CaF2 AR coatings via sol-gel has been in-
vestigated. While the addition of the amino alcohols,
2-methoxyethanol, and 2-(2-n-butoxyethoxy)ethanol
(2) degraded the transmittance of the films especially in
the UV region, ethyleneglycol and cyclohexanol were
effective to prepare the highly transparent films. By
changing the amount of cyclohexanol in the coating
solution, it was possible to control the optical thick-
(3) ness of the CaF2 films. The wavelength giving the
maximum transmittance could be controlled in the UV
region.
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