Thin Solid Films 524 (2012) 62–66

Contents lists available at SciVerse ScienceDirect

Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Thin gas-barrier silica layers from perhydropolysilazane obtained

through low temperature curings: A comparative study
Arnaud Morlier a, b,⁎, Stephane Cros b, c, Jean-Paul Garandet b, c, Nicole Alberola a, b
a
LEPMI/LMOPS, UMR CNRS-UJF-UDS-INPG 5279, Bat. IUT, avenue du Lac d'Annecy, 73376 Le Bourget du Lac, France
b
National Institute for Solar Energy (INES), 50 avenue du Lac Léman, 73377 Le Bourget du Lac, France
c
CEA/DRT/LITEN/DTS, 50 avenue du Lac Léman, 73377 Le Bourget du Lac, France

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

Article history: Perhydropolysilazane (PHPS) conversion to silica through different low temperature routes has been studied.
Received 19 May 2012 This study showed the influence of main conditions such as moisture and temperature on the conversion ki-
Received in revised form 18 September 2012 netics. Catalytic effects of ammonia both in solution and in the gas fraction and hydrogen peroxide were in-
Accepted 18 September 2012
vestigated. Possible conversion mechanisms in the presence of ammonia and peroxide catalysts are proposed,
Available online 5 October 2012
since both appear to play a significant role in the conversion of PHPS, although the effect is limited to the first
Keywords:
conversion step. Barrier properties against water and oxygen shown by polymer films coated by thin inorgan-
Perhydropolysilazane ic layers obtained following these curing routes have then been compared using an innovative permeation
Flexible gas-barrier coating measurement method. Oxygen and water permeability measurements show that the curing method has a
Gas permeation noticeable effect on gas barrier efficiency. The most efficient barrier layers tested in this work led to a barrier
Silicon oxide improvement factor against oxygen of circa one order of magnitude.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
For a growing field of applications, there is a need for large areas of
transparent and flexible gas barrier materials. Depositing thin inorganic
coatings on polymers is the most usual way [1] to obtain such flexible
and transparent materials. Among these inorganic coatings, thin silica
layers are of significant interest. Obtaining large areas through fast
and cheap processes is also an important issue. Common vacuum depo-
sition techniques such as plasma enhanced chemical vapor deposition
or atomic layer deposition may be used to form good quality thin inor-
ganic layers. Nevertheless, the use of these techniques for large scale
applications is hindered by their limited throughput. Therefore, the pos-
sibility to obtain such coatings by in situ conversion of a cast inorganic
precursor is a promising way to coat large areas of polymer. Among
the soluble inorganic precursors, silazane polymers constituted of a
Si\N backbone and various organic side chains have attracted much
attention in the past decade for their versatility as they enable the prep-
aration of silicon carbonitride ceramics with fine tuned composition [2].
Among these precursors, perhydropolysilazane (PHPS) is of particular
interest for the synthesis of carbon free silicon oxides or nitrides. It is
an inorganic polymer composed only of Si\N, Si\H and N\H bonds.
In the early literature, PHPS conversion into dense layers through high
⁎ Corresponding author at: ISFH, Institute for Solar Energy Research Hamelin, Am Ohrberg
1, 31860 Emmerthal, Germany. Tel.: +49 5151 999 303; fax: +49 5151 999 400.
E-mail addresses: arnaud.morlier@univ-savoie.fr (A. Morlier), stephane.cros@cea.fr
(S. Cros), jean-paul.garandet@cea.fr (J.-P. Garandet), nicole.alberola@univ-savoie.fr
(N. Alberola).
temperature curing has been investigated. Many studies have been fo-
cused on the formation of either silicon nitride or silica [3,4] and have
shown the dependence of the curing atmosphere on the nature and
structure of the obtained layer. The pyrolytic conversion at tempera-
tures above 800 °C under nitrogen allows silicon nitride formation
with high yields [3,4], opening a large area of applications from
anticorrosion coatings on metallic parts [5] to microelectronic dielectric
layers. The same pyrolytic treatment under dry air leads to the total
oxidization of PHPS, eliminating hydrogen and nitrogen present in the
structure [6]. Nevertheless, according to investigations on PHPS
oxidization at temperatures ranging from 100 to 600 °C [7], only higher
temperatures lead to almost hydrogen and nitrogen free materials.
This method is not easy to apply to thin coatings on polymers.
Since curing temperature range of coatings on polymer substrates is
limited, heat-promoted conversion will not be well-suited.
Bauer [8] studied low temperature curing kinetics of PHPS and gave
evidence for the influence of both moisture and temperature in the
reaction mechanism. At low temperature under air, conversion of
perhydropolysilazane into silica follows a two step reaction path of
which a simple representation is given in Fig. 1. This route consists in
the hydrolysis of the perhydropolysilazane to form silanols, eliminating
hydrogen and nitrogen from the structure, forming gaseous hydrogen
and ammonia as byproducts, followed by the polycondensation of the
silanols into an amorphous silica lattice by eliminating water. It should
be noted however that cross linking of the silanols starts before all the
Si\N bonds are hydrolyzed.
This study [8] shows that in the presence of moisture, the curing of
PHPS is remarkably accelerated. But, at low temperatures, the material

0040-6090/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tsf.2012.09.065
 A. Morlier et al. / Thin Solid Films 524 (2012) 62–66
Fig. 1. Curing of perhydropolysilazane into silica at low temperature in the presence of
moisture. a) Hydrolysis, b) polycondensation.
is still not completely converted over a timescale of hours. Nevertheless,
with this curing method Ohishi [9] reports barrier improvement factors
of 1.2 and 12 against water and oxygen respectively for PHPS layers de-
posited on polyethylene terephthalate substrates previously coated
with a thin layer of indium-doped tin oxide.
Some other catalytic processes have been tested in literature.
Some authors [10–12] have reported that the presence of gaseous
ammonia may promote the conversion of PHPS into silica. Kubo re-
ports that after 6 h of ammonia exposure, PHPS thin films are totally
converted into a material similar to amorphous silica.
Lee et al. [13] have performed the conversion of perhydropolysilazane
by immersing samples into a hydrogen peroxide solution and have
shown that the decomposition kinetics of original PHPS is very fast com-
pared to that of thermal hydrolysis.
In this work, we will compare the PHPS curing rates of each method
described in the literature, such as immersion in hydrogen peroxide so-
lution, exposure to ammonia vapors and heating at relatively low tem-
perature with or without moisture. Material composition over time will
be monitored by Fourier transform infrared spectroscopy (FTIR). Since
the role of each catalyst not well known until now, we will discuss
their potential effect. We show that various experimental conditions
are leading to materials with different chemical structures.
In the end, the barrier properties provided by thin layers of the
obtained materials deposited by various processes on polymer sub-
strates will be investigated using different gasses (nitrogen, oxygen
and water) by means of a high precision permeameter designed and
built in house [14].
2. Materials and method
About 1 ml of perhydropolysilazane in di(n-butyl)ether (NN-120-20
(A), Clariant) was spin coated (1000 rpm) on 50×50 mm2 silicon wa-
fers (725 μm, Czochralski grown, p-type, Siltronix), forming a 250±
30 nm thick deposit. A reference infrared spectrum was recorded before
the beginning of the curing, circa 1 min after deposition. For all types of
curings investigated, conversion was monitored by periodically record-
ing infrared (IR) spectra. FTIR spectra were recorded in transmission
mode on a ThermoElectron Corporation Nicolet 5700 spectrometer, tak-
ing the bare silicon wafer as blank. This method allows the semi-
quantitative analysis of the composition of the deposits by monitoring
the relative absorbance of characteristic vibrational peaks over time as
compared to their intensity in the uncured PHPS. Thickness and
refractive indexes were measured after the curing by spectroscopic
ellipsometry with a Horiba JobinYvon UVISEL spectrometer on the spec-
tral region of UV–vis from 1.5 eV to 6.0 eV and an incidence angle of 70°.
PHPS coatings were treated following different ways. A reference
was made by pyrolyzing a coated sample on a furnace at 600 °C
under air for 30 min. Hydrolysis was performed in an oven in which
humidity was kept at a high level by constantly sweeping the atmo-
sphere with externally generated steam. Catalytic effect of ammonia
vapors has been investigated by positioning samples on a grid
63
suspended over 20 ml of saturated ammonia in closed glassware.
The oxidizing effect of hydrogen peroxide was studied by immersing
samples on a 20% aqueous H2O2 solution (Aldrich) at 23 °C.
Permeation samples were prepared by coating 50 μm thick
Melinex 501 polyethylene terephthalate (PET) (Micel Industries)
and 125 μm thick high glass transition temperature bisphenol A
and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane polycar-
bonate copolymers (Bayer Makrofol DP 1202 1-1 CC) with PHPS by
means of a Mayer rod coater (Erichsen K Hand Coater set).
Permeation measurements were performed with a patented home-
made permeameter [14,15] which consists in a cell containing the sam-
ple in which the upstream side is filled with the gas of which the
permeability is to be measured and the downstream side is an ultra
high vacuum chamber equipped with a quadrupolar analyzer mass
spectrometer equipped with an ion trap detector (MKS Instruments).
The targeted ion current is considered proportional to the partial
pressure of the gas in the downstream chamber. Using such a device al-
lows one to use isotopes as permeant, thus increasing the sensitivity of
the measurement by discriminating the signal from the ambient atmo-
sphere contamination. Water permeation measurements were done
using deuteriated water (D2O) and oxygen permeability was measured
with 18O2. All measurements have been performed at 38 °C with an at-
mosphere composed of 99% of targeted gas. Upper side pressure was
about 300 hPa for oxygen and helium permeation measurements and
40 hPa for water permeation measurements. The tested surface is a
disk of 55 mm diameter.
3. Results and discussion
3.1. Comparison of curing processes
3.1.1. High temperature curing
The relatively short curing time of 30 min at 600 °C is supposed to
be sufficient for achieving total conversion of deposited PHPS [7]. This
allows comparing the structures of as deposited material and perfectly
converted material. PHPS FTIR spectrum (Fig. 2) exhibits a set of strong
vibration bands which can be attributed respectively to N\H (3380
and 1090 cm−1), SiH2 (2160 and 890 cm−1) and SiN (840 cm−1).
Converted PHPS spectrum only shows SiO bands at 1070, 810,
and 440 cm−1. Characteristic absorption peaks of SiH and SiN have
disappeared. This shows that any trace of SiH and SiN has been
converted, at the resolution level of the FTIR technique.
Considering the intensity of the main vibration peaks, it is relevant
to follow the bands at 840 and 2160 cm −1 to monitor precursor de-
composition which is the first conversion reaction step (Fig. 1).
Fig. 2. Transmission FTIR spectra of (solid line) as-deposited PHPS and (dashed line)
pyrolyzed at 600 °C for 30 min.
64 A. Morlier et al. / Thin Solid Films 524 (2012) 62–66
3.1.2. Effect of moisture and temperature
Effects of humidity and temperature have been investigated by
hydrolyzing the PHPS samples at 80 and 180 °C in the absence of hu-
midity or in the presence of steam sweeping and compared to the
conversion at room temperature under a standard hygrometry
(40% RH). This shows (Fig. 3) that although the conversion of SiH
bonds occurs rather slowly, SiN bonds' hydrolysis rate is even slower
at ambient temperature and does not lead to a total conversion even
over a long period of time.
Temperature plays a key role on the Si\H and Si\N bond conver-
sion: the higher the temperature, the faster the conversion. Hygrometry
is also promoting the conversion, especially for SiN bonds.
Even under optimal conditions of high temperature and humidity,
conversion is still incomplete over a time scale of 5 h, with a few re-
sidual precursor bonds still present as shown in Fig. 4. Conversion
seems to be completed only for the longest curing time of about
24 h (Fig. 3).
3.1.3. Catalytic effect of ammonia
The effect of ammonia on the curing speed of PHPS has been
observed both in solution and in gaseous phase (Fig. 5). In both
cases, the presence of ammonia has a drastic effect on the conversion
of the SiH and SiN precursors both in terms of efficiency and conver-
sion rate compared to the same conditions without ammonia. It is in-
teresting to note that immersion in water alone is not a sufficient
condition to significantly accelerate the decomposition of PHPS.
Nevertheless, immersion in the ammonia solution leads to a faster
decomposition compared to simple gaseous exposure. This tends to
suggest that the strong acceleration effect is due to ammonia only.
Although this acceleration effect is noticeable on the SiH and SiN
bonds scission, formation of Si\O\Si network is not complete. Indeed,
FTIR spectroscopy reveals a broad absorption peak in the range
3000–3700 cm−1, characteristic of OH bonds (Fig. 6). Extended expo-
sures to ammonia vapors up to 24 h showed that even for these long
durations, total cross-linking of silanols does not occur.
It is interesting to note that this large absorption band was not so
visible in the FTIR spectrum of the thermally hydrolyzed PHPS on
Fig. 4. This suggests that SiOH polycondensation is promoted by
elevated temperature.
In order to activate the polycondensation step, a thermal post-
curing of 30 min at 150 °C was implemented. However, the complete
cross-linking into a Si\O\Si network could not be achieved. In conclu-
sion, ammonia catalysis allows a faster but still incomplete conversion
by only promoting the first reaction step.
Despite the strong effect on the SiN bonds' conversion rate, the
role of ammonia in the curing process is unknown. Ammonia may
Fig. 3. Evolution of normalized absorbance at a) 2100 cm−1 (SiH) and b) 840 cm−1
(SiN) over time of exposure to ■ 25 °C/40% RH, ○ 80 °C/10% RH, ● 80 °C/steam atmo-
sphere, Δ 180 °C/10% RH, and ▲ 180 °C/steam atmosphere.
Fig. 4. Transmission FTIR spectra of (solid line) as-deposited PHPS and (dashed line)
after curing at 180 °C under steam atmosphere for 300 min.
actually act either as a nucleophilic agent or as a base. In the latter
case, the catalytic effect could be attributed to the pH of the solution.
To verify this assumption, curing was performed in a 0.01 mol.l −1 so-
dium hydroxide solution, which shows a pH similar to the concen-
trated ammonia solution. This resulted in a fast etching of the PHPS
deposit, totally removing the precursor layer instead of converting
it. On another hand, the increase in the absorbance at 840 cm −1
recorded immediately after the beginning of the conversion (Fig. 5)
suggests that the fast hydrolysis of SiH bonds results in the formation
of additional SiN bonds. This may be attributed to the role of ammo-
nia as promoting agent for the formation of an intermediate SiN lat-
tice subsequently hydrolyzed to SiO bonds. Then, two processes
may be considered. On the one hand, the replacement of SiH bonds
by more polarized SiN bonds may in turn make the nucleophilic sub-
stitution by a water molecule more favorable, leading to a silanol
group after deprotonation. On the other hand, the acceleration of
SiN bonds' hydrolysis may be explained by the easy substitution of
an intramolecular Si\N bond of the polymer chain by a terminating
Si\N bond, resulting in a reduced steric hindrance for the hydrolysis
to take place.
3.1.4. Effect of a peroxide catalyst
Catalyst with an aqueous hydrogen peroxide solution strongly ac-
celerates SiH and SiN bond scission. Fig. 7 shows that after immersion
for 10 min into a hydrogen peroxide solution, the conversion of SiN
and SiH is almost achieved.
However, the material resulting from this curing is highly hydrox-
ylated silica (Fig. 8). Conversion shows the same limitation as that
Fig. 5. Evolution of normalized absorbance at a) 2100 cm−1 (SiH) and b) 840 cm−1 (SiN)
over time of exposure at 25 °C to ■ atmosphere 40%RH, □ immersion in deionized water,
● gaseous ammonia in atmosphere, and ○ immersion in aqueous ammonia solution.
 A. Morlier et al. / Thin Solid Films 524 (2012) 62–66
Fig. 6. Transmission FTIR spectra of (plain solid line) as-deposited PHPS and (dashed
line) a sample submitted for 60 min to ammonia vapors.
observed with the ammonia catalyst, since only the first reaction step
seems to be catalyzed. In this case, it is assumed that two competitive
reactions occur in the presence of HO • radicals and water: PHPS SiH
and SIN bonds can either be slowly hydrolyzed by water as in previ-
ous experiments or rather be quickly dissociated with the formation
of radicals by HO • species. Radicals resulting from this bond scission
may then recombine with other hydroxyl radicals. Both reactions
are leading to the same silanol species, the latter being faster.
3.2. Permeation measurements
To start with, the influence of temperature of curing under damp
heat conditions (i.e. referring to high (>80%) relative humidity and
temperatures of 80 °C or 180 °C) has been evaluated with deposits
performed on polycarbonate substrates, which could withstand rela-
tively high temperatures (below glass transition at 200 °C). Never-
theless, the difference of thermal expansion between the substrate
and the inorganic layer may cause the cracking of the coating or
permanent deformation of the foil. Therefore, we choose to limit the
curing temperature in the conditions as described in Section 3.1.2 to
a maximum of 130 °C. Thus, the permeability of thin PHPS films
converted at 80 °C and 130 °C on polycarbonate has been measured
(Fig. 9). Only data obtained for oxygen and nitrogen permeability
are presented here, since water permeability measurements are
impossible to carry out with polycarbonate substrates because of
the high sensitivity of the mass spectrometer embedded in our
Fig. 7. Evolution of normalized absorbance at a) 2100 cm−1 (SiH) and b) 840 cm−1
(SiN) over time of immersion at 25 °C in ■ deionized water, and ○ 20% hydrogen per-
oxide solution.
65
Fig. 8. Transmission FTIR spectra of (solid line) as-deposited PHPS and (dashed line) a
sample soaked for 10 min in 20% aqueous hydrogen peroxide solution.
permeameter. Barrier improvement factor (BIF) brought by the thin
layers as compared to bare polymeric substrate rises with the thick-
ness. Nevertheless, beyond a maximal value, the permeability of the
coated polymer samples may increase with thickness, and the results
show a large data dispersion. This permeability increase and this dis-
persion are attributed to cracks appearing in thicker coatings due to
the increased mechanical stresses induced. Although temperature
does not seem to have a significant impact on BIF, it is worth noting
that at higher temperatures, thick samples undergo a permanent
deformation due to the tensile stress exerted by the inorganic layer
on the substrate. Under such conditions, the permeation measure-
ment is hindered as a non planar sample cannot be properly installed
in the permeameter. In some cases, this stress also provokes the
cracking of the thickest samples.
A strong correlation is observed between BIFs for oxygen and
nitrogen. This similar behavior can result from a similar molecular
volume of both species and from the absence of chemical interaction
between the permeating species and the material.
Considering that damp heat-cured PHPS of thickness ranging
between 200 nm and 600 nm on polycarbonate substrate exhibit a
significant BIF, curing methods based on the use of catalysts have
been tested on layers deposited on PET substrates. The use of catalytic
methods was not possible with polycarbonate substrates due to their
high chemical sensitivity to high pH solutions. However, in order to
keep the curing temperature below the glass transition temperature
of PET, thermal conversion could not be performed at temperatures
higher than 70 °C. Fig. 10 shows the barrier improvement factors con-
ferred to 50 μm PET substrates by PHPS deposits converted by hydro-
lysis and catalyzed hydrolysis. The uncertainty bars shown in Fig. 10
Fig. 9. Evolution of nitrogen and oxygen barrier improvement factor with thickness for
PHPS layers on polycarbonate converted at ▲ 80 °C and □ 130 °C.
66 A. Morlier et al. / Thin Solid Films 524 (2012) 62–66
Fig. 10. Comparison of oxygen (filled symbols) and water (open symbols) BIF for
220 ± 20 nm (squares) and 600 ± 30 nm (circles) thick PHPS layers converted by dif-
ferent methods.
are related to the measurement dispersion. Issues show that the best
barriers are obtained by hydrolyzing the coating at 70 °C. It is worth
to note that although a significant BIF against oxygen can be obtained,
the coating provides only limited protection against water ingress
(BIF = 3). This poor water barrier effect may also be observed for
other conversion methods. This high water permeability is assumed
to be related to the large amount of silanol functions on the silica ma-
trix resulting from the low temperature incomplete curing, as these
silanol groups promote chemical interaction with water and increase
its solubility in the material.
It thus appears that although the inorganic layer may indeed be
homogeneous enough to be a barrier against gasses like nitrogen or
oxygen, the high solubility of water in highly hydroxylated silica is
detrimental to the water barrier performance. More generally, the
high solubility of water in such materials may also compromise this
conversion method for anticorrosion coatings.
4. Conclusion
In this paper, some known alternative ways to promote conver-
sion of perhydropolysilazane (PHPS) into silica were compared. It is
shown that a simple thermal curing in the presence of humidity is
not sufficient to efficiently convert the PHPS on polymer substrates
because of the limitation that they impose on the curing temperature.
Investigations of PHPS conversion in the presence of some catalysts
have shown that the main effect of known catalysts is the promotion
of the precursor degradation into silanol. However, the subsequent
total conversion of the silanol groups into a stable and dense silicon
oxide network is not possible at low temperatures. Nevertheless,
our results suggest that the use of a catalyst combined with a high
temperature may be sufficient to significantly promote both the first
and second reaction steps, making the fast conversion of PHPS into
silica possible on less temperature-sensitive substrates. Such a tech-
nique could for example be used for anticorrosion coatings on metal-
lic parts.
Measurements of gas barrier improvements conferred by thin de-
posits of PHPS cured following these various processes have shown
that the obtained materials can be quite efficient as barriers against
apolar gasses like oxygen or nitrogen. On the other hand, the large
amount of hydroxyl groups leads to high water solubility and therefore
to a poor efficiency against water permeation. However, it is suggested
that a more complete polycondensation may lead to a better water
barrier performance. The most perfectly converted material provides a
barrier improvement factor of about one order of magnitude against ox-
ygen or nitrogen and about 4 against water. For applications such as the
encapsulation of organic photovoltaic devices, the barrier improvement
factor with respect to polymeric membranes is not sufficient. A perspec-
tive is therefore to use such PHPS-derived thin coatings in association
with organic layers in multilayer structures.
Acknowledgments
The authors would like to thank Region Rhône-Alpes for funding,
Mr. Can Vu (Clariant) for interest and collaboration, Bayer Material
Science for supplies and Mr. Anthony Favier for useful discussion
about FTIR.
References
[1] Y. Leterrier, Prog. Mater. Sci. 48 (2003) 1.
[2] E. Kroke, Y.-Li Li, C. Konetschny, E. Lecomte, C. Fasel, R. Riedel, Mater. Sci. Eng. 26
(2000) 97.
[3] S. Schwab, R. Graef, C. Blanchard, S. Dec, G. Maciel, Ceram. Int. 97 (1998) 411.
[4] O. Funayama, Y. Tashiro, A. Kamo, M. Okumura, T. Isoda, J. Mater. Sci. 29 (1994) 4883.
[5] A. Shimomura, H. Horikawa, J. Shimomura, Y. Hasegawa, T. Ogihara, Trans. Mater.
Res. Soc. Jpn 37 (2012) 27.
[6] Y. Iwamoto, K. Sato, T. Kato, T. Inada, Y. Kubo, J. Eur. Ceram. Soc. 25 (2005) 257.
[7] K. Kamiya, A.I. Oka, H. Nasu, T. Hashimoto, J. Sol–Gel Sci. Technol. (2000) 495.
[8] F. Bauer, U. Decker, A. Dierdorf, H. Ernst, R. Heller, H. Liebe, R. Mehnert, Prog. Org.
Coat. 53 (2005) 183.
[9] T. Ohishi, J. Non-Cryst. Solids 330 (2003) 248.
[10] H. Kozuka, M. Fujita, S. Tamoto, J. Sol–Gel Sci. Technol. 48 (2008) 148.
[11] T. Kubo, E. Tadaoka, H. Kozuka, J. Sol–Gel Sci. Technol. 31 (2004) 257.
[12] A. Yamano, H. Kozuka, J. Phys. Chem. B 113 (2009) 5769.
[13] J. Seo Lee, J. Hun Oh, S. Woon Moon, W. Suk Sul, S. Dong Kim, Electrochem.
Solid-State Lett. 13 (2010) H23.
[14] S. Cros, R.D. Bettignies, S. Berson, S. Bailly, P. Maisse, N. Lemaitre, S. Guillerez, Sol.
Energy Mater. Sol. Cells 95 (2011) S65.
[15] M. Firon, S. Cros, P. Trouslard, Method and device for measurement of perme-
ation, U.S. Patent US2007186622, 2007.