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Journal of Sol-Gel Science and Technology KL648-79-VOROTILOV November 2, 1998 17:40

Journal of Sol-Gel Science and Technology 13, 467–472 (1998)

°
c 1998 Kluwer Academic Publishers. Manufactured in The Netherlands.

Thin ORMOSIL Films with Different Organics

K.A. VOROTILOV, V.A. VASILJEV, M.V. SOBOLEVSKY AND A.S. SIGOV

Moscow State Institute of Radioengineering, Electronics and Automation, 117454, Vernadsky prosp.,
78, Moscow, Russia

Abstract. Structural, optical and electrical properties of silicate films modified by structure fragments containing
different organic groups were studied. The ORMOSILs were produced by a cohydrolysis of tetraethoxysilane with
different types of alkyl (aryl) substituted alkoxysilanes. Film structure and its evolution during heat treatment were
studied by ellipsometry and IR spectroscopy. For methyl- and phenyl-modified silicate films the shrinkage is lower
than for silicate ones in the range of annealing temperature from 200 to 500◦ C. The shrinkage of phenyl-modified
silicate film is more than three times lower than of methyl- and trimethyl-modified ones. The presence of single or
double C C bonds in the organic chain leads to an increase in the film shrinkage due to the thermodestruction of
the bond as it is confirmed by IR data. In the case of phenyl- and methyl-modified silicate films this process starts
from 500◦ C and it is accompanied by abrupt film shrinkage. The dielectric constant and the loss tangent of methyl
and phenyl groups decrease due to reduction of hydroxyl content and film density. Other groups are not effective
due to their thermodestruction at lower temperatures.

Keywords: organically modified silicates, thin films, structural properties, electrical properties

1. Introduction a growing interest in sol-gel processed films in micro-

Recent research on sol-gel science has focussed on
inorganic-organic hybrid materials. In these materials
organic fragments are built into silicon-oxide networks
(organically modified silicates—ORMOSILs) or, in the
general case, into metal-oxide networks (organically
modified ceramics—ORMOCER). A typical method
of producing such inorganic-organic hybrids is by a co-
hydrolysis of an alkoxide and an alkyl(aryl)-substituted
alkoxysilane (in the case of ORMOSILs). Alkyl(aryl)
groups, in contrast to alkoxy ones, do not undergo hy-
drolysis and, as a result, are incorporated into growing
silicon-oxide gel network.
A combination of inorganic and organic networks
facilitates the design of new engineering materials with
exciting properties for a range of applications (see, for
example, [1–3]). In addition inorganic-organic hybrids
are of particular scientific interest as a new solid-state
medium.
Thin films and coatings were the earliest and remain
so far one of the most important applications of the
sol-gel technology. Recent years have been marked by
electronics, optics, and many other areas. One of the
most important application of sol-gel films in micro-
electronics, discussed in this paper, is the process of
planarization of multilevel metallization of very-large
scale integration (VLSI) and ultra-LSI (ULSI) devices
[4, 5].
It is clear that the type, concentration, and spatial
arrangement of organic groups within the metal-oxide
skeleton will substantially determine the material prop-
erties. Thus, practical applications of the inorganic-
organic hybrids require fundamental understanding of
their structural and physical peculiarities. The present
work deals with the study of optical and electrical prop-
erties of silicate films modified by structural fragments
containing different organic groups.
2. Solution Preparation and Film
Coating Process
The ORMOSIL structures were produced by a co-
hydrolysis in n-butanol of tetraethoxysilane with dif-
ferent types of alkyl(aryl) substituted alkoxysilanes:
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468 Vorotilov et al.

Table 1. Some chemical and physical properties of solutions. Table 2. Film covering properties of ORMOSIL solutions.

Organics Viscosity Density Conductivity Refractive R/Si

R/Si = 0.5 (cPs) (g/cm3 ) (Ω−1 cm) index pH
0.15 0.3 0.6
Silicate 3.1 0.8615 8.0 ∗ 10−5 1.3938 1.1
Silicate Good
Me 3.0 0.8546 1.9 ∗ 10−4 1.3959 0.9
Me Good Good Good
3Me 2.8 0.8467 3.6 ∗ 10−5 1.3958 1.7
3Me Good Good Bad
Et 3.4 0.8544 3.1 ∗ 10−5 1.3965 4.3
Bad with APa
Vin 3.0 0.8596 1.4 ∗ 10−4 1.3985 1.0
Et Good Good Good
Hex 3.4 0.8559 3.0 ∗ 10−5 1.4020 6.5
Vin Good Good Good
Ph 3.5 0.8696 3.2 ∗ 10−5 1.4058 5.6
Allyl Middle — —
Hex Good Middle Bad
Good with APa
methyltriethoxysilane, trimethylethoxysilane, ethyltri- Ph Good Middle Middle
Good with APa
ethoxysilane,vinyltriethoxysilane,allyltriethoxysilane,
hexyltriethoxysilane, phenyltriethoxysilane (PTEOS), DPS Good Middle —
and diphenyl diethylhexyloxy diethoxy disiloxane a AP—adhesion promoter: γ -aminopropyltriethoxysilane

(DPS). The equivalent silicon content in the solutions
was 4 wt% and the molar ratio of components was
H2 O/HCl/[Si(OEt)4 + Rx Si(OEt)4−x ] = 4/0.04/1. The
number of organically modified bonds of each silicon
atom R/Si was varied between 0.15 and 0.6.
All solutions were clear after mixing and suitable
for film deposition, except those with high allyl and
hexyl content. Allyl-modified solutions had gelated
after a few hours (12–15 h at R/Si = 0.3, and 3 h at
R/Si = 0.6), whereas hexyl-modified ones (hexyl to sil-
icon ratio 0.6) strongly sedimented immediately after
mixing. No gelation was observed in all the other solu-
tions for at least three months (the solutions remained
clear, except for some sedimentation after 20 days in
the methyl- and vinyl-modified ones). Some charac-
teristics of the ORMOSIL solutions with an organic to
silicon ratio of 0.5 are given in Table 1. These prop-
erties were measured 3 days after the preparation of
solutions. It is important for film deposition that the
nature of organic group has only a slight effect on the
solution viscosity.
The films were deposited on silicon substrates by a
spin-on technique and were annealed at temperatures
from 200 to 900◦ C for 30 min. An important problem
in ORMOSIL film deposition is a loss of film continu-
ity as a result of nonwetting of the substrate surface.
This problem usually arises in the case of high or-
ganic to silicon ratios and extended organic groups (see
Table 2).
γ -Aminopropyltriethoxysilane was used as an adhe-
sion promoter and gave good results in all cases except
for solutions prepared with trimethylethoxysilane.
NH2 CH2 CH2 CH2 Si(OC2 H5 )3 .
3. Evolution of Film Structure During
Heat Treatment
Information concerning film structure and its evolution
during heat treatment was obtained from ellipsometry
and IR spectroscopy data. The film thicknesses and re-
fractive indexes were measured at four points of each
film (in a central part of the substrate) by multiangle
ellipsometry at 632,8 nm and at incident irradiation an-
gles from 45 to 70◦ [6]. The real and imaginary parts
of the refractive index of the uncoated silicon substrate
was determined to be 3.85 and −0.02, respectively.
The measurement errors were ±0.0005 for the refrac-
tive index, and ±0.5 nm for the film thickness. The
deviation in the refractive index and the film thickness
for a given substrate were less than ±0.005 and ±5 nm,
respectively.
Figure 1 presents the dependence of the film thick-
ness of the ORMOSIL films as a function of annealing
temperature. As described above, the initial solutions
had the same concentration of silicon and practically
same viscosity. Therefore, we can consider the change
in the film thickness as an effect of the distortion of the
silicon-oxide network by the organic groups. This sug-
gestion is confirmed by the fact that after annealing at
high temperature (800◦ C) all the films have practically
the same thickness (an increase in the film thickness
for the films annealed at 900◦ C is due to oxidation of
silicon substrate). Therefore, distortion of silicate
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Figure 1. The dependence of the thickness of ORMOSIL films with different organic groups (R/Si = 0.5) as a function of heat treatment
temperature.

Figure 2. The shrinkage of ORMOSIL films with different organic groups (R/Si = 0.5) as a function of heat treatment temperature.
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470 Vorotilov et al.
network is increased as the size of organic group in-
creases (except in the case of vinyl-modified silicate).
This effect is most pronounced in phenyl-modified sil-
icate films the thickness of which are two times the
thickness of unmodified silicate films.
Film shrinkage as a function of annealing tempera-
ture is shown in Fig. 2. Methyl- and phenyl-modified
silicate films have lower shrinkages for annealing tem-
peratures between 200 and 500◦ C than silicate films.
The shrinkage of the phenyl-modified silicate film is
more than three times lower than that of the methyl-
and trimethyl-modified ones (less than 1% shrinkage
from 200 to 400◦ C). The presence of single or double
C C bonds in the organic chain leads to an increase
in the film shrinkage due to its thermodestruction, as
Figure 3. IR spectra of phenyl-modified silicate films annealed at different temperatures.
November 2, 1998 17:40
confirmed by the IR data. In the case of phenyl-
and methyl-modified silicate films this process starts
at 500◦ C and it is accompanied by abrupt film shrink-
age. The process of thermodestruction is illustrated
by the IR spectra of phenyl-modified silicate films (see
Fig. 3). An increase in the annealing temperature from
450 to 600◦ C leads to disappearance of the absorption
peaks of phenyl groups (475, 705, 750, 1140, 1440,
3075 cm−1 ), as well as the shifting of the Si O band
from 1075 to 1080–1085 cm−1 . The latter shift is in-
dicative of a densification of the silicon oxide skeleton
during destruction of phenyl groups. It should be noted
that the IR spectra of phenyl-modified silicate films af-
ter the heat treatment at 600◦ C is different from the
silicate spectra because of the presence of absorption
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Figure 4. The dependence of the refractive index of ORMOSIL films with different organic groups (R/Si = 0.5) as a function of heat treatment
temperature.

Figure 5. The shrinkage and the refractive index of phenyl-modified silicate films prepared from PTEOS and DPS.
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Journal of Sol-Gel Science and Technology KL648-79-VOROTILOV November 2, 1998
472 Vorotilov et al.
peaks resulting from the thermodestruction of phenyl
groups (e.g., absorption peaks at 1705 cm−1 and 1305
cm−1 , conceivably CH3 COC6 H5 and C6 H5 CHO, re-
spectively, [7]). A negative slope in the film shrink-
age at 900◦ C is due to oxidation of the silicon
substrate.
The process of elimination of organic groups as a
result of thermodestruction is clearly seen in the tem-
perature dependence of refractive index, especially,
for phenyl-modified silicate films (see Fig. 4). The
refractive index of this film dramatically falls at an-
nealing temperature 600◦ C from 1.46 to 1.28 as a result
of thermodestruction of the phenyl group and void
production. Annealing at higher temperatures leads to
densification of the film structure due to viscous sinter-
ing, so that the films annealed at 900◦ C have practically
the same refractive index (1.45).
Figure 5 illustrates how the phenyl to silicon content
and the spatial distribution of phenyl groups affect the
refractive index and shrinkage of the films. The in-
crease in silicon to carbon bonds in the films blocks the
polycondensation reaction in some directions and thus
reduces film shrinkage. Films prepared from PTEOS-
based solutions have a more dense structure and lower
shrinkage than ones prepared from DPS. After comple-
tion of hydrolysis of alkoxy-groups, the DPS molecule
differs from the PTEOS one by the presence of two
phenyl groups bonded with two silicon atoms. Al-
though it is hard to obtain direct information concern-
ing film structure, it would appear reasonable that lower
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shrinkage of the films prepared from PTEOS is due to
their greater effectiveness in blocking the polyconden-
sation reaction (at the same Ph/Si content the phenyl
groups in the PTEOS precursor are more uniformly dis-
tributed in silicon matrix, and block higher numbers of
polycondensation chains, than with the DPS precursor
where the two phenyl groups are rigidly fixed.
Acknowledgments
The research described in this work was made possi-
ble in part by grant N 97-02-17822 from the Russian
Foundation for Basic Research and grant 218/68/1–2
from the SSTP “Advanced Technologies and Devices
of Micro- and Nanoelectronics.”
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