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Vacuum 71 (2003) 349–359

Intermediate gas phase precursors during plasma

CVD of HMDSO

D. Theirich*, Ch. Soll, F. Leu, J. Engemann

Universit.at Wuppertal, Forschungszentrum f .ur Mikrostrukturtechnik-fmt, Campus Freudenberg, Geb. FM, Rainer-Gruenter-Strasse 21,

42119 Wuppertal, Germany

Received 28 May 2002; accepted 7 November 2002

Abstract

In plasma enhanced chemical vapor deposition (PECVD) from complex molecules like hexamethyldisiloxan

(HMDSO) often not the molecules themselves but intermediate and reactive radicals or molecules are the precursors for

film growth. Additionally, such PECVD processes are volume or mass flow limited under many process conditions. In

these cases growth rate and film homogeneity is mainly dominated by the precursor content and its spatial distribution

in the gas or plasma phase. Therefore the identification of such intermediate precursors is an important task to optimize

a PECVD process and also helps us to understand the plasma chemical reactions during PECVD. A combined mass

spectrometry and IR absorption study is used to identify intermediate gas phase precursors in HMDSO/O2 PECVD

remote plasmas. For this study a microwave plasma CVD system was used with HMDSO/O2 ratios between 0.1 and 1

at typical operating pressures between 20 and 70 Pa. Three reactive intermediate species are proposed to act as aprecursor for SiO

x film growth from HMDSO/O2 plasmas. All three having a mass of 148 amu. The related reactive

groups are the silanon (Si=O), silanol (Si–OH) and aldehyde (C=O) groups.

r 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Plasma; Polymerization; CVD; HMDSO; Infrared absorption; Mass spectrometry; Precursor

1. Introduction

In recent years plasma enhanced chemical vapor

deposition (PECVD) of silicon containing filmshas become a widely used technique for thin film

deposition especially for semiconductor, optical,

wear protection, diffusion barrier and many other

applications [1–6]. Besides silane, tetraethyloxysi-

lane (TEOS) and others hexamethyldisiloxane

(HMDSO: (CH3)3SiOSi(CH3)3) is a commonly

used precursor gas for the PECVD of SiO2 and

non-stochiometric SiOx

films, whereby the latter

may have varying hydrocarbon contents. HMDSO

is much easier to handle as for example silane andyields a high deposition rate up to more than 1 mm/

min [7]. HMDSO also represents a trend to use

more and more complex organic molecules as

precursors for PECVD and plasma polymeriza-

tion, because they often yield a very versatile

control of film properties by controlling the degree

of retention of molecular structure, functional

groups and elemental composition. For example

the control of the hydrocarbon and oxygen

content in SiOx

films deposited from HMDSO

*Corresponding author. Fax: +49-202-439-1412.

E-mail address: [email protected]

(D. Theirich).

0042-207X/03/$ - see front matter r 2003 Elsevier Science Ltd. All rights reserved.doi:10.1016/S0042-207X(02)00763-7

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also gives control over film hardness and elasticity

and its optical and diffusion properties [5,7,8].

High rate PECVD processes with complex

organic molecules such as HMDSO especially onflat substrates are mostly performed in a volume

limited process regime. This means that the film

deposition rate is limited by the content of the

precursor in the plasma phase. As a result film

deposition is usually inhomogeneous on three-

dimensional substrates and thus those processes

are used for flat or almost flat substrates. This is in

contrast to conventional thermal CVD processes as

for example the CVD of silane [9] and some earlier

work on HMDSO which was performed in a

different process regime [10,11]. In both cases the

process was surface limited. For example the silane

is adsorbed on the surface and is thermally

decomposed by the surface temperature and forms

a thin film. The volume limitation of the PECVD

of complex molecules is caused by the relative

stability of the used molecules. Only when they

undergo collision processes in the plasma they

dissociate into reactive intermediate radicals. These

reactive intermediate radicals undergo further

reactions, some of them actually resulting in film

growth, others resulting for example in powder

growth, in etching or in stable volatile products,which are pumped away from the reaction chamber

[12,13]. To control the deposition process in terms

of rate, homogeneity or resulting film properties it

is necessary to control the density and spatial

distribution not only of the precursor gas but also

of the reactive intermediate precursor radicals in

the PECVD reactor. Therefore it is necessary to

identify the reactive intermediate precursors actu-

ally forming the film. This paper presents a study

based on mass spectrometry and infrared absorp-

tion spectroscopy to identify possible intermediateprecursors in HMDSO/O2 remote plasmas for

SiOx

film deposition.

2. Experimental

2.1. Plasma system

All diagnostic experiments were performed in a

vacuum chamber with a microwave remote plasma

setup, which can also be used as a plasma CVD or

plasma polymerization system for the deposition

of scratch resistant SiOx

films from HMDSO. A

SLAN I microwave plasma source is mounted ontop of a cubic stainless steel vacuum chamber

(400 400 400 mm3). The plasma source, which

is described in detail elsewhere [14] can be

separated from the chamber by a stainless steel

grid with a transparency of 50%. The source

basically consists of a ring shaped circular wave-

guide, which couples microwaves via slot antennas

into a quartz dome with 160 mm inner diameter,

where the plasma is ignited. The non-film forming

carrier gases argon and oxygen are introduced into

this quartz dome by a gas inlet. The plasma source

is powered by a 6 kW microwave generator via a

circulator and sensor for reflected power. The

generator can be operated in cw and pulsed mode.

HMDSO is introduced directly into the vacuum

chamber by a gas shower ring downstream the

separation grid. The whole process gas is pumped

b y a 6 0 m3 h1 rotary pump with a 500 m3 h1

roots blower. Pumping speed and pressure can be

controlled by a butterfly valve. Flow rates of argon

and oxygen are controlled by mass flow control-

lers. HMDSO is vaporized in a tank at a

controlled temperature of 351C and introducedinto the chamber through a precise leakage valve.

All components connecting the monomer tank

with the vacuum chamber are heated to avoid

condensation of the monomer. Pressure measure-

ments are made with a gas independent pressure

sensor (baratron). Base pressure of the system is

3 102 Pa. Typical operating pressures were

between 20 and 70 Pa. Typical flow rates were

20–50 sccm for HMDSO and 0–300 sccm for

oxygen and argon. When the plasma is switched

on the ionized, dissociated or excited argon andoxygen flows out of the plasma source where it

mixes with the HMDSO forming a remote plasma

in the deposition chamber. For deposition pur-

poses a substrate can be placed 200 mm down-

stream the plasma source outlet in the center of

the vacuum chamber. A detailed description of the

whole setup as well as data for typical ion and

radical densities can be found elsewhere [7,15,16].

In order to identify reaction products in-

cluding possible reactive intermediate precursors

D. Theirich et al. / Vacuum 71 (2003) 349–359350

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information on the molecular weight as well as on

the molecular structure of the molecules and

radicals in the remote plasma zone is needed.

Mass spectrometry together with infrared absorp-tion spectroscopy are well suited to gain this

information. Since the HMDSO/O2 plasma is a

strongly depositing plasma several measuring

signal degradations can occur during in situ

measurements. Therefore diagnostical methods

which obtain many data in a short time are

necessary. To meet all these demands we chose

neutral particle mass spectrometry and FTIR

absorption spectroscopy for this study.

2.2. Mass spectrometry

For mass spectrometry the substrate is removed

and a mass spectrometer (Balzers PPM 421) is

flanged to a side flange of the vacuum chamber.

The neutral particles enter the spectrometer

through a 100mm aperture. In the spectrometer

the particles sequentially pass a cross beam

ionization source, an energy filter consisting of a

cylindrical mirror analyzer (which is not active

during neutral particle analysis) and a quadrupole

mass filter. Then they are detected by a secondaryelectron multiplier. Electrons of 70 eV energy were

used for post-ionization in the spectrometer for all

experiments shown in this work. The whole

spectrometer is differentially pumped. The whole

system is mounted with a bellow on a carriage and

can be separated from the chamber by a shut-off

valve. When the spectrometer is moved into the

chamber the aperture, through which the neutrals

are extracted into the spectrometer, is placed

200 mm downstream the plasma source. Due to

this construction the mass spectrometer is exposedto the depositing plasma only during the measure-

ment and therefore contamination by film deposi-

tion or powder formation inside the spectrometer

are minimized. Nevertheless the transmission of

the energy analyzer still shifts during a single

measurement due to deposition effects of the ion

optics. Therefore in all experiments at least

10sccm argon have been added and all mass

signals have been detected relative to the argon

signal at 40 amu.

2.3. FTIR

The mass spectrometer was replaced by a FTIR

spectrometer (Bruker Equinox 55) for the infraredgas phase absorption experiments. The infrared

beam is coupled through KBr windows into the

vacuum chamber. An external MCT detector is

used to detect the infrared light passing through

the gas and plasma, respectively. The whole

optical path outside the vacuum chamber is

purged by dry and CO2 free air. The beam is

positioned 200 mm downstream the plasma source.

Therefore the IR beam probes the same plasma

region as the mass spectrometer and the same

region where thin films could be deposited. At a

typical operating pressure of 60 Pa in the vacuum

chamber a single beam pass is enough to gain a

good absorption signal. Before each measurement

a reference spectrum was taken without HMDSO

and plasma. After each measurement Ar/O2plasma cleaning of the chamber and test spectra

recording was done consecutively until no change

in two consecutive test spectra could be detected.

The last test spectrum was then taken as a new

reference for the next measurement. The plasma

cleaning was done in order to remove organic

residues from adsorbed HMDSO and to yield afull oxidation of the silicon films on the walls and

especially on the KBr windows.

3. Results and discussion

Fig. 1 shows some typical results for deposition

rates and deposition characteristics in a HMDSO/

O2 microwave remote plasma. Argon was intro-

duced additionally for these experiments to keep

the total gas flow rate (600 sccm) and thus themean residence time in the reaction zone constant

while varying the oxygen/HMDSO ratio. First of

all the absolute deposition rates are quite high and

achieve values close to 800 nm/min (for cw

plasmas). The second result from Fig. 1 is that

the whole deposition process in the remote region

of an HMDSO/oxygen/argon plasma is flow rate

limited in terms of oxygen flow. This is reflected in

the increase of the deposition rate with increasing

oxygen content in the total gas flow. Plasma

D. Theirich et al. / Vacuum 71 (2003) 349–359 351

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chemical reactions with oxygen being dominant

for the film deposition process over electron

collision processes can also be assumed comparing

the relevant particle densities in the remote region(here 200 mm downstream the plasma source) and

taking into account the electron energy distribu-

tion function. In a comparable set-up electron

densities of 108 –109 electrons/cm3 and electron

temperatures of 1–3 eV have been measured whilethe oxygen radical density reach values of 1013 –

1014 radicals/cm3 [15,16]. Additional to oxygen

flow rate effects an influence of the time modula-

tion of the plasma power can be observed (cw case

and 100 Hz rectangular pulses with 50% duty

cycle).

In order to get a more inside view of the plasma

process first neutral particle mass spectrometry has

been carried out. Neutral particle mass spectro-

metry needs a postionization in the spectrometer.

As a drawback this leads to a strong additional

dissociation of the HMDSO in the mass spectro-

meter itself. Fig. 2 shows a mass spectrum of pure

HMDSO without plasma. This spectrum reflects

the dissociation in the spectrometer. As expected a

very large number of various fragments occur in

the spectrum whereas the peak at 162 amu of the

unfragmented HMDSO is very small. For mass

line identification see for example Ref. [17]. The by

far strongest peak in the spectrum appears at

147 amu. It can be attributed to Si2OðCH3Þþ5 ;

which is produced by dissociative ionization of

0

200

400

600

800

1000

0 2 4 86 10

Oxygen/HMDSO ratio

D e p o

s i t i o n r a t e ( n m / m i n )

Fig. 1. Deposition rate as a function of the oxygen/HMDSO

ratio for cw (J) and pulsed (; 100 Hz, 50% duty cycle)

plasma. Mean power: 2 kW; pressure: 40–70 Pa; 30sccm

HMDSO; 0–300sccm oxygen; 0–270 sccm argon. Concerning

the difference between the deposition rate in the pulsed and cw

plasma see Ref. [18] and the discussion of Fig. 5a.

Fig. 2. Neutral mass spectrum of HMDSO at 50 Pa chamber pressure.


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HMDSO under dissociation of a methyl group.

This leads to the result that dissociation of a single

methyl group is the most probable dissociation

appearing in the spectrometer under the appliedoperating conditions.

Adding oxygen and measuring under plasma

conditions changes the mass spectrum. Especially

the oxygen itself and the oxidation products of

HMDSO like H2O, CO and CO2 now occur in the

spectrum much above their residual gas level. In

order to investigate the role of oxygen we observed

the mass lines of these oxidation products and the

strongest lines of HMDSO fragments at 59, 66, 73,

131, 133 and 147 amu while varying the oxygen

flow. The results are shown in Fig. 3 for a pulsed

plasma at 10 Hz and 50% duty cycle and in Fig. 4.

for 200 Hz, respectively. The oxidation products in

Fig. 3(a) increase with increasing oxygen flow.

Typical oxidation chains can be observed. First the

CO line increases. Adding more oxygen to the

plasma leads to a further oxidation of CO and

consequently also the CO2 line increases. Finally,

also the O2 line increases, because more oxygen is

introduced than is needed for the oxidation of

carbon and hydrogen. But oxygen is also needed

for the oxidation of silicon in the gas phase or at

the surface. Fig. 3(b) shows a decrease of allHMDSO fragments except the fragment at

133 amu, which shows a strong increase. The

results at 200 Hz pulsing frequency are very

similar. The only differences are the increase of

the O2 line at even smaller oxygen flows (Fig. 4(a))

and the not so strongly developed increase of the

133 amu line (Fig. 4(b)). But also at 200 Hz pulsing

frequency the line at 133 amu still reveals a

different behavior than the other fragment lines.

Assuming that similar to the dissociative ioniza-

tion of the HMDSO molecule the detected ion at133 amu is most probably created by dissociative

ionization under dissociation of a methyl group in

the spectrometer, the 133 amu line originates from

a species with 148 amu. The question now is, can

the species at 148 amu be an intermediate gas

phase precursor for SiOx

film growth with x close

to 2. The Si:O ratio in the HMDSO molecule is

2:1. To grow a SiOx

film with a Si:O ratio close to

1:2 a silicon containing precursor plus additional

oxygen is needed. For a volume or flow limited

deposition process the growth rate should dependmainly on the precursor impact rate on the

surface. In this case and at constant pressure and

temperature the precursor content in the gas phase

and the growth rate of the film should be positively

correlated. Therefore above results suggest the

species at 148 amu to be the dominant silicon

containing precursor for SiOx film growth from

HMDSO. This correlation has additionally been

investigated when varying the pulse frequency and

the pressure. The results are shown in Fig. 5(a) for

0

0.8

0.6

0.4

0.2

1

0 100 200 300

Oxygen flow (sccm)

I / I m a x

1

1.2

0.8

0.6

0.4

0.2

I / I m a x

(a)

0 100 200 300

Oxygen flow (sccm)(b)

Fig. 3. Relative intensities of mass lines in a pulsed HMDSO/

O2/Ar microwave remote plasma (20 sccm HMDSO, 15 sccm

Ar, 50Pa, 2 kW mean power, 10 Hz, 50% duty cycle) as a

function of the oxygen flow rate: (a) data for oxidation

products CO (’); H2O (); CO2 (J); O2 (&), and (b) data

for monomer fragments at 59 amu (’); 66amu (&); 73amu

(); 131amu (J); 133amu (m); 147 amu (+).


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the deposition rate and in Fig. 5(b) for the gasphase content of the precursor with 148 amu. At a

pressure of 50 Pa a minimum appears for 200 Hz

pulse frequency for the growth rate as well as for

the precursor content. At a lower pressure of 20 Pa

both curves are much more flat indicating only a

small influence of the pulse frequency on film

growth rate and precursor content. Reasons for

the pulse frequency influencing the growth process

of SiOx films from HMDSO has been discussed

elsewhere [18]. Summarizing, film growth rate and

the content of the 148 amu species in the gas phase

show a strongly positive correlation when varying

oxygen flow, pulse frequency and pressure. All this

indicates the 148 amu species to be a precursor forSiO

x film growth. This is in contrast to some other

work, which proposed the Si2O(CH3)5 radical to

be one of the dominant precursors [19]. But the

same work also reports about a strong signal in the

positive ion spectra at 148 amu, which is attributed

to a HSi2OðCH3Þþ5 ion (see also Eq. (1)). But

signals at 148 amu may result from several other

molecules or radicals as will be discussed below.

First of all there is a fragment of HMDSO after

dissociation of a methyl group and attachment of

a hydrogen atom

Me32Si2O2Si2HMe2; ð1Þ

where Me means a methyl group. Another

possibility is a molecule with a silanon type of

bond (Eq. (2)).

O

Me3−Si−O−Si .

Me

ð2Þ

There are several reactions possible that canresult in such a molecule. Some of them are

described below. First there can be a reaction

scheme (Eq. (3)) starting with a dissociative

ionization by an electron and followed by a

reaction with atomic oxygen similar to the

proposed mechanism in an Argon plasma by

Wr !obel et al. [12,20].

Me32Si2O2Si2Me3þe-

Me32Si2O2Si2Me2þMe þ 2e;ð3aÞ

Me3232Si2O2Si2Meþ2 þO-

Me32Si2O2Si2O2Meþ2 ;

ð3bÞ

Me32Si2O2Si2OMeþ2-

Me32Si2O2Si2O2Me þ Meþ

:

ð3cÞ

Another possibility might be a direct reaction

with atomic oxygen und dissociation of two

0

0.2

0.4

0.6

0.8

1

0 100 200 300

Oxygen flow (sccm)

0 100 200 300

Oxygen flow (sccm)

I / I m a x

0.2

0.4

0.6

0.8

1

1.2

I / I m a x

(a)

(b)

Fig. 4. Relative intensities of mass lines in a pulsed HMDSO/

O2/Ar microwave remote plasma (20sccm HMDSO, 15 sccm

Ar, 50Pa, 2kW mean power, 200Hz, 50% duty cycle) as a

function of the oxygen flow rate: (a) data for oxidation

products CO (’); H2O (); CO2 (J); O2 (&), and (b) data

for monomer fragments at 59 amu (’); 66amu (&); 73amu

(); 131amu (J); 133amu (m); 147 amu (+).


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methyl groups

Me32Si2O2Si2Me3þO-

Me32

Si2

O2

Si2

O2

Me þ 2Me; ð4Þ

or a reaction with molecular oxygen forming a

CH2 group and methanol

Me32Si2O2Si2Me3 þ O2-

Me32Si2O2Si2O2Me þ CH3OH þ CH2:ð5Þ

Besides these also other reaction channels may

result in a molecule with a silanon group (Si=O).

Moreover this molecule can rearrange into a

molecule with a silanol group (Si–OH) and a

silene group (Si=CH2)

O OH

Me3−Si−O−Si Me3−Si−O−Si .

Me CH2

↔ ð6Þ

Both molecules in Eq. (6) might act as a

precursor for SiOx

film growth and would be

detected in the mass spectrometer after dissocia-

tion of a methyl group at 133 amu. The silanon

type of bond was found under liquid phase

chemistry conditions to oligomerize easily into

cyclic and linear polysiloxanes [21] as it is

10 100 1000

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

50 Pa

20 Pa

10 100 1000

Pulse frequency (Hz)

R e l a t i v e d e p o s i t i o n r a t e

d / d c w

2 kW

40 sccm HMDSO

200 sccm O2

10 100 1000

0.6

0.8

1.0

1.2

1.4

20 Pa

10 100 1000

Pulse frequency (Hz)

R e l a t i v e I n t e n s i t y I / I c w

2 kW

40 sccm HMDSO

200 sccm O2

50 Pa

(a)

(b)

Fig. 5. Deposition rate (a) and mass line intensity of the precursor at 133 amu (b) as a function of the pulse frequency for different

pressures. Plasma parameters are: 50% duty cycle; 2 kW mean power; 40 sccm HMDSO; 200 sccm Oxygen; 15 sccm Argon at 50 Pa and

100 sccm Ar at 20 Pa, respectively. Deposition rate and mass line intensities are given relative to their cw values.


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necessary for film formation under plasma chemi-

cal conditions. Several authors have proposed

molecules containing silanol groups to be pre-

cursors for SiOx film growth [22–24]. Two silanolgroups can react to a siloxane group and water

(Eq. (7)) and form polysiloxanes

2 R2Si2OH-R2Si2O2Si2R þ H2O: ð7Þ

Both possible precursor molecules in Eq. (6)

represent oxidized HMDSO molecules. This ex-

plains why the intensity of the 133 amu line in

Fig. 3(b) shows a variation with the oxygen flow

similar to the oxidation products in Fig. 3(a). The

less significant behavior in Fig. 4(b) might be

caused by a larger contribution of the non-

oxidized HMDSO fragment from Eq. (1) to the

signal at 133 amu in case of 200 Hz pulse

frequency. This also explains, why the oxygen

signal in Fig. 4(a) (200 Hz) increases earlier than in

Fig. 3(a) (10 Hz). Under conditions of Fig. 3(a)

more oxygen is needed to oxidize also HMDSO

molecules and therefore the oxygen signal in-

creases only at higher oxygen flows compared to

Fig. 4(a). Moreover under those conditions also a

higher growth rate can be observed (Fig. 5(a)).

To identify the molecular structure of the

plasma chemical reaction products infrared ab-sorption experiments have been performed. Fig. 6

shows an absorption spectra of HMDSO and

argon gas in the vacuum chamber at 60 Pa without

plasma. The typical absorptions of the siloxan

bond (Si–O–Si), the Si–CH3 bond and the methylgroup itself can be identified [13, 19, 25]. The

Argon does not add any signal. The spectrum in

Fig. 7 was measured with the plasma switched on

plus an additional oxygen flow of 100 sccm. The

O2:HMDSO ratio was 90:50. Several additional

absorption signals can be identified in Fig. 7.

Amongst others there are H2O, CO, CO2, OH,

SiHn

absorptions and an interesting region around

1.700 cm1 where a H2O signal overlaps with the

C=O stretch signal either from CH2O or CH2O2[19]. A detailed analysis of the infrared absorption

results will be published elsewhere. Of special

interest for this paper are the oxygen flow

dependences of the oxidation products and the

monomer fragments, which are shown in Fig. 8(a)

and (b), respectively. All intensities are evaluated

from peak areas and are normalized to their

maximum. If necessary a peak decomposition

analysis has been done.

The following signals were used to evaluate the

absorption intensities in Fig. 8: CO: area under

CO rotational spectrum between 2000 and

2250 cm1

; H2O: area of a single line at3854 cm1; CO2: area under CO2 asymmetric

Si(CH3)n bend

Si(CH3)n bend

SiOSi bend

CH3 stretch

SiOSi asym. stretch

4000 3000 2000 1000

0.0

0.2

0.4

0.6

A b s o r b a n c e

Wavenumber cm−1

Fig. 6. FTIR absorption spectrum of a HMDSO/Ar mixture at 60 Pa chamber pressure without plasma. Flow rates:

HMDSO:Ar=50:300.


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Summarizing the results from this study there

are three candidates for intermediate precursor

molecules in HMDSO/O2 plasmas presented inEqs. (6) and (8). Between these IR absorption

spectroscopy was not able to decide due to two

reasons. First data on IR absorption of the silanon

group (Si=O) are not available and second

possible absorption signals from the silanol group

(Si–OH) are almost not detectable due to the large

amount of OH and water as volatile oxidation

products of HMDSO. Therefore one, two or all

three of the precursors found may contribute to

SiOx

film growth from HMDSO.

4. Conclusion

Three reactive intermediate species have been

proposed which can act as a precursor for SiOxfilm growth in HMDSO/O2 plasmas. All three

having a mass of 148 amu. The related reactive

groups are the silanon (Si=O), silanol (Si–OH)

and aldehyde (C=O) groups. Further work is

necessary to distinguish between theses groups.

The gas phase content of these precurors can be

used to control and to optimize the deposition

process.

Acknowledgements

This work was supported by the Federal

Ministry for Education and Research under

contract no. 13N6720 and the state Ministries of

Economics and Technology and of Science and

Research of Northrhein-Westfalia. We also like to

thank Dr. Kim for intense and fruitful discussions

of our results.

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