J Nanopart Res (2008) 10:1225–1229
DOI 10.1007/s11051-008-9373-4
BRIEF COMMUNICATION
A version of Stöber synthesis enabling the facile prediction
of silica nanospheres size for the fabrication of opal photonic
crystals
Diego Adolfo Santamarı́a Razo Æ Luca Pallavidino Æ Edoardo Garrone Æ
Francesco Geobaldo Æ Emiliano Descrovi Æ Angelica Chiodoni Æ
Fabrizio Giorgis
Received: 1 August 2007 / Accepted: 4 February 2008 / Published online: 11 March 2008
Ó Springer Science+Business Media B.V. 2008
Abstract A sol-gel synthesis procedure based on
the method proposed by Stöber et al. (J Colloid
Interface Sci 26:302–315, 1968) has been adopted for
the one-step preparation of mono-dispersed silica
nanospheres. An excellent control of the particle
diameter over a wide range is obtained by varying the
amount of silicon alkoxide only, while the concen-
tration of all other components is kept fixed: this
allows the fabrication of artificial opals with a finely
tuned and precisely predictable lattice parameter.
Keywords 3-D Photonic crystals
Synthetic opals

Bragg reflection peak
Monodispersed silica
nanospheres
Self assembly
Colloids
Introduction
Since the early stages of the sol-gel process (Stöber
et al. 1968; Bogush et al. 1988), hydrolysis of silicon
D. A. Santamarı́a Razo
L. Pallavidino

E. Garrone
F. Geobaldo (&)
Materials Science and Chemical Engineering Department,
Politecnico of Torino, C.so Duca degli Abruzzi 24, 10129
Torino, Italy
e-mail: francesco.geobaldo@polito.it
E. Descrovi
A. Chiodoni
F. Giorgis (&)
Materials and Microsystems Laboratory vLab-Physics
Department, Politecnico of Torino, C.so Duca degli
Abruzzi 24, 10129 Torino, Italy
e-mail: fabrizio.giorgis@polito.it
alkoxides has been aimed to obtaining monodisperse
SiO2 nanospheres. Final particle sizes strictly depend
on the reagent concentrations and reaction tempera-
tures, so that difficulties are usually encountered in
obtaining both a good control of the spheres size in a
wide dimensional range and monodispersity with size
distribution as narrow as possible. This has become a
key requirement after the discovery of photonic
crystals. In such structures, the dielectric constant is
spatially modulated in several dimensionalities (i.e.,
1D, 2D or 3D), by imposing a periodicity of the order
of the light wavelength. As a consequence, the
structure yields the appearance of an energy range not
available to the electromagnetic wave propagation
(Joannopoulos et al. 1995), known as photonic band
gap (PBG).
Opal structures obtained from silica nanosphere
colloidal suspensions allowed the fabrication of 3D
photonic crystals (Mı́guez et al. 1997; Lopez et al.
2003; Pallavidino et al. 2006). Under suitable condi-
tions involving spheres self-assembling, such as dip-
coating, sedimentation or centrifugation, an ordered
3D packing is obtained, with face-centered cubic
(fcc) structure and the {111} plane parallel to the
substrate. For this purpose, the nanosphere size
dispersion has to be as low as possible (polydispersity
\5%).
Among 3D photonic crystals, synthetic opals
present several advantages. For instance, they allow
the synthesis of inverse opals, (i.e., a silicon matrix
filling the interstices between air spheres), exhibiting
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a high refractive index contrast. This fact may even
lead to a complete PBG, with a forbidden energy
range independent of the direction and polarization
states of the radiation (Vlasov et al. 2001). Besides
the intrinsic linear optical properties of silica opaline
structures, appealing features were recently analyzed
in terms of electrically controlled optical birefrin-
gence and laser-like emission obtained through liquid
crystal (Gottardo et al. 2006) and dye infiltrations,
respectively (Frolov et al. 1999).
Synthesis of silica spheres is commonly carried
out following the well-known Stöber–Fink–Bohn
method (Stöber et al. 1968), where hydrolysis and
condensation of a silicon alkoxide are catalyzed by
ammonia.
Spheres formation is the result of a complex
mechanism of nucleation and growth. By varying the
composition of the starting solution, it is possible to
change the particles diameter: available studies,
however, have not yet reached clear-cut conclusions
as to the mechanism.
The common synthesis procedure consists in fixing
the TEOS amount and playing with the molar ratio
between H2O/NH3/C2H5OH in the starting solution:
in this way a wide range of sphere diameters can be
obtained (Giesche 1994a, b; Van Blaaderen et al.
1992; Lindberg et al. 1997; Vacassy et al. 2000;
McComb et al. 2001). Most previous analyses of the
relationship between water/NH3 concentrations and
final spheres diameter do not show any monotonic
behavior: even empirical fitting procedures do not
reliably predict the spheres diameter in different
synthesis cycles, in particular for large sizes (Giesche
1994a, b; Van Blaaderen et al. 1992; Lindberg et al.
1997; Vacassy et al. 2000; McComb et al. 2001).
Bogush et al., Giesche, and Chen et al. obtained
much better results, both in terms of size prediction
and control of polydispersity by means of a seeded
growth technique, a two step procedure (Bogush
et al. 1988; Giesche 1994a, b; Chen et al. 1996).
First, small spheres, constituting the seeds for
successive growth, are synthesized through the stan-
dard procedure. In a second step, an amount of TEOS
is added: under appropriate conditions, TEOS only
interacts with the nuclei surface, no additional nuclei
being formed. In excess of H2O, TEOS hydrolysis is
complete and the dimension increase of the spheres is
simply controlled by the mass of the precursor
alkoxide: consequently, a cubic-root dependence of
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J Nanopart Res (2008) 10:1225–1229
the particle diameter over the TEOS concentration
has been found (Bogush et al. 1988; Giesche 1994a,
b; Chen et al. 1996).
In the present work, we show how the same type of
results (reproducibility, monodispersity, cubic-root
dependence) can be obtained in a much simpler one-
step procedure, consisting in the control of the
amount of the silica source, while the molar ratios of
all other components in the starting solution are kept
fixed. Under these conditions, spheres were obtained
with diameter ranging between 160 and 600 nm with
less than 3% of polydispersion.
Experimental
Silica nanospheres were synthesized following the
Stöber–Fink–Bohn method (Stöber et al. 1968) start-
ing from tetraethyl orthosilicate (TEOS [98%,
Aldrich), doubly distilled water (Labochem), ammo-
nia (33%, Riedel), and absolute ethanol (99.9%,
Labochem) as precursor alkoxide, hydrolyzing agent,
catalyst and solvent, respectively. Two mother solu-
tions were prepared: one containing ammonia–water
with a fixed mole ratio, the other containing TEOS–
ethanol with variable amount of the former and a
fixed amount of the latter. The same volumes of the
two solutions were always mixed in a thermostati-
cally controlled water bath (30 ± 1 °C), so that the
only actual variable was the TEOS amount.
After 180 min, the resulting spheres were physi-
cally separated from the liquid phase and then re-
dispersed into distilled water. Subsequently, opals are
produced through a dip-coating technique (Jiang
et al. 1999). This self-assembling method involves
dipping a nearly vertical substrate (glass slide) into
the suspension of nanospheres (0.5–1 vol%). Thanks
to meniscus forces at the substrate surface, the
evaporation of water at a temperature around 60 °C
leads to the deposition of ordered 3D fcc sphere
packing with a rather uniform thickness up to
20–30 lm.
Opals were characterized by means of field
emission scanning electron microscopy (FESEM),
laser scanning confocal microscopy (LSCM) and
optical reflectance spectroscopy.
Two sets of experiments were actually carried out,
differing by the composition of the former mother
solution, the one with constant composition and only
J Nanopart Res (2008) 10:1225–1229
containing water and ammonia. In set A (the one
basically referred to in this article), the mole number
of ammonia, water and ethanol was: 0.46, 2.89, and
2.15, respectively. For set B, mostly used for
comparison, the same mole number was: 0.41, 2.20,
and 2.15. Note the higher basicity of the latter
solution.
Results and discussion
Figure 1a–b shows typical FESEM pictures of silica
opals which evidence the high quality of the top
layer. Because of the partial transparency of the silica
spheres, the LSCM technique allows a direct imaging
of the neighboring stacked layers. In Fig. 1c–e, we
show reflectance maps of three different layers
starting from the top (Fig. 1c) and moving toward
the bottom (Fig. 1d–e) of the artificial opal. As bright
spots identify the opal vertexes, hexagons put in
evidence the fcc packing symmetry of the spheres.
The vertexes of the hexagons associated to each layer
never overlap. Furthermore, their spatial arrangement
reveals a vertical A–B–C layer packing.
The close packed opaline structure yields a
reflectance peak corresponding to a Bragg reflection
Fig. 1 Images of silica
opals with different sphere
dimensions: (a–b) FESEM
planar viewgraphs of silica
opals with diameters
480 nm and 540 nm; (c–e)
LSCM characterization of
the first three stacked
layers, obtained by
selectively choosing the
object plane of the
microscope. Three
hexagons with vertexes
corresponding to the opal
spheres evidence the fcc
structure
1227
from the {111} planes at a characteristic wavelength
k111 (Waterhouse and Waterland 2007):
rffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2
k111 ¼ 2 d  n2eff  sin2 ðhÞ ð1Þ
3
where h is the light incidence angle, d is the sphere
diameter, neff is the PC effective refractive index.
This can be estimated within the effective medium
approximation as
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  ffi
neff ¼ n2air
1  fsphere þ n2SiO2
fsphere ð2Þ
f being the volume fraction (fsphere = 0.74 for the
ideal fcc structure).
Figure 2 illustrates the dependence of the 111
Bragg peak wavelength k111 upon the sphere diam-
eter d, as evaluated from SEM pictures, for set A of
samples. Most of the synthesized samples are repre-
sented in the diagram as square dots: for a selection
of specimens, the actual reflectance spectra are
reported. According to Eq. 1, the peak wavelength
k111 is expected to be proportional to the diameter d
of the opal spheres. This is what observed: the
proportionality constant results *0.46, which implies
a realistic refractive index nSiO2 *1.44 if we assume
fsphere = 0.74.
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1228 J Nanopart Res (2008) 10:1225–1229

Results in Fig. 2 suggest that a reliable estimation The proportionality constant ks depends on the on
of the sphere diameter d can be readily obtained the fixed NH3/H2O/C2H5OH mole amounts. That for
through Eq. 1 by taking the reflectance spectra of the set A is:
self-assembled fcc opaline structures.  
nm
In Fig. 3, the dependence of the sphere diameters ka ¼ ð1227  2) 3p ffiffiffiffiffiffiffiffi
on the TEOS amounts in the second mother solution mol
is shown for both sets A and B, obtained with and for set B:
different H2O/NH3/C2H5OH mole amounts.  
nm
The dependence of diameter d and TEOS amount kb ¼ ð1486  14) p3
ffiffiffiffiffiffiffiffi :
molTEOS is neatly illustrated by a cubic-root mol
relationship: A discussion of the mechanism of silica spheres
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi formation is outside the scope of the present work. We
d ¼ kS 3 molTEOS ð3Þ
note, however, that the dependence of d on the cubic root
of the TEOS concentration (Eq. 3), already found for
seeded growth (Bogush et al. 1988; Giesche 1994a, b;
700
Chen et al. 1996), agrees with a naı̈ve model in which
600 the constant composition of ammonia, ethanol, and
Reflectance [arb. units]

water plays a major role in the nucleation process (in

Sphere Diameter [nm]

500
particular in dictating the nuclei volume density), as
400 compared to the TEOS concentration at constant
300 composition of the other ingredients. The total TEOS
mass is then partitioned among the growing nuclei, so
200
explaining the cubic-root law. Such a model is obvi-
100 ously valid only at low TEOS amounts. In fact, the
cubic-root relationship between d and molTEOS is no
0
400 600 800 1000 1200 1400 longer followed for large TEOS amounts. The different
Wavelength [nm] value of ka and kb seem to correspond to a lower value of
the density of nuclei in the more basic solution.
Fig. 2 Normalized reflectance spectra of opals with several
lattice parameter evidencing {111} Bragg reflection; measured The monotonic dependence of d on molTEOS shown
sphere diameters are reported on the left axis (squares in Fig. 3 offers a straightforward means for the accurate
symbols); the straight line evidences the direct proportionality prediction of the sphere diameter, in particular, as it
concerns the tailored making of artificial opals.
700

600 Conclusions
Sphere diameter [nm]

B
500
The experimental conditions for obtaining silica
400 nanospheres following the Stöber method have been
A set so control the particle diameter and monodispersity,
300 which can be reached by simply fixing the NH3/H2O/
C2H5OH mole amounts and varying the TEOS mass.
200 This method, a one-step procedure, allows a repro-
ducible fabrication of the desired opaline structure.
100
0.01 0.02 0.03 0.04 0.05 0.06 0.07
TEOS moles
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