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Influence of Argon and Nitrogen Admixture in


HMDSO/O2 Plasmas onto Powder Formation

Marina Ricci,* Jean-Luc Dorier, Christoph Hollenstein, Pierre Fayet

In situ Fourier transform infrared spectroscopy was used to study the powder formation of
hexamethyldisiloxane/O2 plasmas. The spectra show that oxygen plays an important role at
the beginning of the process. A large amount of oxygen is responsible for intense powder
formation. The admixture of inert or non-reactant gases,
such as Ar or N2, into the plasma promotes polymeri-
zation of the monomer. The formation of the particulates,
the evolution of their size, and chemical characteristics
give evidence of a multistep growth process. The size, as
well as the production rate, undergoes a reduction once
the Ar or N2 amount is increased in the plasma admixture.

Introduction In previous studies of SiH4 plasmas,[69] also the


formation of powder particles was observed; RF power
Organosilicon-based plasma enhanced chemical vapor limitations strongly reduced the powder radius and
deposition is a promising method for depositing both density.[1013] High substrate temperatures in SiH4 plasmas
inorganic SiO2-like films and polymer-like SiOxCyHz films. were observed to retard the powder formation.[1214] An
These films have found many applications in electronics,[1] improvement in deposition rate of amorphous hydroge-
optics,[2] as barrier films for food packaging,[3] and as corrosion nated silicon films with a drastic suppression of powder
protection layers.[4] The most industrially employed organo- concentration has been seen for RF discharges in silane
silicon precursor for the deposition of SiO2 and related diluted with a rare gas.[15,16] Inert gases introduced into the
SiOxCyHz films is hexamethyldisiloxane (HMDSO). The gas admixture reduced or completely suppressed the
deposition of SiO2-like films is obtained by adding O2 to this powder formation, stimulating at the same time plasma
precursor. Besides SiOx film deposition, in most cases also polymerization. As SiH4 is a pyrophoric gas, needing oxygen
intense formation of dust particles is observed. Dust particles to combust, other monomers, such as organosilicon
represent a main source of contamination of the films, which compounds, are preferred in industry for SiOx deposition.
could cause severe defects in the final product.[5] Furthermore As demonstrated in previous studies, HMDSO has been
the powder formation represents a considerable loss channel shown to be a good solution for these purposes. A high
for the monomer; therefore a more efficient use of the concentration of O2 in the HMDSO plasma allows to obtain
monomer and with it an increased deposition rate could be SiOx films close to stoichiometry, with good barrier
obtained by minimizing powder formation in the PECVD properties, nevertheless powder particles, in particular
process for silicon dioxide deposition. SiOx particles, appear. In the SiH4 plasma it has been shown
that trapping of negative ions in the RF plasma leads to
clusters, which then can evolve to nano-sized particles,
M. Ricci, J. L. Dorier, Ch. Hollenstein
which finally agglomerate to micrometer sized particles.[17]
Centre de Recherches en Physique des Plasmas, Ecole
Polytechnique Federale de Lausanne, 1015 Lausanne, Switzerland
However powder formation in HMDSO plasma has not yet
Fax: 41 21 693 51 76; E-mail: marina.ricci@epfl.ch been investigated in details and no mechanism leading to
P. Fayet particles in these plasmas has been identified. Knowledge
Tetra Pak (Suisse) SA, Development and Engineering, 1680 of SiO2 powder formation is an important issue for
Romont, Switzerland industrial processing of SiOx for various applications, but

Plasma Process. Polym. 2011, 8, 108117


108 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/ppap.201000052
Influence of Argon and Nitrogen Admixture in HMDSO/O2 Plasmas . . .

also for fundamental purposes such as the formation of SiOx


powder in astrophysics.[18]
In this work the influence on the particle formation by
the presence of argon and nitrogen in HMDSO/O2 plasmas
will be addressed.

Experimental Part
Setup and Parameters

The experiments were performed in a capacitively coupled RF


plasma reactor described in ref.[19]. The reactor consists of two
stainless-steel electrodes of 13 cm in diameter and is operated at a
frequency of 13.56 MHz. HMDSO was injected into the chamber
through heated tubing in order to avoid condensation along the
line. The experiments were performed at different gas pressures
and RF powers (from 0.13 to 0.3 mbar and from 22 to 33 W). The flow
rate of HMDSO was set to 5 sccm, while the O2/Ar and O2/N2 Figure 1. Time evolution of density, particle radius with three
ratios were modified keeping a constant total flux of 50 sccm. Time- different growth phases (a, b, and c) and fundamental RF har-
resolved in situ Fourier Transform Infrared Absorption Spectro- monic in comparison with particle size evolution. The density
scopy in the spectral range between 4 000 and 600 cm1 with a goes from 1013 to 1012 m3.
spectral resolution of 2 cm1 was applied. A spectrum was recorded
every 4 s. The infrared absorption of the gas and the plasma phases
was monitored by means of a Bruker IR Fourier Equinox 55
(Figure 1), the analysis of the scattering data shows that the
spectrometer. The infrared beam leaving the spectrometer was
particle growth develops in two-three distinct phases not
directed through the plasma via ZnSe windows mounted onto the
reactor and the transmitted radiation is focused onto a liquid N2- yet understood in detail. In a first phase (a) the particles
cooled HgCdTe detector by means of a gold-coated off-axis mirror. grow to a size of a few tenth of nanometer. This phase is
Furthermore, the optical path underwent N2 purging to reduce followed by a fast increase of the particle size up to about
CO2 and water vapor contamination. The peak positions were 200 nm (phase b). Finally the particle size seems to be
identified and numerically deconvoluted, using a commercial constant in the range of about 200250 nm. In same cases,
software. late in time (not shown here) the large particulates start to
Ex situ Fourier transform infrared spectroscopy (FTIR) absorp- form a so-called plasma crystal.
tion analysis of films, deposited onto silicon wafers, have been The particle growth in these plasmas is confirmed by the
performed, within 10 min after the deposition, in transmission
measurement of the first harmonic of the RF plasma
mode using the same Bruker FTIR spectrometer apparatus; the
excitation frequency.[21] A comparison between the ampli-
wavenumber range 4 000500 cm1, with a 4 cm1 resolution, was
tude of the first harmonic and the particle growth is
used. Powder particles, deposited onto the RF electrode and
collected with a pair of pliers, have been analyzed in attenuated presented in the Figure 1. At the beginning of the particle
total reflection (ATR) modality, using the same FTIR spectrometer formation an instability can be observed. This instability
and the same wavenumber range and resolution. might be similar to the heartbeat instability reported
Optical emission spectroscopy (OES) measurements were elsewhere.[21] This instability usually appears when a large
performed on the HMDSOO2Ar or N2 discharges by collecting density of small dust particles (few hundreds of nan-
the UVVis spectra in the range 200800 nm, by means of a quartz ometers) is produced.
optical fiber and the light was analyzed by an Ocean Optics S2000 In all the cases of the investigated HMDSOO2 plasma
spectrometer, with an integration time of 500 ms. about the same powder size evolution could be observed
starting from nanometer sized particles. In the following
Results and Discussion we restrict ourselves to the investigation of the chemistry of
the particle formation in these HMDSOO2 plasmas
Illumination of the plasma with the argon laser shows that, whereas the development of the dusty cloud within the
starting with a HMDSOO2 plasma, small powder particles plasma until the formation of a plasma crystal is
are first formed. With time the particle size increases, as investigated separately and will be reported elsewhere.
determined from the scattered light in the infrared region
from 3 000 to 4 000 cm1, as shown in Figure 1. The Rayleigh
In Situ Measurements
approximation has been used to estimate the particle size
within the plasma. The method is well described in the Figure 2 shows time resolved in situ FTIR spectra recorded
Appendix C of ref.[20] In the case of HMDSOO2 plasma for HMDSOO2 plasma with an oxygen/monomer ratio

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2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plasma-polymers.org 109
M. Ricci, J. L. Dorier, Ch. Hollenstein, P. Fayet

Table 1. IR absorption bands of the species present in the


HMDSO/O2 plasma.

Species Vibrational mode Wavenumber

cm1

SiOSi Bending 830


SiOSi Stretching 1 074
SiO or Stretching 1 200
LO mode
Si(CH3)x Stretching 1 260
H2O OH bending 1 4001 800
CH2O CO stretching 1 725
CH2O2 CO stretching 1 783
Figure 2. Time evolution of FTIR absorption spectra of the plasma
CO Stretching 2 140
phase (5 sccm HMDSO, 45 sccm O2, 22 W, 0.13 mbar). A spectrum is
recorded every 4 s. CO2 Asymmetric stretching 2 349
CH3 Asymmetric stretching 2 913
CH3 Symmetric stretching 2 966
equal to 5 at a RF power of 22 W and a gas pressure of CH4 Stretching 3 017
0.13 mbar. SiOH OH stretching of 3 400
The evolution of different absorption peaks in the H-bonded OH
infrared absorption spectra (Figure 2) indicates the presence
SiOH OH stretching in free SiOH 3 650
of gaseous and as well of solid matter within the discharge.
The significant deviation from the background absorption
for wavenumber greater than 2 000 cm1 is due to light shown in literature.[29] It is found that this ratio increases
scattering on plasma formed particles.[22] with time, implying a growing disorder degree.
The main vibrational modes are assigned according to Literature mentions the formation of chains from
the literature,[2326] such as: the absorption band at organosilicon cyclo-compounds, due to monomer fragmen-
800 cm1 to rocking vibration of the CH3 group of the tation. Their FTIR spectra show the expected above-
molecule Si(CH3)x or the absorption bands at 1 260 cm1 mentioned vibrations, some attributed to chain-terminat-
and assigned to the vibration of the molecule Si(CH3)x, the ing-group, some in form of shorter chains, as the LO4 mode
asymmetric and symmetric stretching of CH3 at 2 960 at 1 139 cm1,[3032] whose presence is linked to the AS2/AS1
and 2 900 cm1, respectively, and the broad band at ratio growth.
3 400 cm1 to OH stretching vibrations in SiOH (Table 1).
Additional peaks have been identified by deconvolution of
the spectra in the bending and stretching regions (Table 2)
Table 2. Additional absorption bands identified by the deconvo-
and are shown in Figure 4.
lution of the spectra in the bending and stretching regions.
The main peak at 1 074 cm1 (SiOSi asymmetric
stretching vibration or TO mode) shifts with time to Species Vibrational mode Wavenumber
1 073 cm1. As reported in literature, the shift of this
absorption peak towards lower wavenumbers is linked to a cm1
decrease of the stoichiometry in SiOx.[27] In our case, as the
resolution is 2 cm1, the shift by 1 cm1 is not significant. A Si(CH3)3 Stretching 758
slight shift to lower wavenumbers of the SiO-LO mode at Si(CH3)3 Rocking 795
1 200 cm1 is seen. The shift of TO and LO modes is linked to Si(CH3)2 Rocking 849
a deviation from SiO2 stoichiometry, related to a replace- SiOH Stretching 950
ment of SiO bonds with SiSi bonds.[28] This replacement SiCH2CH2Si 1 030
decreases the bonding angles in the tetrahedral basic unit.
TO3 mode Stretching 1 050
TO and LO modes refer to vibrations in which oxygen atoms
submitted to the asymmetric stretching mode are in phase TO mode Stretching 1 074
with each other (AS1) and are at 1808 out of phase (AS2). The SiO Symmetric stretching 1 100
ratio AS2/AS1 gives an indication of the disorder degree, as LO4 mode Stretching 1 140

Plasma Process. Polym. 2011, 8, 108117


110 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201000052
Influence of Argon and Nitrogen Admixture in HMDSO/O2 Plasmas . . .

would be the rings. In our case, TO mode


shifts to lower wavenumber and the long
chains or small rings increase at expenses
of the shorter chains or larger rings.
Concerning the spectral region from
880 to 740 cm1, it is possible to
estimate the evolution of the carbon
content in the plasma phase. For simpli-
city, we can ascribe this region to the
carbon content, because, except for the
presence of the SiOSi bending vibration,
we can visualized a lot of CHx vibrations.
From the deconvolution of all the
principal peaks contained in this region,
it is observed that all the band integrals
appear to increase with time, indicating
higher carbon content in the plasma, as
might be also confirmed by the increase
of the Si(CH3)x vibration intensity at
1 260 cm1.
The time evolution of each peak
Figure 3. Deconvolution of the FTIR spectrum (5 sccm HMDSO, 45 sccm O2, 22 W, (Figure 4) reveals that at the beginning
0.13 mbar). of the process the particle formation is
induced by polymerization of the mono-
mer, since in the first 40 s of discharge
The deconvolution of the stretching region (1 200 each band integral is constant, afterwards there is an
900 cm1) of the spectra recorded for the plasma phase increase of all the band integrals. This means that
(Figure 3) clearly shows LO4 mode and other bands, as the the particles grow and are coated with a thin SiOxCyHz
TO3 mode at 1 050 cm1, which indicates the presence of layer (Figure 5).
long chain of SiOSi or small rings of the SiO2 as indicated by A large amount of oxygen in the plasma gas admixture is
the asymmetric stretching at 1 100 cm1.[3033] responsible for large powder particles. The chemical
The TO mode shift towards higher wavenumbers may be processes take part just at the beginning of the discharge;
connected with rearrangement of the oxide lattice, leading as shown by the time evolution of each peak and infrared
to the formation of oxygen bridges with larger SiOSi spectra, the oxidized species as CO, CO2, and silanol (SiOH)n,
bond angles;[34] the larger the bonding angle, the bigger immediately appear, we observed an increase of all these
structures due to fragmentation and recombination of the
monomer in the discharge.
These last ones spectra evidence that in the development
up to a particle size of about 80 nm the particle composition
has a large amount of silanol. In a following phase the

Figure 5. Radius and chemistry evolution of particles produced


indifferent HMDSOO2 plasmas. The particle formation is
Figure 4. Time evolution of band integrals related to deconvo- induced by polymerization, after that they grow and are coated
luted peaks in the stretching region. with a thin SiOxCyHz layer.

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2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plasma-polymers.org 111
M. Ricci, J. L. Dorier, Ch. Hollenstein, P. Fayet

particle composition changes and particles mostly contain- mode, as well as the LO mode, seems to decrease once the
ing SiOx are found. It is presently supposed that the particles argon content is increased in the admixture, indicating a
undergo a dehydration or dehydroxylation. This mechan- reduction of the disorder degree. The carbon content,
ism is supported by a strong release of OH and the represented by the first right part of each spectrum (740
production of water as detected also by FTIR. The jump 880 cm1), decreases as the argon content increases; all the
visualized in the particle size behavior could be associated peaks related to Si(CH3)x vibrations tend to be smaller and
to a coalescence phase in particle evolution, during which smaller in amplitude, as well as the absorption band at
the size increases rapidly and at the same time the density 1 260 cm1 (related to Si(CH3)x stretching vibration) and
drops (Figure 1). Chemistry processes influence the plasma the CH3 symmetric and asymmetric stretching vibrations,
only in the first 40 s, after that we assisted to a rise of all the with the simultaneous appearance of a CH4 peak. CH4 is
species playing a role in the film and powder formation. formed by recombination of CH3 and H; when increasing
The effect of the introduction of argon into the gas argon, CH3 decreases and so there is the formation of CH4 at
admixture, by keeping a constant total flux is shown in high value of argon. Thus, a large argon amount limits the
Figure 6. increase of all the peaks containing carbon. In ref.[24] a
In all cases (O2/Ar ratio equal to 0.5, 1, and 2) the main reduced O2/HMDSO ration leads to an increase of carbon
vibrational lines in the in situ FTIR spectra remain the same, content; in our case we assisted to the contrary effect,
but their time evolution changes, as well as the light because the Ar ion has an energy threshold (13 eV) higher
scattering intensity (Figure 6). Rising the argon content than O ion (12 eV), and immediately react with the
leads to a clear decrease of all observed band integrals. The monomer, as explained later. They tend to be constant in
SiOSi stretching peak (or TO mode), for example, shifts to time; this is a clear indication of HMDSO polymerization. It
1 072 cm1, since due to the lower and lower oxygen clearly appears that the dissociation, polymerization and
presence in the admixture; anyway the shift is not particle growth processes are strongly dependant on the
significant, due to used resolution. In addition, the TO dilution ratio of HMDSOO2Ar.
The time evolution of each peak (Figure 7) reveals that the
process of the particle formation is dominated by the
polymerization of the monomer, because each band
integral is more or less constant in time. The polymerization
process influences the powder particle size; their radius
does not modify significantly.
In Figure 8 it is shown that the radius becomes smaller
and smaller, once the O2/Ar ratio in gas admixture is
reduced. Thus, a higher presence of argon limits the powder
particles formation and growth, as we can notice from the
evolution of the light scattering intensity. The powder

Figure 6. Effect of Ar introduction in the plasma admixture on the


last FTIR spectra (t 240 s). (a) 5 sccm HMDSO, 45 sccm O2, 22 W,
0.13 mbar; (b) 15 W, 0.28 mbar; (c) 30 W, 0.3 mbar; (d) 30 W, Figure 7. Time evolution of all band integrals related to decon-
0.3 mbar (f O2/Ar). voluted peaks in the stretching region (O2/Ar 0.5).

Plasma Process. Polym. 2011, 8, 108117


112 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201000052
Influence of Argon and Nitrogen Admixture in HMDSO/O2 Plasmas . . .

Figure 8. Time evolution of particle radius as a function of the Ar


admixture on the FTIR spectra.

particles formed in HMDSOO2Ar plasma (O2/Ar equal to


0.5) have a radius of about 50 nm.
This result is an additional confirmation of the poly-
merization in the plasma phase, due to the presence of inert
gases in plasma admixture. In the plasma, dissociation and
ionization of HMDSO molecule represent an essential initial
step in the process of polymerization. It is supposed that, in
case of argon admixture, among all the fragments, the
pentamethyldisiloxane (CH3)3SiOSi(CH3)2 cation plays a
fundamental role in the subsequent chemistry:[26,3537]
CH3 3 SiOSiCH3 3 Ar ! CH3 3 SiOSiCH3
2 Ar CH3 Figure 9. Effect of N2 introduction in the plasma admixture on the
last FTIR spectra (t 240 s). (a) 5 sccm HMDSO, 45 sccm O2, 22 W,
By replacing argon with nitrogen (Figure 9), under similar 0.13 mbar; (b) 25 W, 0.3 mbar; (c) 27 W, 0.3 mbar; (d) 33 W, 0.3 mbar
plasma conditions, the same vibrational lines have been (f O2/N2).
identified as in the previous cases, with a better visualiza-
tion of SiOH stretching peak at very high wavenumbers
(3 4003 600 cm1). No other peak, such as SiN or NH The strength of absorption of the SiH bond varied with
stretching peak, has been found in this system. This is different carrier gases, indicating a different degree of
explained by the triplet bond of the nitrogen molecule monomer molecular fragmentation during formation of
which is difficult to break. Deconvolution (Figure 10) shows cross-linking polymer products. The absorption peak area
the presence of SiCH2CH2Si peak at 1 030 cm1, a clear ratio SiH/(SiCH3)x characterizes the molecular fragmenta-
indication of the polymerization process in plasma phase. tion of the SiCH3 and CH bonds.
The time evolution of the deconvoluted peaks does not In the case of argon or nitrogen introduction (Figure 11a
show any significant modification in band integral: carbon and b), it looks that the ratio increases with increasing
content, disorder degree and angular bond are rather carrier gas in the plasma admixture. This means that a
constant. By increasing the oxygen amount in the gas higher degree of monomer molecular fragmentation is the
admixture, we observe the same effects as in the case of effect of the higher polymerization rate.
argon: an increase of carbon content, disorder degree, It seems that argon is inducing the polymerization
scattering intensity and particle radius (for O2/N2 equals to process more efficiently with respect to nitrogen, although
0.5, the radius is around 50 nm, as in the previous case with this difference is small, since the two threshold energies of
argon). Ar and N2 are quite close.
In plasma, the SiH bonding peak (absorption at 2 150 The same plasma conditions have been analyzed by
2 100 cm1) appears as a result of the molecular fragmenta- means of OES. The main lines that are observed in the
tion of SiCH3 (1 260 cm1) which breaks to detach the CH3. HMDSOO2 plasmas (Figure 12) are reported in Table 3,

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2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plasma-polymers.org 113
M. Ricci, J. L. Dorier, Ch. Hollenstein, P. Fayet

Figure 10. Deconvolution of the FTIR spectrum (5 sccm HMDSO,


15 sccm O2, 30 sccm N2, 33 W, 0.3 mbar). Figure 12. OES spectrum of a HMDSOO2Ar plasma.

with the corresponding wavelengths, as given in the atomic


lines databases in ref.[38] and the molecular structures
reported in ref.[39] No emissions from SiO radicals, C, SiH,
and Si atoms occurring at low wavelengths (200300 nm)
have been observed. The absence of SiH and SiO might be
due to dissociation of these species in the plasmas as
explained by Raynaud in the case of the dense DECR
plasmas.[40] The first hundreds of nanometers (300
450 nm) of the measured OES spectrum is dominated by
emission from the H2 primary system,[41] followed by a
weak emission of CH at 431 nm and the complex secondary
spectrum of H2.[42] It is also possible to observe a weak
presence of several systems of CO, CO, CO 2 ; they might be
generated by the monomer oxidation in the plasma phase
or by desorption from the reactor walls. A very weak
emission of Ha at 656 nm is observed; however we do not
observe any emission of hydrogen or atomic hydrogen
lines. The time evolution of the principal bands, such as H2,
CH, and of the principal Ar line (756 nm), shown in Figure 13
a reduction of the intensity of the line emissions in the first
40 s, due to the beginning of the powder formation; a clear
enhancement of the electronic excitation rate takes place
when the particles appear in the reactor. In a later stage, we
see a stabilization of the light intensities. Thus, we might
conclude that the nucleation of the powder particles starts
at the beginning of the discharge. As the oxygen fraction is
increased in the gas admixture, by keeping constant the
total flux, the atomic oxygen line (777.3 nm) is more and
more visible, while the CH and H2 systems seem to decrease,
because the oxidation leads to CO, CO, CO 2 , and H2O.
The OES spectra recorded for different HMDSOO2N2
admixtures show very well a dominance of N2 second
positive system; no SiN or NH bands have been seen in the
Figure 11. (a and b) Molecular fragmentation of the SiCH3 and spectra, in all studied situations, confirming the absence in
CH bonds in all plasma admixtures for Ar and N2 admixture the stretching region (1 200900 cm1) of the in situ FTIR
ratios. spectra of N containing peaks and the force of N2 triplet

Plasma Process. Polym. 2011, 8, 108117


114 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201000052
Influence of Argon and Nitrogen Admixture in HMDSO/O2 Plasmas . . .

Table 3. Emission systems and lines identified in a HMDSOO2Ar plasma.

Emitting species Transitions and system name Wavelength (line) or


spectral range (system)

nm

3
H2 Sg 3 Su primary system 200320
G 1
S 1
g B Su G !B 453464

d 3
Pu a3 S
g Fulcher-a 580650
2 2
CH A D  X P 4 300 A system 431.4 (0,0)

2
B2 SX P 3 900 A system 388.9, 387.1 (0,0)
Ha n(>2) ! n 2 (Balmer line) 656.3
N2 C3 Pu  B3 Pg second positive
CO Kaplan bands 252, 275
b3 Sa3 P third positive 283370
and 5B Bands 266383
Q
d3~  a3 triplet bands 401647
1 1 451608
B SA P angstrom system
03 1 575800
a Sa P asundi bands
CO B2 SX2 S first negative system 255315
2 2 309640
A PX S comet-tail system
CO
2
2 2
A S X P ll 2 883 and 2 896 288.3, 289.6
Ar 750.4, 751.1, 763.5, 772.3, 772.4
O 3s 5S8-3p 5P 777.2, 777.4, 777.5

bonds. Also in the case of N2, the time evolution of the Ex Situ Measurements of Collected Powder and
principal bands (H2, CH, and N2) are reduced in intensity; Deposited Films
the reduction is consistent in case of low N2 content, related
to the particle growth. The ex situ ATR-FTIR spectra of collected powder particles,
for different HMDSOO2Ar and HMDSOO2N2 admix-
tures, are shown in Figure 14a and b. The vibrational modes
are the same as previously described in Table 1. The SiOSi
stretching peak (or TO mode) at 1 075 cm1, found for
low O2/Ar or O2/N2 ratios, shifts to 1 072 cm1, because of
the oxygen reduction in the admixture; the decrease of the
stoichiometry in SiOx is more efficient. In addition, the TO
mode, as well as the LO mode, seem to decrease once the
argon or nitrogen content is increased in the admixture,
confirming a reduction in disorder degree of the layers. The
carbon content, represented by the first right part of each
spectrum (700800 cm1), decreases as the Ar (or N2)
content increases; all the peaks related to Si(CH3)x vibra-
tions tend to reduce in amplitude, as well as the Si(CH3)x
stretching vibration at 1 260 cm1 and the CH3 symmetric
and asymmetric stretching vibrations. The powder chem-
Figure 13. Time evolution of the line intensity of principal optical istry is quite similar to the plasma phase chemistry; in both
lines in the HMDSOO2Ar plasma. cases a large amount of argon or nitrogen reduces carbon

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2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.plasma-polymers.org 115
M. Ricci, J. L. Dorier, Ch. Hollenstein, P. Fayet

Figure 14. (a) Absorbance spectra of powder particles produced in HMDSOO2N2 plasmas with different O2/N2 ratio (f O2/N2).
(b) Absorbance spectra of powder particles produced in HMDSOO2Ar plasmas with different O2/Ar ratio (f O2/Ar).

content and promotes monomer polymerization, in terms


of dominance of polymerization.
Films deposited under all the conditions investigated in
the previous section, show chemical characteristics quite
similar to those already described for plasma phase and
powder spectra (Table 1): the SiOSi stretching peak at
1 073 cm1, as shown in Figure 15, shifts to lower
wavenumber if nitrogen or argon is introduced in the
plasma admixture; the peak is less evolved and as well as its
intensity, that, in comparison with LO mode, gives an idea
about the variation of disorder degree. As the argon or
nitrogen flux is increased, both peaks tend to decrease,
reducing the disorder degree. The carbon content is reduced
because of the change of O2/(argon, nitrogen) in the plasma
admixture. In the recorded spectra we noticed the CO and
CO2 peaks at 2 100 and 2 300 cm1, that explain the
monomer oxidation in plasma phase or the desorption from
the reactor walls, as already confirmed by the presence of
oxidized carbon species found in OES spectra.

Conclusion

In this work we have studied the different aspects of


powder in HMDSOO2 plasmas. Oxygen dilution is
Figure 15. Absorbance spectra of deposited film produced in responsible for the particle formation; the higher the
HDMSOO2N2 plasmas with different O2/N2 ratio (f O2/N2). oxygen content is, the larger the particles are. The chemistry

Plasma Process. Polym. 2011, 8, 108117


116 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201000052
Influence of Argon and Nitrogen Admixture in HMDSO/O2 Plasmas . . .

influences the process only within the very first phase of the [14] J.-L. Dorier, Ch. Hollenstein, A. A. Howling, U. Kroll, J. Vac. Sci.
development. Later in time, accretion leads to larger and Technol. A 1992, 10, 1048.
[15] Y. Watanabe, M. Shiratani, Y. Kubo, I. Ogawa, S. Ogi, Appl.
larger particles which can finish up in particles forming a
Phys. Lett. 1988, 53, 3.
plasma crystal. In the case of the introduction of Ar or N2 in [16] A. Bouchoule, A. Plain, L. Boufendi, J. Ph. Blondeau, C. Laure,
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