Full Paper 45

Summary: In this paper, the gas phase composition of
hexamethyldisiloxane (HMDSO) microwave plasma at
4
103 mbar and of the corresponding films were studied
by FTIR spectroscopy under different power conditions. At
low powers, species with a chemical structure very similar to
that of HMDSO were observed in the gas phase, whereas the
film essentially contained short [(CH3)2SiO]n-like chains
with a low branching rate and the end group Si(CH3)3. At
higher powers, the chemical entities present in the gas phase
contained several (SiO)x bonds, whereas the branching
rate in the film increased with the amount of SiH, SiC and
SiO bonds. The interpretation of these observations led to a
proposal involving a chemical mechanism. In this mechan-
ism, the increasing decomposition of HMDSO into by-
products, which themselves increasingly decompose as the
power is raised, plays a determining role.

Comparison of FTIR plasma and deposit spectra showing the relationship

between the HMDSO by-products present in the plasma phase and the different
functional groups and end groups present in the deposited films.

FTIR Plasma Phase Analysis of Hexamethyldisiloxane

Discharge in Microwave Multipolar Plasma at Different
Electrical Powers
Patrice Raynaud, Bernard Despax,* Yvan Segui, Hubert Caquineau
Laboratoire de Genie electrique (UMR 5003), 118 Route de Narbonne, F-31062 Toulouse Cedex, France
E-mail: despax@lget.ups-tlse.fr

Received: July 9, 2004; Revised: September 13, 2004; Accepted: September 29, 2004; DOI: 10.1002/ppap.200400034
Keywords: gas-phase infrared spectroscopy; microwave discharges; plasma; polysiloxanes; thin films

Introduction tant for deposition and film properties, deposition, in our

Under plasma conditions, thin film deposition often results
fromthesurfacereactionsofneutralactivespecies.Therefore,
the properties and the quality of deposited films depend on the
relative contribution of these species to the film growth.
Understanding how the dissociation conditions affect these
contributions provides important guidance in finding mech-
anisms that lead to film formation from initial precursors.
This paper focuses on the hexamethyldisiloxane
(HMDSO) dissociation mechanism and the resulting spe-
cies as well as the relationship between these species and
the nature of the deposit. Although ions can also be impor-
case, is mainly due to neutral active species. No direct
analyses of the HMDSO dissociation products can be found
in the literature. It has only been indirectly studied. The
works carried out by Magni and Alexander in radio-
frequency discharges using mass spectrometry suggested a
breaking of both the SiO and SiC bonds after electron
impact.[1,2] Besides, studies in microwave discharge using
direct electron cyclotronic resonance (DECR) have shown
that a large production of hydrocarbon molecules is evid-
ence of CSi bond breaking in HMDSO plasma.[35]
Additionally, the HMDSO dissociation may also lead to
other organosilicon species.[6]

Plasma Process. Polym. 2005, 2, 4552 DOI: 10.1002/ppap.200400034 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
46
A determination of HMDSO by-products under different
radiofrequency plasma conditions (100 mTorr) was under-
taken by Fracassi et al.[7] Their results were obtained by
analyzing the gas effluent in a cold trap. Under their
operating conditions, a coupled gas chromatography-mass
spectrometry (GC-MS) setup allowed them to essentially
detect many linear and cyclic oligomers containing a
(CH3)2SiO chemical group.
The aim of this work is to contribute to the understand-
ing of HMDSO plasma deposition mechanism at very low
pressures (few mbar) by FTIR analysis of the gas phase and
the chemical analysis of the deposits.
Experimental Part
The experimental reactor coupled to the gas FTIR measure-
ment setup, schematically represented in Figure 1, has been
described elsewhere.[3,4] It consists of a 30-cm-diameter
central cylindrical section and two smaller cylindrical sections
above and below the housing spherical mirrors. The optical
length of the IR beam can be adjusted by multi-reflection to a
maximum of 44 m. The spectra were recorded by means of
Biorad FTS 60A FTIR spectrometer. The data reported were
obtained with a resolution of 0.5 cm1. The detection threshold
of our IR setup was around 5
1010 molecules  cm3. The
plasma was generated in a microwave multipolar (MMP)
reactor excited by distributed electron cyclotron resonance
(DECR) at 2.45 GHz. The analyses were carried out at a
total pressure of 4
103 mbar with power ranging from 60 to
600 W. Because the mirrors and KBr windows can become
covered with a deposit during the plasma run, particular
attention was paid to the estimation of the mirror coverage by
the deposit. Before each experiment, a baseline was recorded
as the background for the new experiment. Moreover, spectra
of the empty reactor were recorded after each run, their
Figure 1. Microwave reactor coupled to the gas IR measurement
setup.
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P. Raynaud, B. Despax, Y. Segui, H. Caquineau
amplitudes were very low and negligible with respect to the IR
measurements in the plasma gas phase.
FTIR spectroscopy gives information on the neutral species
present in the plasma. However, plasma gas IR spectra exhibit
numerous bands (Figure 3) from several chemical groups; this
makes precise product identification somewhat difficult as seen
later.
Results
Pure Hexamethyldisiloxane (HMDSO)
FTIR Spectra
The Beer Lambert law was checked at different pressures
with a 40-m path length within the pressure range used in
our experiments. Figure 2 shows a typical HMDSO spec-
trum. An identification of HMDSO bands has been already
done.[1,3,4,8] Table 1 lists the bands observed in the present
study. In the nCH regions, the asymmetric stretching CH3
mode [nas], the symmetric bending CH3 mode [ds CH3 in
Si(CH3)x 1  x  3] and two rocking modes [rCH3 in
Si(CH3)x] respectively appear at 2 964, 1 260 and 850,
and 834 cm1 (weak shoulder). Besides, in the nSiO regions,
the stretching mode of SiOSi bridge band appears at
1 072 cm1.
HMDSO Plasma
Three spectra were recorded under various microwave
power conditions of discharge (Figure 3). At a low power,
i.e., 60 W, some remarkable features were observed
(Figure 3a, Table 1). First, all the monomer bands decreased
in intensity under these plasma conditions showing a partial
HMDSO consumption. Nevertheless, the band intensity
decreases of SiCH3 at 1 260 and Si(CH3)3 at 850 cm1 were
Figure 2. HMDSO FTIR spectrum at a pressure of 4

103 mbar.
2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 FTIR Plasma Phase Analysis of Hexamethyldisiloxane Discharge in Microwave Multipolar Plasma at Different Electrical Powers 47

Table 1. Comparison of the IR bands of HMDSO gas phase and the bands present under low power conditions (60 W) and high power
conditions (600 W) (see Figure 1 and 2).a)

HMDSO gas phase Plasma HMDSO (60 W) Plasma HMDSO (600 W)

cm1 cm1 cm1

(L12) 3 660 (vw) 3 660 (w)

Small rovibrational acetylene band structure 3 290
centered at (L13) 3 290
(L14) 3 016 methane Q branch and 3 016
its rovibrational structures
(L1) 2 964 (s) CH a-stretching (L1) 2 965 2 958 (vs)
(L2) 2 907 (w) CH s-stretching (L15) 2 916 (L23) 2 924
(L16) 2 894 (L24) 2 873
(L17) 2 138 (L25) 2 132
(L18) 2 128
(L3) 1 587(vw) 1 587
(L4) 1 452(vw) 1 457 1 457
1 443 ethylene 1 404
(L5) 1 414(vw) 1 415
1 305 CH4 1 303 CH4
(L6) 1 260 (s) CH3 s-bending in Si(CH3) 1 261 1 256
1 135 (w) 1 135
(L7) 1 072 (vs) SiOSi a-stretching 1 072 1 072
(L8) 1 017 (vw) (L26) 1 022
(L19) 949 ethylene
(L20) 914
(L21) 903
(L9) 850(vs) CH rocking in Si(CH3)3 850
(L10) 834(vw) CH rocking 837
(L27) 796
(L11) 759(qs) SiC s-stretching in Si(CH3)3 759
(L22) 729 acetylene 729 acetylene
689(w) 694
a)
(vs): very strong, (s) strong, (qs) quite strong, (w) weak, (vw) very weak.

lower than the absorbance decrease of the SiOSi band at
1 072 cm1. These observations were confirmed by com-
paring the absorbance ratios (R) of the SiOSi and SiCH3
bands (R0 2.44 HMDSO without plasma, R60W 2.02 at
Figure 3. Plasma FTIR spectra at different microwave powers:
a) 60, b) 170 and c) 600 W.
60 W in HMDSO plasma). This variation in R indicates the
presence of species other than HMDSO in the plasma.
Besides, the shapes and the relative amplitudes of the
asymmetric stretching mode in the nCH regions around
2 965 cm1 were modified. Second, new absorption bands
were identified in this spectrum. First of all, sharp bands
appeared at 2 128 and 2 138 cm1. Three other weaker
bands appeared at 914, 903 and 3 660 cm1. Finally, several
other absorption bands appeared in the CH regions. For
instance, methane with the main band of the Q branch at
(3 016 cm1) overlapped the stretching band of the CH3
group belonging to the HMDSO molecules. Also, the main
bands of acetylene at 729 cm1 and between 3 330 and
3 200 cm1 and that of ethylene at 944 cm1 were detected.
Under powers equal or superior to 600 W (Figure 3c), the
most remarkable features were: (i) the shift to a lower
energy of CH3 asymmetric stretching mode, (ii) a clear
increase of a band around 2 873 cm1(CH2), (iii) the
appearance of a broad band around 1 022 cm1 (iv) the main
band of HMDSO at 1 072 cm1 almost disappeared
whereas the bands around 1 260 cm1 remained. The sharp
band at 2 128 cm1 disappeared and a band around

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48
2 130 cm1 was weakened. Bands at around 910 cm1 were
not detectable. Also, the presence of a weak, but broad band
at 3 660 cm1 was observed.
Discussion
Analysis of the Gas Phase
In order to accurately examine the HMDSO by-products in
the plasma phase, we have to eliminate residual HMDSO
spectrum bands. Actually, the FTIR spectrum was obtained
by subtracting the remaining HMDSO spectrum of the gas
phase from the plasma spectrum: a step-by-step subtraction
was carried out until we observed a very small inversion of
the pure HMDSO bands. The spectra obtained just before
this slight inversion were used for the analyses.
At low microwave powers, Figure 4a clearly shows the
bands mentioned above, but without the HMDSO vibra-
tional spectrum disturbances. The presence of vibrations at
3 660, 2 138, 2 128.5, 1 260, 850 and 834 cm1 is confirmed.
The presence of hydrocarbons is also confirmed. The bands
at 2 128.5, 2 138, 914, 903 cm1 are in the range of SiH
bands. The main difference with respect to the initial plasma
spectrum is the appearance of an important band at
1 068 cm1, which could be the signature of a SiOSi
bridge whose band normally appears at 1 072 cm1 for the
HMDSO monomer. This slight wave number shift is
probably due to a small change in the Si environment. A
very small shoulder also appears at 1 025 cm1.
A study of HMDSO radiofrequency discharges at about
100 mbar showed the production of tetramethylsilane
(TMS), trimethylsilanol (TMSOH) ethyltrimethylsilane
(ETMS), pentamethyldisiloxane (PMDSO), ethylpenta-
methyldisiloxane (EPMDSO).[7] At low plasma power in
DECR (60 W), our spectra do not show any TMS bands such
as the absorption bands at 868.7 (vs) and 1 254 cm1.[4] A
Figure 4. Plasma FTIR spectra at different microwave powers:
a) 60, b) 170, and c) 600 W, obtained after spectrum subtraction of
remaining HMDSO.
Plasma Process. Polym. 2005, 2, 4552 www.plasma-polymers.org
P. Raynaud, B. Despax, Y. Segui, H. Caquineau
theoretical work from McKean for (CH3)3SiH (TriMS)
predicted a very strong absorption at 2 128.5 cm1.[9]
Table 2 summarizes the similarity between bands of the
trimethylsilane (TriMS) and some bands obtained under
low power plasma conditions. Except for the very strong
band around 2 128.5 cm1, the TriMS bands are more
difficult to identify in the plasma because of their low
intensities with respect to the other bands. Nevertheless,
one of the bands either at 903 or at 914 cm1 can be assigned
to the SiH bending mode of TriMS. According to McKean,
this mode is at 908 cm1.[9] The presence of this species at
low power can partly explain the m/z peaks at 73 [Si(CH3) 3,
M
TriMS  1) and 59 [SiH(CH3)2 , MTriMS  15] observed in
the mass spectrum.[2] The band at 1 068 cm1 together with
the remaining bands at 1 262 and 850 cm1 also indicate the
presence of some products with the same structure as
HMDSO. PMDSO should be the molecule involved con-
sidering the SiH stretching band at 2 139 cm1 and one of
the SiH bending bands at around 910 cm1. The m/z peak at
133 [H(CH3)2SiOSi(CH3)
2 , MPMDSO  15] in the mass
spectrum also detected by Alexander suggests the presence
of PMDSO.[2] Finally, the very weak band at 3 660 cm1
could indicate traces of trimethylsilanol. Thus, PMDSO,
TriMS and hydrocarbons seem to be the main HMDSO
by-products present in the gas phase under low power
conditions.
The situation seems to be more complicated under high
power conditions (600 W) with the presence of bands at
2 956, 2 924, 2 878 and 1 025 cm1 (Figure 4c). However,
with respect to the gas phase spectrum under low power
conditions (60 W), the strong increase of the CH stretching
bands in the 2 900-cm1 range, the disappearance of the
bands at 2 128.5, 850 and 759 cm1, and the band shift from
1 068 to 1 022 cm1 are worth mentioning and can draw
comments. The first interesting observation concerns the
TriMS absence which is unambiguously characterized by
the disappearance of the band at 2 128.5 cm1. The dis-
appearance of the band at 1 068 cm1 clearly indicates no
significant amount of PMDSO present. As a confirmation of
the absence of these molecules (TriMS, PMDSO), the band
at 850 cm1, an indication of Si(CH3)3 presence in these
monomers, shifted to 837 cm1. This behavior implies a
modification of the chemical environment of Si(CH3)3
group. Moreover, the Si(CH3)3 amount is low at this power
as revealed by the low intensity of the 837-cm1 band and
the disappearance of the weak band at 760 cm1 corres-
ponding to SiC in Si(CH3)3.
The modification of the main band at 1 072 cm1
attributed to SiOSi bridges in pure HMDSO also draws
comments on the evolution of the gas phase species. Under
low power conditions, the appearance of species such as
PMDSO leads to a band at 1 068 cm1. This 4-cm1 shift
is consistent with the slight chemical modification of
HMDSO to PMDSO. Under high power conditions, only a
broad band at 1 022 cm1 appears as a signature of SiOSi.
2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 FTIR Plasma Phase Analysis of Hexamethyldisiloxane Discharge in Microwave Multipolar Plasma at Different Electrical Powers 49

Table 2. Comparison of bands of HSi(CH3)3 and bands present in HMDSO plasma (60 and 600 W) (see Figure 1 and 2).a)

SiH(CH3)3 (TriMS) theoretical bands, ref.[9] Bands present in plasma without Bands present under high
HMDSO bands (60 W) power conditions (600 W)

cm1 cm1 cm1

3 118 s (L12) 3 660 (vw) 3 660 (w)

3 069 s Methane left branch of rovibrational
structure of methane (10 bands)
2 965.1 (nas CH3) Stretching asym (vs) 2 963 (vs)
(L30) 2 956 (vvs)
(L31) 2 924 (vs)
(L32) 2 873 (vs)
(L17) 2 137 (qs)
2 128.5 (n SiH) stretching(vvs) (L18) 2 128 (vs) 2 132 (vw)
1 268 (ds CH3) (qs) (L 6) 1 262 (vs) 1 256 (vs)
1 256 (ds CH3) (qs)
Bending sym. (qs)
(L28) 1 068 (vs)
(L29) 1 025 shoulder
(L26) 1 022 (vs)
SiCH2Si
or SiOSi
908.1 (d SiH) bending s 903 (w) and 914 (w)
856 (qs) 850 (vs) 837 (s)
842 (s) (L27) 796 (s)
(r CH3) rocking
(L11) 759 SiCH3 in Si (CH3)3
a)
(vs): very strong, (s) strong, (qs) quite strong, (w) weak, (vw) very weak.

This 50-cm1 shift from the reference position in pure or CH2 branching on silicon site.[10] Actually, the deposit
HMDSO and the broadening of the band result from a larger spectra recorded at low and high power are different
structural change in the SiOSi bridge-containing mole- (Figure 5, spectra normalized with regard to the same
cules. Based on Li et al.,[10] this wave number shift to lower thickness). At low power (60 W), the spectrum exhibits a
energy can be attributed to the molecules containing small main band at 1 032 cm1 (Table 3, Figure 5a), whereas the
siloxane chains with a gradually increasing molecular deposit spectrum under a high power shows a broad band at
weight. The appearance of a band at 796 cm1 indicates around 1 022 cm1 (Table 3, Figure 5c). Another feature in
either the presence of SiOSi bending mode or that of the deposit spectrum under a low power (60 W) is a very
SiC with an environment different from that of Si(CH3)3. small amount of SiH, whereas the amount of deposits
Under high power conditions, the slight increase in the
amplitude of the OH band at around 3 660 cm1 is also
worth noting and reveals the reaction between SiO. and
the hydrogen at the deposit surface to form SiOH-contain-
ing products in the gas phase. Notice that in the gas phase of
HMDSO/oxygen plasma, Creatore et al. detected a large
amount of such products.[11]

Relationship between Gas Phase Composition and

Deposit Composition
The band between 1 040 and 1 020 cm1 pertaining to the
FTIR spectrum of HMDSO plasma deposits (Figure 5a:
60 W) has been ascribed to SiOSi stretching mode in a
disturbed environment [(CH3)2SiO]n. Recall that the Si
OSi stretching mode in the HMDSO gas phase peaked at
1 072 cm1 and that the difference between the monomer Figure 5. Deposit FTIR spectra at different microwave powers:
and the deposit was mainly due to carbon substitutions by a) 60, b) 170, and c) 600 W. The spectra are normalized with regard
oxygen atoms to form the (SiO)n backbone with some CH3 to the thickness.

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50
Table 3. Comparison of the IR bands of HMDSO plasma deposits obtained under different power conditions (compare Figure 5).a)
Plasma HMDSO (60 W)
1
cm
(P1) 2 960 (s) CH a-stretching
(P2) 2 902 (w) CH s-stretching
(P3) 2 129 (vw)
(P4) 1 412 (vw)
(P5) 1 257 (s) CH3 s-bending in Si(CH3)
(P6) 1 034 (vs) SiOSi a-stretching
(P7) 834 (vw) CH rocking
(P8) 796
687 (w)
a)
(vs): very strong, (s) strong, (qs) quite strong, (w) weak, (vw) very weak.
obtained at higher powers (>150 W, Figure 5b and c,
Table 3) is larger.
Taking into account the preceding gas phase analysis, the
following global comment can be made. Under low power,
the gas phase mainly contains hydrocarbon molecules,
trimethylsilane, pentamethyldisiloxane and a large amount
of HMDSO, whereas the deposit is characterized by SiO
Si bridges (1 034 cm1), a small SiC (or SiO) amount
(796 cm1), a large Si(CH3)3 amount (840 and 760 cm1)
and a very small amount of SiH bonds (2 129 cm1). On
the other hand at high power (600 W), molecules possibly
containing (SiO)x coupled with a large amount of hydro-
carbon branching seems to be dominant in the gas phase.
Here, the deposit contained SiOSi bridges (1 023 cm1)
as well as a significant SiH amount (2 139 cm1), a high
SiC (or SiO) amount (796 cm1) and very few Si(CH3)3
groups (834 cm1). Note, no significant SiOH bonds were
detected in the deposit, although the IR spectra show the
presence of few silanol groups in the gas phase. The low
concentration in the gas phase could explain the absence of
SiOH in the deposit.
The following interpretation can be given to the pre-
ceding observations. Although the presence of a (SiO)n
backbone is on the whole unquestionable, the occurrence
of a few SiCH2Si bridges or SiCH2CHx is possible.
Indeed, recent papers on thin film deposition from hexa-
methyldisilane indicate that the IR spectrum of deposits
exhibits a broad band at 1 020 cm1 which has been
ascribed to the Si(CH2)nSi bridge (wagging mode
1  n  2).[1214] Obviously, this deposit does not contain
SiO bonds. The presence of the CH2 groups at 2 873 cm1
in the gas phase and 2 876 cm1 (Figure 3c, Table 3) in the
deposit could indicate the presence of some SiCH2Si or
SiCH2CHx bridges.
Taking into account the presence of molecular species in
the gas phase such as CH4, TriMS and PMDSO as assumed
Plasma Process. Polym. 2005, 2, 4552 www.plasma-polymers.org
P. Raynaud, B. Despax, Y. Segui, H. Caquineau
Plasma HMDSO (170 W) Plasma HMDSO (600 W)
1
cm cm1
(P1) 2 960 2 958 (vs)
(P9) 2 905 (P13) 2 905
(P10) 2 894 (P14) 2 876
(P11) 2 136 (P15) 2 140
(P12) 2 128
1 570
1 457
1 411 1 406
1 258 1 257
1 032 (P16) 1 022
837
(P8) 796 (P8) 796
694
by mass spectrometry[2,5,7] and confirmed by our work, it is
clear that the radicals associated with these species, e.g.,
.
CH3, .Si(CH3)3 and (Me)3SiOSi.(Me)2 could be involved
in the deposition process.
In addition to the deposit, we emphasize that the disso-
ciation products after gas-phase recombination or species
desorption by surface recombination or both lead to the
formation of stable volatile molecules. This competition
between the formation of volatile products and the deposi-
tion process must be considered when tackling the key
problem of the plasma deposition mechanism. At pressures
lower than 5
103 mbar (very low probability of chemical
reactions in the gas phase), surface reactions cannot
be ignored in the correct diagnosis of the origin of some
neutral species. Besides, under high power, the large
HMDSO consumption can favor the electron interaction
with HMDSO by-products leading to a partial modification
of the deposition process chemistry.
In this respect, the large hydrocarbon production in the
gas phase explains the carbon deficit in the deposit as
measured by XPS. Indeed, the C/Si ratio decreases below 2
in the deposit instead of 3 in HMDSO. Moreover, taking
into account the global oxygen deficit concerning the
HMDSO by-products, it is reasonable to find an increase in
[O]/[Si] ratio in the deposit with respect to HMDSO ([O]/
[Si] 0.5). This was found to be the case in ref.[2] at a low
power ([O]/[Si] 0.7) and in ref.[15] at a high power ([O]/
[Si] 1). These last observations lead to the conclusion that
both carbon and silicon atoms are missing in the deposit
as compared to the HMDSO atomic composition. This is
consistent with the large amount of stable species such
as hydrocarbons, HSi(CH3)3 or [(CH3)3(CH3)2SiO]x
SiH(CH3)2, present in the gas phase which are pumped out.
This view is confirmed by the work of Fracassi et al.[7] who
detected these kinds of products in HMDSO radiofrequency
discharges. Alexander et al.[2] have shown by means of ToF-
2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 FTIR Plasma Phase Analysis of Hexamethyldisiloxane Discharge in Microwave Multipolar Plasma at Different Electrical Powers
SIMS analysis of deposits that a lot of heavy ionized frag-
ments involved few (Si CH2) units which were attributed
to SiCH2Si bond breaking. Nevertheless, as already
shown, the deficit of both carbon and silicon compared to
oxygen in the deposit is compensated by their excess in the
gas phase.
Mechanism Proposal
At a low power, the mechanism assumed by Magni et al.[1]
appears to be quite consistent with our results. They
proposed the following dissociation reactions:
CH3 3 SiOSiCH3 3 e ! CH3 3 SiO SiCH3 2
CH3 e
CH3 3 SiOSiCH3 3 e !  SiCH3 3 CH3 3 SiO e
or
CH3 3 SiOSiCH3 3 e !  SiCH3 3 CH3 2 SiO
 CH3 e 3 CH bands at around 2 957, 2 924 and 2 873 cm1 with
Three of the obtained radicals, (CH3)3SiO.Si(CH3)2,
CH.3 and .Si(CH3)3 can explain the presence of TriMS,
PMDSO and methane in the gas phase as described above.
Of course, these radicals may also contribute to the deposit
and to polymer chain ends. For instance, the large content of
Si(CH3)3 (840 cm1) in the deposit could be related to the
.
Si(CH3)3 radicals which react with a dangling bonds.
The main structure of the deposit based on a (SiO)
backbone probably arises from the other two radicals whose
generic formula is (CH3)xSiO. Two arguments are in favor
of this proposal. First, the atomic composition of these
radicals is quite close to the O/Si ratio observed in the film.
Second, the very weak band at 3 660 cm1 (OH bonds)
could confirm the presence of a (CH3)3SiO. radical which
can induce the silanol production by hydrogen abstraction
from the deposit surface.
Moreover, the FTIR spectrum of the gas phase at
intermediate power (170 W, Figure 4b) shows a broad band
with a maximum between 1 055 and 1 030 cm1. This indi-
cates the presence of molecules containing [(CH3)2SiO)x,
2  x  3] as shown by Fracassi et al.[7] in radiofrequency
discharge and confirmed by mass spectrometry.[2] Based on
the proposed mechanism, the only means to obtain these
small oligomers is the reaction of (CH3)xSiO species with
each other to increase the (SiO)y chain length (Figure 6).
In any situation, the deposit composition (O/Si  1) leads to
the conclusion that the most reactive and probably the main
mechanism for deposition is:
either
nCH3 3 SiO ! CH3 3 SiOSiCH3 2 n2SiCH3 3
n  2CH3
Plasma Process. Polym. 2005, 2, 4552 www.plasma-polymers.org
51
1 Figure 6. Simplified reaction pathway for deposition at low
powers.
or
2
dangling bond nCH3 2 SiO ! siteCH3 2 SiOn1
CH3 2 SiO 5
At higher powers (400 W) in the gas phase, the strong
respect to Si(CH3)x and SiOSi bands let us think that
heavy stable hydrocarbon molecules are produced or hydro-
carbon groups are grafted onto siloxane-like species con-
taining chains such as [(CH3)2SiO]xSi(CH2)ySi or
[(CxHy)2SiO]z or both. If we consider the corresponding
deposits, the hydrocarbon group content (between 2 959
and 2 876 cm1) is very low with respect to that of the SiH,
SiCH3 and SiOSi groups. In the layer, the importance of
the bands at 796 cm1 (SiC or SiO) with respect to the
very weak band at 834 cm1 [Si(CH3)3] indicates the
disappearance of the Si(CH3)3 group from the deposit.
These last observations on the deposition process could
be explained based on a modification of the discharge com-
position. At a high power, HMDSO is almost totally
consumed, and the gas phase is dominated by its by-
products. Then, electrons can also interact with these by-
products to form new radical species which can contribute
to the deposition process (Figure 7). For instance, reactions
such as the following might be possible:
CH4 e ! CH3 and CH
2 and CH

xH e 6
HSiCH3 3 e ! H SiCH3 2  CH3 e 7
PMDSO e ! HCH3 4  Si2 O CH3 and
HCH3 2  SiO or HCH3 SiO  CH3   SiCH3 e
8
It can be noticed that the obtained radicals contain SiH
bonds, which can explain the presence of such bonds in the
deposit.
As observed in the IR spectra of both the gas phase and
4 the deposit, the gradual change in composition from low
2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
52
Figure 7. Simplified reaction pathway for deposition at high
powers (>100 W).
power to high power is due to a combination of HMDSO
depletion and HMDSO by-product formation. This ob-
viously leads to a variable chemical composition of the
deposits even though the main chain is controlled by SiO
oligomerization.
Conclusion
Plasma deposition processes from siloxane monomers have
only been described so far in the literature as the forma-
tion of a (SiO)n backbone resulting from the siloxane
monomer break-up of organic groups in the gas phase or at
the surface. The power should just change the amount of
CHx groups in the film. Moreover, it is commonly assumed
that the dominant reactive gas phase species are the main
deposit precursors. The present work reveals a more com-
plex situation.
It is especially interesting to note that the deposit
structure is more or less a kind of reverse of what is in the
gas phase. Broadly speaking, given the chemical structure
of the initial monomer and its fragmentation, just a few
basic chemical species are involved in the deposition
process, whereas the other active radicals partly react with
the surface to form volatile molecules. At low powers, the
species produced during the primary HMDSO dissociation
stages dominate the process. The radical surface reaction
Plasma Process. Polym. 2005, 2, 4552 www.plasma-polymers.org
P. Raynaud, B. Despax, Y. Segui, H. Caquineau
produces stable species such as TriMS, PMDSO and CH4
obtained after a radical recombination. On the other hand,
(CH3)xSiO seems to be the main deposit precursor.
At a higher power, the HMDSO by-products in the gas
phase are also dissociated by electronic impact producing
new radicals which contribute to the deposit. This leads to
an increase of the grafting rate of the (SiO) chains in the
films. Meanwhile, the length of the siloxane chains in the
gas phase increases. This is also the case in the deposit as
shown by the shift of the SiOSi stretching towards energy
as low as 1 020 cm1 and a large decrease in the amount of
the Si(CH3)3 group. This shift could also be favored by the
formation of SiCH2Si bridges.
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