J Sol-Gel Sci Technol
DOI 10.1007/s10971-014-3417-2
ORIGINAL PAPER
Thickness–concentration–viscosity relationships in spin-coated
metalorganic ceria films containing polyvinylpyrrolidone
A. Calleja • S. Ricart • M. Aklalouch •
N. Mestres • T. Puig • X. Obradors
Received: 12 November 2013 / Accepted: 27 May 2014
Ó Springer Science+Business Media New York 2014
Abstract Zr-doped ceria thin films were prepared by
spin-coating metalorganic solutions containing polyvinyl-
pyrrolidone (PVP), which serves as a relaxing agent to
relieve the strong mechanical stresses developed during the
thermal decomposition step. The precursor solutions were
deposited on silicon substrates and subsequently heated in
air at 500 °C. The complete decomposition of organics was
checked by infrared spectroscopy with attenuated total
reflectance. The molar ratio between PVP and total metal
ions was varied between zero and one. Furthermore, the
effect of using two different PVP molecular weights was
also investigated. For the high molecular weight of PVP,
crack-free films as high as 150 nm could be obtained
compared to 30 nm when no PVP is added. Thickness after
spin-coating and after thermal decomposition were deter-
mined by profilometry and correlated with the polymer
concentration in the precursor solution, showing a linear
dependence with PVP concentration in both cases. The
main controlling parameter of the final thickness is the
viscosity, with similar power law dependencies both before
and after thermal treatment, which would indicate that the
porosity fraction remains essentially constant in the final
films. Furthermore, AFM analysis was used to investigate
the flatness and surface porosity of the films after the
thermal treatment.
A. Calleja (&)
S. Ricart
N. Mestres
T. Puig
X. Obradors
Institut de Ciència de Materials de Barcelona-Consejo Superior
de Investigaciones Cientı́ficas (ICMAB-CSIC), Campus de la
UAB, 08193 Bellaterra, Catalonia, Spain
e-mail: acalleja@icmab.es
A. Calleja
M. Aklalouch
OXOLUTIA SL, Edifici Eureka, Parc de Recerca de la UAB,
Campus de la UAB, 08193 Bellaterra, Catalonia, Spain
Keywords Sol–gel
Films
Ceria
Metalorganic
decomposition
Polymer
Thickness
1 Introduction
During the preparation of ceramic thin films via sol–gel
routes, strong mechanical stresses appear during drying and
pyrolysis which can lead to fatal cracking of the films [1].
Such stresses become even more important as the film
thickness is increased. In general, a critical thickness
appears which depends on mechanical film toughness,
plasticity, strain and adherence to the substrate [2].
In order to increase the film thickness in a single coat,
mechanical relaxation at these stages of film formation
should be promoted. Towards this goal, several approaches
have been tried either modifying the processing, for
instance, via slower heating ramps or flux flow adjustment
[3] or using additives in the solution [4]. The alternative
option is to stack different films by multicoating approa-
ches. One of the most successful approaches is using inkjet
printing deposition on a hot plate [5], which allows high
thicknesses by sequential multideposition of thinner films
with intermediate heating steps.
In the case of CeO2, increasing the film thickness is
advantageous for a large number of applications: as buffer
layer for simplified architectures of coated conductors [6],
electrolytes for intermediate-temperature fuel cells and
membranes [7], UV-protection layers [8, 9], corrosion
resistance coatings on steel [10] or heterogeneous catalysis
[11]. However, producing crack-free CeO2 films with
thicknesses higher than 100 nm has proven troublesome.
Related to this, chemical doping of CeO2 with rare-earth
cations has been shown to be a useful strategy in increasing
the critical thickness [12, 13]. Moreover, Zr-doping
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 J Sol-Gel Sci Technol

promotes ionic mobility at crystallization temperatures in Table 1 Summary of tested precursor solutions describing metal and
ceria films, diminishing surface roughness, which is highly PVP concentrations, length of PVP chain and [PVP]/[Ce ? Zr] molar
ratio
desirable in buffer layers for coated conductors and
favouring removal of carbon impurities [14, 15]. Sample Ce ? Zr PVP Mw [PVP]/
On the other hand, chemical solution deposition (CSD) reference [M] [M] PVP [Ce ? Zr]
offers a cost-effective methodology to prepare functional A-1 0.500 0.000 Low 0.00
oxides in thin film form [16]. It starts from a precursor A-2 0.500 0.125 Low 0.25
solution containing the metallic salts in stoichiometric A-3 0.500 0.250 Low 0.50
amounts dissolved in a suitable solvent. In this case, large A-4 0.500 0.375 Low 0.75
stresses develop in the early stages of drying and pyrolysis A-5 0.500 0.500 Low 1.00
which should be suitably managed to preserve the B-1 0.500 0.000 High 0.00
mechanical integrity of the films.
B-2 0.500 0.125 High 0.25
In this respect, in-plane tensile stress during thermal
B-3 0.500 0.250 High 0.50
treatment of the as-deposited films can be reduced by
B-4 0.500 0.375 High 0.75
adding polyvinylpyrrolidone (PVP) to the precursor solu-
B-5 0.500 0.500 High 1.00
tion, as first proposed by Kozuka et al. [17]. Since then,
progress has been made in increasing the critical thickness Low and high stand for the PVP molecular weights 5.8 9 104 and
1.3 9 106, respectively
of several technologically relevant advanced ceramics in
the form of thicker films [18–20]. PVP impacts favourably
the processing of CSD films in different ways: (1) PVP crack-free thick films. Moreover, the dependence of the
amide groups coordinate to metal cations [21] and thus polymer concentration on the final film thickness is
diminishes the condensation reactions that produce rigid investigated when spin-coating is used as the deposition
metalloxane networks, which increase stiffness; (2) The technique, in order to obtain clues about the evolution of
excellent film-forming properties of PVP help relax the porosity in this system.
tensile stress by increasing plasticity of the gel as reported
by Kozuka et al. [22]; (3) The fact that PVP decomposes at
temperatures higher than the metalorganic decomposition 2 Experimental
process (250–350 °C, typically) allows the retardation of
the condensation reactions during the sharp shrinkage and The doped-ceria precursor solution was prepared by
(4) Last but not least, PVP is considered a non-toxic weighing appropriate amounts of cerium(III) 2,4-pentadi-
chemical [23]. onate hydrate and zirconium(IV) 2,4-pentadionate
However, the addition of significant amounts of organic (Aldrich) in propionic acid (PANREAC) as a solvent. The
polymers in the precursor solution implies large volumes of nominal formula was Ce0.90Zr0.10O2. Then, two different
decomposition gases that should escape from the film types of PVP (–(C6H9NO)n–) were used with
during the heating process at some stage. This usually Mw = 5.8 9 104 and 1.3 9 106 (K-29/32 from ISP Global
causes entrapped porosity inside the final oxide layer that Technologies and Alfa Aesar, respectively). For the low
leads to poor performing films, especially when a flat and molecular weight PVP, the capped vial was stirred mag-
dense epitaxial oxide structure is sought. This porosity netically for 24 h at room temperature to accomplish full
problem should be more severe in thicker layer as the solubilization. In the case of high molecular weight PVP, it
decomposition gases should be released through the film was necessary to let the mixture stand for 12 h in order to
travelling longer diffusion paths. In this respect, the get swelling of the polymer prior to the stirring stage.
mechanical properties of the surrounding remains of the Metal molarity is expressed as the sum of cerium and
metalorganic salts, either partially or totally decomposed, zirconium cations whereas PVP molarity is expressed as
should also play an important role in the degree of com- mols of repetitive unit of the polymer with M = 111.1.
pactness of the final structure. In fact, little is known about Each film was prepared from a unique solution. In Table 1,
the effect of the polymers during the thermal decomposi- the data of the precursors solutions are displayed. Series A
tion in CSD approaches. In general, the benefits of the and B correspond to low and high molecular weight,
polymers in relieving mechanical stresses due to their respectively. In each series, PVP to metal cation molarities
viscoelastic characteristics are hindered by excessive ranges from 0 to 1. Solution volumes were 2 ml. Stability
porosity in the final film. of solutions varies between 1 and 4 weeks.
In this work, PVP has been studied as a stress-relaxing Then 15 ll of the fresh yellowish precursor solution
additive in the metalorganic precursor solution of zirco- were spin-coated onto single crystal polished squared-
nium-doped ceria films with the ultimate aim to obtain shaped silicon pieces cut from a large wafer. All substrates

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J Sol-Gel Sci Technol
100
µ (mPa·s)
10
1
0,000 0,125 0,250 0,375 0,500
PVP (M)
Fig. 1 Semi-log plot showing the exponential dependence of
viscosity for the low (filled square) and high molecular weight (filled
triangle) series versus polymer concentration
were carefully washed with acetone and methanol before
spin-coating deposition. Dimensions were 5 9 5 mm2.
Acceleration rate up to 6,000 rpm was 2 s and spinning
was maintained for 2 min.
The films were then heated in air using a hot plate
applying a thermal profile up to 500 °C with a heating
ramp of 5 °C/min followed by a 30-min dwell. The final
thickness was determined with an average of 5 height
measurements at different regions of the profilometric
image. Film thickness was obtained by scratching the
heated film with a sharp stainless steel knife and measuring
the depth of the produced step by means of a Nanopics
2,100 atomic force profilometer from Seiko.
TGA/DTA analysis was performed under flowing air on
a Mettler Toledo 851e thermobalance with a resolution of 1
lg on powders obtained by drying the metalorganic solu-
tions at 105 °C in an oven. Heating rate was set at 10 °C/
min.
Dynamic viscosities of the solutions were determined by
a Haake cone-plate rheometer at 22 °C. Topographic ana-
lysis of 1 9 1 lm2 windows was performed by AFM in a
Nanotec Cervantes model in tapping mode.
3 Results and discussion
3.1 Thickness after spin-coating
Thickness after spin-coating strongly depends on the vis-
cosity, l of the precursor solutions [24]. For this reason,
viscosity has been determined for all the tested metalor-
ganic solutions, which is shown in Fig. 1, where log l
versus PVP molarity has been chosen.
The viscosity is 2.5 mPa s for the PVP-free solution and
reaches values as high 99 mPa s when the [PVP]/
[Ce ? Zr] ratio is 1.0 and using high PVP molecular
weight. A monotonic increase dependency is observed for
each series in accordance with the expected rise in vis-
cosity caused by increasing additions of PVP in the solu-
tions, exhibiting a tendency towards exponential behaviour
of the type l * e[PVP], as evidenced by the observed lin-
earity in the semi-log plot. This behaviour is in agreement
with the general viscosity dependence on polymer con-
centration reported for soluble polymers [25] and aqueous
PVP in particular [26]. In addition, viscosity is always
higher in the case of the high molecular weight PVP, as
expected from the longer polymer chain.
Once spin-coated, the thickness of the films was deter-
mined. In Fig. 2, the profilometric image corresponding to
sample B-4 is shown. As observed on the right side, the
ceria film appears flat and uniform, despite it has been
prepared from a rather viscous precursor solution. Then,
Fig. 3a, b display the obtained values of the thickness
derived from similar images.
Concerning series A (Fig. 3a), with low molecular
weight PVP and lower solution viscosities, the thickness
increases proportionally to the PVP concentration from
[PVP] = 0.250 M approximately. This linear tendency is
clearly observed in series B (high Mw) in all the PVP
concentration range (Fig. 3b), showing higher thicknesses
after deposition, consistent with the higher values of the
viscosity.
In order to understand this result, the precursor solution
used in this work can be considered to have basically two
different solutes: a metalorganic salt (cerium(III) 2,4-
pentadionate) and a soluble polymer (PVP), assuming that
the doping zirconium metalorganic salt used for doping
ceria has a negligible effect. In general, concentration of
both solutes will influence thickness after spin-coated (tSC).
Here only PVP concentration has been changed in each
solution series, keeping metalorganic salt concentration
constant to 0.5 M. In the literature, reports about the
thickness or final mass of spin-coated films in relation to
the concentration can be found only for single solute pre-
cursor solutions. For the case of metalorganic salts, an
interesting theoretical model was proposed by Van Har-
develd et al. [27] for polymer-free ultra thin films prepared
by spin-coating. According to this, the thickness was
shown to follow a linear behaviour with salt concentration
since the solvent gradient in the drying film could be
neglected. Concerning salt-free polymer solutions, they
have been extensively studied from a practical and theo-
retical point of view considering solution rheology, solvent
evaporation, gas flow dynamics and centrifugal force.
Theoretically, Meyerhofer [28] reported a behaviour close
to a power-law dependence of the thickness as a function of
123

Fig. 2 Profilometric image of
as-spun B-4 used to determined
the film thickness
0 50
0 1.75
25
50
75
100
125
150
175
200
µm
µm
0.6
0.4
0.2
0
0 20 40
polymer concentration in photoresist films. On the other
hand, Extrand et al. [29] found an analytical time evolution
for the liquid height during spinning, being simplified to
final thickness h = (l/qx)1/2
c, where l, q, x and c are the
viscosity, density, spin rate and initial concentration,
respectively. It was shown to be valid for the case of thin
films from 0.5 to 170 nm of thickness. More complex
approaches based on finite-element analysis have been also
reported, like in the work of Flack et al. [30] where non-
Newtonian fluids are also included.
In our case, linearity of the thickness-polymer concen-
tration plot is observed in series B but not completely in
series A at low polymer concentrations. In this latter case,
the viscosity is not totally dependent on the polymer con-
centration but also on the metalorganic salt concentration,
as the low molecular weight of PVP does not produce a
huge increase in viscosity, contrary to series B.
3.2 Thickness after thermal treatment
In order to ensure complete organic removal during ther-
mal decomposition, TGA/DTA analysis was performed. A
typical TGA/DTA curve is shown in Fig. 4, which corre-
sponds to sample B-3 with molar ratio [PVP]/[Ce ? Zr] of
0.5. After weight loss around 130 °C due to solvent
removal, organic decomposition starts, which abruptly ends
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J Sol-Gel Sci Technol
µm
2
100 150 µm
1.5
1.25
1
0.75
0.5
0.25
0
60 80 100 120 140 160 180 µm
at 310 °C, coincides with a strong and narrow exothermic
DTA signal. When pure PVP was analyzed by TGA/DTA
under the same conditions, a two-step decomposition pro-
cess was recorded, which finishes at 650 °C, in accordance
to previous works [31]. Such thermogravimetric behaviour
was equivalent for both PVP molecular weights.
As a consequence, polymer degradation is accelerated in
our case in which seems to be an autocatalytic reaction as
more ceria is able to decompose the surrounding polymer
as it forms [32]. In fact, CeO2 is widely used as a good
oxidizing catalyst for organic matter owing to the ability of
ceria to change the oxidation state of Ce(III)/Ce(IV) and
the oxide transport properties of CeO2 [33].
Although TGA analysis provides an indication that
organics should be completely decomposed at the tested
firing temperature of 500 °C, more sensitive IR-ATR of
heated films was used as a tool to ensure the complete
removal of organic species. This is especially relevant for
the solution containing high loads of PVP.
Figure 5 shows the IR-ATR spectra of the thickest film
B-5. For comparison purposes, powders of PVP of the
same high molecular weight were also analyzed. Main
absorbances are clearly detected for powdered PVP. The
most prominent bands appear at 1,651, 1,422 and
1,278 cm-1 which can be assigned to C=O and N–C
stretching vibrations, CH deformation of cyclic CH2
J Sol-Gel Sci Technol

300 110
(a)
280
260
240
220
200 100

IR-ATR signal
180
tSC (nm)

160 (a)
140
120
100
(b)
90
80
60
40
20 (c)
0 80
0,000 0,125 0,250 0,375 0,500 4000 3500 3000 2500 2000 1500 1000
PVP (M) wavenumber (cm )
-1

900
(b) Fig. 5 IR-ATR spectra corresponding to bulk PVP powder (a), a salt-
800 free PVP film (b) and the sample B-5 (c). The high Mw PVP was used
in these measurements
700

600
tSC (nm)

500
(a) 70
400 after thermal decomposition (nm)
60
300
Thickness of series A

200 50

100 40

0
0,000 0,125 0,250 0,375 0,500 30

PVP (M)
20

Fig. 3 Thickness of series A (a) and B (b) after spin-coating as a

10
function of PVP molarity. The four more polymer concentrated
samples in series B show a power law index of 0.40 ± 0.04
0
0,000 0,125 0,250 0,375 0,500
PVP (M)

(b) 200
100
after thermal decomposition (nm)

20 175
Thickness of series B

150
90
15
DTA (°C/mg)

125
Weight (%)

100
80
10
75

70
50
5

25

0 0
60
100 200 300 400 500 600 700 800 900 0,000 0,125 0,250 0,375 0,500
Temperature (°C) PVP (M)

Fig. 4 TGA–DTA curves corresponding to sample B-3, where Ce/ Fig. 6 Thickness plots after thermal treatment as a function of
PVP molar ratio is 0.5 polymer concentration: low Mw (a) and high Mw PVP (b)

123

200
180
160
140
after thermal treatment (nm)
120
Thickness of series B
100
80
60
40
20
1 10
Viscosity (mPa·s)
Fig. 7 Thickness–viscosity log–log plot for series B after thermal
treatment
groups and C–N stretching of amide group, respectively.
To further compare with a PVP film of similar thickness, a
salt-free solution containing the same PVP molarity as B-3
was also spin-coated and dried at 100 °C, yielding a pure
PVP film. The same PVP absorptions can also be detected
in this sample, although weakened due to the reduced
thickness compared to the PVP powder. In the case of B-5,
the spectra is essentially empty of such absorptions.
Therefore, no signal corresponding to PVP was registered,
which provides further evidence of full polymer decom-
position after the thermal processing at 500 °C.
After the thermal treatment at 500 °C, the thickness of
all films was determined (Fig. 6a, b). From the final
thickness of the layers and comparing them to the as-spin
coated values in Fig. 3a, b, a dramatic shrinkage is rec-
ognized. For instance, thickness is decreased about 80 % in
sample B-5, i.e., the final layer has one-fifth of the thick-
ness after spin-coating. This is a consequence of organics
decomposition of the metalorganic salts and especially of
the polymer leading to a huge reduction of the deposited
volume but also to the compaction during the thermal
decomposition to minimize the surface energy. On the
other hand, the observed dependence of the thickness after
thermal treatment versus polymer concentration for both
PVP molecular weights is not linear but sigmoidal. This is
believed to be a consequence of the fact that there are
actually two solutes in the precursor solution. At low PVP
concentrations, the thickness-dependence should be deter-
mined by the metalorganic salt concentration while at
increasing polymer content, the behaviour is reversed in
favour of the polymer concentration.
To ascertain if the viscosity is the main controlling
factor for the thickness of the films after the thermal
treatment in the case of PVP-containing layers, we focus on
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J Sol-Gel Sci Technol
Ce0.90Zr0.10O2
Silicon
1 µm
Fig. 8 Cross-sectional SEM image of the Zr-doped ceria sample B-5
on the silicon substrate showing good coverage and thickness
uniformity
series B exhibiting less error in the profilometric determi-
100
nation of the thicknesses. A log–log plot (Fig. 7) shows a
good adjustment to a law t * ga, with an a value of
0.47 ± 0.06. In fact, a similar dependency with an
approximate power index of 1/3 was also found in YBCO-
TFA films with polyethyleneglycol as polymer [34].
Now it is possible to analyze the compaction of the
layers with increasing amounts of polymer. As it was
commented above, the thickness of the spin-coated layers
(tSC) follows a linear dependence with polymer concen-
tration. When this is translated to the viscosity of the
precursor solution, a log–log plot reveals a power depen-
dence tSC * gb with b = 0.40 ± 0.04, which in fact lies
very close to the power index obtained after the thermal
treatment.
That would mean that adding more polymer with the
intention of depositing more viscous solutions, and there-
fore thicker ceria films by spin-coating, does not imply an
increase of the entrapped porosity with thickness. In other
words, the escape of the decomposition gases is not limited
by the thickness, at least, in the tested thickness interval. Of
course, this can be only concluded for this particular sys-
tem. Different polymers, solvents or metalorganic salts
may have varying behaviours in terms of the thickness-
polymer concentration behaviour, which will influence the
remaining porosity after thermal decomposition. It also
should be stressed that the thermal profile of the decom-
position should also have a strong influence, since the
kinetics of each of the complex interrelated processes
occurring during the organics removal can affect the final
microstructure: solvent removal, metalorganic and polymer
decomposition and evolution of the nanosized oxide par-
ticles with temperature. For instance, for obtaining thick
and dense films one would wish to have a polymer removal
with a good compacting behaviour, which means that the
viscoelastic properties of the medium should be suitable for
allowing a large amount of decomposition gases being
evolved in a still soft mixture of solid decomposition
products.
In Fig. 8 a cross-sectional SEM image of the thickest
B-5 sample is shown where uniform thickness and correct
J Sol-Gel Sci Technol

Fig. 9 Topographic AFM B-1 B-2

image in regions of 1 9 1 lm2
0 0.2 0.4 0.6 0.8 µm 0 0.2 0.4 0.6 0.8 µm
for series B (high Mw PVP) 0 0
after the thermal treatment at
500 °C 0.1 0.1
0.2 0.2
0.3 0.3
0.4 0.4

0.5 0.5
0.6 0.6
0.7 0.7
0.8 0.8
0.9 0.9

µm µm

B-3 B-4
0 0.2 0.4 0.6 0.8 µm 0 0.2 0.4 0.6 0.8 µm
0 0
0.1 0.1
0.2 0.2
0.3 0.3
0.4 0.4
0.5 0.5
0.6 0.6
0.7 0.7
0.8 0.8
0.9 0.9

µm µm

B-5
0 0.2 0.4 0.6 0.8 µm
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

µm

coating coverage are observed. Interestingly, no macro-
scopic defects like blisters or cracks are detected in this
sample. The thickness derived from the image is
137 ± 20 nm, in good agreement with the value found by
profilometry.
With the aim of investigating the porosity generated
during thermal decomposition, AFM analysis was carried
out for series B (Fig. 9), which gives surface information
about the morphology of the ceria films. Nanometric-size
doped-ceria grains can be identified with a general

123

1,0
0,9
Surface roughness (nm)
0,8
0,7
0,6
0,5
0,4
0,3
0,2
0,000 0,125 0,250 0,375
PVP (M)
Fig. 10 Plot of surface roughness as a function of polymer content
for series B
tendency to grow larger as PVP is increased in both series.
In addition, porosity is also observed between the grains,
which are due to the evolution of decomposition gases and
incomplete densification.
Surface roughness has been analyzed for series B. The
results are displayed in Fig. 10. A maximum value is
observed around [PVP] = 0.250 M. From this value, the
film becomes smoother again. This behaviour is not prop-
erly understood so far but it might arise from changes in the
viscoelastic properties as the ratio between metalorganic
salt and PVP is reduced. Nonetheless, the rms roughness
lies below 1.0 nm for all the members of the series.
4 Conclusions
Ceria-based films were prepared by MOD of spin-coated
solutions containing the soluble polymer PVP, with rec-
ognized stress-relieving properties during the large
shrinkage as thermal decomposition takes place. This
polymer-loaded MOD solutions are an interesting case
study in spin-coating of precursor solutions owing to the
presence of two different types of solutes: metalorganic salt
and organic polymer. Moreover, two different molecular
weight PVP were used to investigate the effect of chain
length. The thickness of the deposited layers was deter-
mined after the spin-coating process and after the thermal
decomposition at 500 °C. The longer polymer chain
expectedly increases the viscosity of the precursor solution
and produces thicker films by spin-coating. At this point,
the thickness scales with l0.40 as PVP concentration is
increased. After thermal decomposition, the films dramat-
ically shrink while the thickness follows a l0.47 power law,
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J Sol-Gel Sci Technol
close to the dependence of the corresponding as-deposited
films. Thus, it is concluded that the porosity fraction does
not increase substantially in the studied thickness range.
AFM analysis of the film surface reveals nanometric ceria
grains with porosity also in the nanometric scale. Surface
roughness increases with PVP additions up to 0.25 M
approximately and then drops below the initial PVP-free
film, possibly indicating some unknown change in the
viscoelastic properties at this polymer concentration.
Altogether, this will strongly influence the film micro-
structure during the crystallization step at higher
temperatures.
As an outlook for this work, it should be mentioned that
0,500
organic polymers are a large and versatile family of com-
pounds that find many applications due to the possibility of
tailoring their properties to specific requirements. MOD
approaches for preparing thick films should be no excep-
tion. However, more insight into the mechanisms of ther-
mal decomposition in these multicomponent films is
needed to fully exploit the benefits of polymer additions in
the precursor solutions.
Acknowledgments We acknowledge financial support from MIC-
INN (Spanish Ramón y Cajal program, MAT2011-28874-C02,
CSD2007-0041 and IPT-2011-1090-920000) and Generalitat de Ca-
talunya (Catalan Pla de Recerca 2009-SGR-770 and XaRMAE). Prof.
P. Roura and Dr. J. Farjas from Universitat de Girona are also rec-
ognized for the TGA/DTA data.
References
1. Lange FF (1996) Science 273:903–909
2. Thouless MD (1995) Annu Rev Mater Sci 25:69–96
3. Zalamova K, Romà N, Pomar A, Morlens S, Puig T, Gázquez J,
Carrillo AE, Sandiumenge F, Ricart S, Mestres N, Obradors X
(2006) Chem Mater 18:5897–5906
4. Kuzmina NP, Ibragimov SA, Makarevich AM, Martynova IA,
Kharchenko AV, Korolev V, Kardashov SV (2010) Chem Mater
22:5803–5813
5. Gallage R, Matsuo A, Fujiwara T, Watanabe T, Matsushita N,
Yoshimura M (2008) J Am Ceram Soc 91:2083–2087
6. Obradors X, Puig T, Pomar A, Sandiumenge F, Mestres N, Coll
M, Cavallaro A, Romà N, Gázquez J, González JC, Castaño O,
Gutierrez J, Palau A, Zalamova K, Morlens S, Hassini A, Gibert
M, Ricart S, Moretó JM, Piñol S, Isfort D, Bock J (2006) Su-
percond Sci Technol 19(3):S13
7. Tsipis E, Kharton V (2008) J Solid State Electrochem
12:1039–1060
8. Yan B, Zhao W (2004) Mater Sci Eng B 110:23–26
9. Aklalouch M, Calleja A, Granados X, Ricart S, Boffa V, Ricci F,
Puig T, Obradors X (2013) Sol Energy Mat Sol Cell. doi:10.1016/
j.solmat.2013.08.040
10. Fransen T, Gellings PJ, Fuggle JC, van der Laan G, Esteva JM,
Karnatak RC (1985) Appl Surf Sci 20:257–266
11. Carrettin S, Concepción P, Corma A, López Nieto JM, Puntes VF
(2004) Angew Chem Int Ed 43:2538–2540
12. Gilioli E, Baldini M, Bindi M, Bissoli F, Pattini F, Rampino S,
Ginocchio S, Gauzzi A, Rocca M, Zannella S (2007) Phys C
463–465:609–614
J Sol-Gel Sci Technol
13. Phok S, Bhattacharya RN (2006) Phys Status Solidi A
203:3734–3742
14. Coll M, Gázquez J, Hühne R, Holzapfel B, Morilla Y, Garcı́a-
López J, Pomar A, Sandiumenge F, Puig T, Obradors X (2009) J
Mater Res 24:1446
15. Vlad VR, Zalamova K, Coll M, Pomar A, Palau A, Gutierrez J,
Puig T, Obradors X, Usoskin A (2009) IEEE Trans Appl Su-
percond 19:3212–3215
16. Obradors X, Puig T, Ricart S, Coll M, Gazquez J, Palau A,
Granados X (2012) Supercond Sci Technol 25:123001
17. Kozuka H, Kajimura M, Hirano T, Katayama K (2000) J Sol–Gel
Sci Technol 19:205–209
18. Garcı́a Hernández M, Carrillo Romo F, Garcı́a Murillo A, Jara-
millo D, Meneses M, Bartolo P, Chadeyron G (2010) J Sol–Gel
Sci Technol 53:246–254
19. Kozuka H, Takenaka S, Tokita H, Okubayashi M (2004) J Eur
Ceram Soc 24:1585–1588
20. Gu M, Zhu L, Liu X, Huang S, Liu B, Ni C (2010) J Alloys
Compd 501:371–374
21. Liu M, Yan X, Liu H, Yu W (2000) React Funct Polym
44:55–64
22. Kozuka H, Takenaka S, Tokita H, Hirano T, Higashi Y, Hamatani
T (2003) J Sol–Gel Sci Technol 26:681–686
23. Kroschwitz JI, Howe-Grant M (eds) (1989) Kirk-Othmer ency-
clopedia of chemical technology, vol 24, 4th edn. Wiley, New
York
24. Chen BT (1983) Polym Eng Sci 23:399–403
25. Dill KA (1980) Macromolecules 13(3):620–622
26. Goldfarb J, Rodriguez S (1968) Makromol Chem 116:96–106
27. van Hardeveld RM, Gunter PLJ, van Ijzendoorn LJ, Wieldraaijer
W, Kuipers EW, Niemantsverdriet JW (1995) Appl Surf Sci
84:339–346
28. Meyerhofer D (1978) J Appl Phys 49:3993–3997
29. Extrand CW (1994) Polym Eng Sci 34:390–394
30. Flack WW, Soong DS, Bell AT, Hess DW (1984) J Appl Phys
56(1199):1206
31. Bogatyrev VM, Borisenko NV, Pokrovskii VA (2001) Russ J
Appl Chem 74:839–844
32. Chen W, Li F, Yu J (2006) Mater Lett 60:57–62
33. Trovarelli A (1996) Cat Rev Sci Eng 38:439–520
34. Morlens S, Romà N, Ricart S, Pomar A, Puig T, Obradors X
(2007) J Mater Res 22:2330–2338
123