Journal of Sol-GelScience and Technology8, 581-584 (1997)

9 1997 KluwerAcademicPublishers. Manufacturedin The Netherlands.

ORMOSIL Films: Properties and Microelectronic Applications

K.A. VOROTILOV, V.I. PETROVSKY, V.A. VASILJEV AND M.V. SOBOLEVSKY

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

Abstract. The properties, as well as some issues of microelectronic applications of organically modified silicate
(ORMOSIL) films, prepared by cohydrolysis in various proportions of tetraethoxysilane (TEOS) and phenyltri-
ethoxysilane (PTEOS), or diphenyldiethylhexyloxydiethoxydisiloxane (DPS) 1, are discussed.

Keywords: organically modified silicates, thin film, refractive index, electrical properties

1. Solution Preparation and Film
F o r m a t i o n Process
The initial solutions were prepared by dissolving
TEOS in n-butanol in the presence of some water and
HC1. The equivalent SiO content was 6 wt.% and
the molar ratio of components was [H20]:[HC1]:
[TEOS] = 6 : 0.04 : 1. After prehydrolysis of the initial
solution during 5 min, PTEOS or DPS were added. The
volume fraction of the added component was 10, 20 or
40% of the TEOS volume in the initial solution (the
calculated Ph/Si ratios were 0.085, 0.156 and 0.270, in
the case of PTEOS, and 0.069, 0.129 and 0.230, in the
case of DPS).
The films were prepared by spinning on silicon
wafers with a following bake at 150~ during 3 min (hot
plate) and a final anneal at Ta = 200, 450 or 600~ dur-
ing 20 min. Multiple application with the intermediate
bake was used for thicker film preparation; (two-fold
coatings were used for electrical measurements, and
three-fold ones for IR spectra). Aluminum electrodes
were formed by lithography process, for electrical
measurements.
2. IR Spectra
IIR spectra of the films were measured with a Perkin-
Elmer 1720 spectrometer in the range from 4000 to
400 cm -1 . IR spectra of the silicate films are typical
of silicate materials prepared by sol-gel techniques and
show the presence of hydroxyl groups. Modification
of silicate with organic leads to the production of typ-
ical phenyl infrared bands, the magnitudes of which
increase with increasing organic content (see Fig. 1).
The IR spectra of the films prepared from PTEOS and

C2H5
I
O C6H5 C6H5
I I I
H5Cr--Si--O--C2H5 C2HaC6H 13--O--Si~Si--O----C6Hl 3C2H 4
I I I
O O O
I I I
C2H5 C2H5 C2H5
Phenyltriethoxysilane Diphenyldiethylhexyloxydiethoxydisiloxane
(PTEOS) (DPS)
582 V o r o t i l o v e t al.

0.24'

!
,-- X2-2000.SP

I X3-2OOD.SP
0.22
- PrSos o
....................... i...................... ,i................... i ......................~
i i i ~
ops ! ~ i/"

i
. . . . . . . . . . . . . . .

Ph ~s 0.2 .......................i......................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

a)
0.18i

0.14 . . . . . . . . .i. . . . . . . .i. . . . . i i i

,u
mm

~ 0.05 oh 0.~5 0'.2 0>5 o.a

Ph/Si

1 i
PTEOS o
1.49 .................... "i...........................i.............................!...............................!................. i
t
............................

X 1.48 ......................i.......................J....................i.........................i...........................L...............
O
"0
.E b)
11.47.46-
........................~................ ~..........................i.................................................i...............

m ,4,
1.44"
1.43-
4000.0 auuu auuu r 2000.0 =.,~v =v~ 400.0

1.42"
CM--5[
0 0.05 0.1 0.15 0.2 0.25 0.3
Ph/Si
IR spectra of ORMOSILS films with the different phenyl
F i g u r e 1.
content (heat treatment temperature 200~

~. 15 ................................. ........... .................................................

DPS have therewith practically no difference, indicat-
ing full removal of ethylhexyl groups during hydrolysis
and polycondensation of DPS. c)
11 ........................ i . . . . . . . . . . . + ......................... i .............................. i ...........................
The heat treatment of the films at 4501C does not
cause the spectra to change compared to the spectra of
m 9
the films treated at 200~ but annealing at 600~ leads m
to the destruction of phenyl radicals, accompanied c i i i ; i
",- 7
by some densification of the silicon-oxide skeleton. e-
This spectrum is similar to the silicate one, but it still 5 ~ t i

contains some organic residues, as a result of phenyl 0.05 &l 0.15 0.2 0.25 0.3
thermodestruction. Ph/$i
Figure 2. The thickness (a), the refractive index (b), and the shrink-
age (between 200 and 450~ heat treatment) of ORMOS1LS films
3. Elfipsometry Study as a function of Ph/Si ratio.

A modification of silicate matrix by phenyl groups
leads to increasing film thickness and refractive index,
and to decreasing film shrinkage during heat treatment
(see Fig. 2). The increase of film thickness is mainly
caused by increasing film-forming component concen-
tration. It is very interesting that the refractive in-
dex shows a nonlinear increase with increasing phenyl
content, in contrast to, for example, methylmodified
silicates whose refractive index linearly decreases with
the methyl content [1]. The increase in the refractive
index of phenylmodified silicate films is due to the high
refractive index of phenyl radicals (e.g., the refractive
indices of PTEOS and methyltriethoxysilane are 1.49
and 1.34, respectively [2]). A nonlinear character of the
 ORMOSIL Films 583

refractive index increase indicates decreasing volume { i i

~
11 84 - PTEOS ~ ~S i
density when incorporating phenyl radicals into silicate
matrix. As it might be shown from the Lorentz-Lorenz
relationship for mixtures, in the case of decreasing vol- 9 84 i ~ i i I a)
ume density, the curve of the refractive index of the 8 i i i i
mixture is convex upwards, similar to the present ex- e~ 7 ................................. ~ ............................. i............... :4 ..................

perimental data (for details see [3]).

The increase of silicon-carbon bonds leads to a 5
blocking of some directions of polycondensation and
to reduction of the film shrinkage. The film shrinkage
decreases from 16% for silicate film, to 6% for OR- 0 0.05 0.1 0.15 0.2 0.25 0.3
Ph/Si
MOSIL film. It should be noted that a reduction in the
film shrinkage with Ph/Si content occurs, in spite of in-
creasing film thickness, whereas an increase in the film
thickness of silicate films leads to significant increase
of their shrinkage (see e.g., [4]). A rise in annealing 0 . 1 6 ~ ...................I .........i..........................
i.............................
i...............................
temperature upto 600~ leads to a sharp increase of ~o.12 L ' i i b)
the film shrinkage and to a reduction of their refrac-
tive index, due to organic decomposition, consistent 0.08 ............... '
"! ......................... r- ....................... zr . . . . . . . . . . . . . . . ~ ............................. t . . . . . . . . . . . . . . . .

with the IR spectroscopy data. It should be stressed ,..I

that the films prepared from PTEOS-based solutions 0.04 . . . . .
have lower shrinkage (especially for high Ph/Si con-
tents) than those prepared from DPS. This testifies that
O0 0.05 0.1 0.15 0.2 0.25 0.3
the PTEOS molecule is more mobile to block polycon-
Ph/Si
densation chains than the DPS molecule in which two
phenyl groups are rigidly fixed in the neighborhood.
I E - 0 6 I _ .................~. . . . . . -:: ...........................
~ - - - ~ ..............................................

4. Electrical Properties
9.. .....................i...................i...............i....................... c)
The dependence of the dielectric constant and the loss
1 E-08 ............i ..............................
~ ...............
tangent, measured at 1 MHz, for the films annealed
................ ~ .............................
~ .......................... i.............................
~ ............
at 450~ as a function of phenyl to silicon ratio, are
shown in Figs. 3(a) and (b). High hydroxyl and water , 00 : : i i :iii;i::i i ~ 7 i !
......
content in the silicate film cause unusually high dielec- iT.
| l
tric constant and loss tangent. The value of the dielectric 1E-1C i i
constant of silicate film is 11.7 and the loss tangent 0 0.05 0.1 0.15 0.2 0.25 0.3
Ph/Si
reaches 0.19. Similar results, indicating the strong
influence of hydroxyls on the dielectric properties of Figure 3, The d i e l e c t r i c c o n s t a n t (a), t h e l o s s t a n g e n t (b), a n d t h e
sol-gel silicate films, were reported earlier (e.g., [4]). f i x e d c h a r g e (c), o f O R M O S I L S f i l m s a s a f u n c t i o n o f P h / S i ratio.

Modification of silicate with phenyl radicals leads to

a practically constant dielectric constant and loss tan-
gent up to the values of about 3.5 for dielectric constant
and 0.02-0.05 for loss tangen, with decreasing Ph/Si ra-
tio. The conceivable reason for this may be the decrease
of material density when phenyl groups are incorpo-
rated into the silicate matrix, as evidenced, in particular,
by the dependence of refractive index upon the phenyl
content, as well as the decrease of hydroxyl content, as
demonstrated by the IR spectra. The semiconductor-
dielectric interface was studied by capacitance-voltage
(CV) measurements at the frequency of 1 MHz. Polar-
izability of hydroxyls causes a counter-clockwise hys-
teresis (injection type) of CV characteristics of silicate
films and a high value of the fixed charge (Fig. 3(c)). As
the phenyl content in the increases, this hysteresis first
goes down, but then changes its direction (polarization-
type hysteresis). Most likely, the reversal of hysteresis
direction is associated with the polarization of phenyl
radicals in high electric field, which is opposite to
584 Vorotilov et al.
hydroxyls. The value of the fixed charge is reduced,
with increasing organic content, from 1.3.10 -7 C/cm 2
for silicate film, up to 10 -9 C/cm 2, for phenylmodified
silicate film.
. Application of Phenylmodified Films
in the Process of Planarization
of Multilevel Interconnections
One of the possible applications of ORMOSIL films is
the process of planarization of multilevel interconnec-
tions of integrated circuits (ICs). Decreasing of IC ele-
ment sizes complicates the topography relief, with the
result that subsequent metal layer is broken or thinned,
leading to decreasing yield and reliability of ICs. Thus,
planarization or smoothing of topography relief is a
crucial point in the fabrication technology of state-of-
the-art ICs.
Silicate films have a low cracking resistance over
surface topography, due to high shrinkage during bake.
Because of this, only thin films (usually 0.1--0.2/zm)
on not too high metal relief can be prepared without
cracking. To improve the planarization coefficient, two
or three-fold applications of silicate films are needed.
This complicates the production process and may ac-
count for defect generation.
By contrast, phenylmodified silicate smoothing
layer gave good planarization coefficient on rather
complex topographies: better than two fold applica-
tion of silicate layers. The films were crack-free over
all tested surface topographies. These results suggest
that phenylmodified silicates are promising materials
in the process of planarization of multilevel intercon-
nections.
6. Conclusions
1. The silicate film prepared by sol-gel techniques
represents a porous body with a rigid metal-oxide
skeleton and high hydroxyl content. A high shrink-
age and rigid network structure cause their low
cracking resistance and poor planarization proper-
ties on complex topographies. Electrical and optical
properties of silicates are mainly determined by hy-
droxyl groups.
. Phenyl radicals, introduced into the silicate net-
work, reduce cross-linking in the polymer struc-
ture, their density and hydroxyl content. These
provide low shrinkage, high cracking resistance,
low dielectric constant and loss tangent of OR-
MOSIL films. Phenyl radicals have good ther-
mal stability, but, at high concentration, they may
develop mobile charges due to their polarizabil-
ity, The PTEOS molecule is more effective to
block polycondensation chains than the DPS one,
in which two phenyl groups are rigidly fixed in
the neighbourhood. The results obtained suggest
that phenylmodified silicates are promising ma-
terials for the planarization of multilevel inter-
connections.
Acknowledgments
The research described in this work was made possible
in part by Grant N MRQ 300 from the International
Science Foundation.
References
1. T. Nakano,K. Tokunaga,and T. Ohta,PLANAR94, June 6, 1994,
Sunnyvale,p. 11.
2. C.J.Brinkerand G.W.Scherer,Sol-GelScience: The Physics and
Chemistry of Sol-Gel Processing (AcademicPress, San Diego,
CA, 1990), 3.
3. K.A. Vorotilov,V.A. Vasiljev,M.V. Sobolevsky,V.1. Petrovsky,
and N.I. Afanasyeva(submittedto Thin Solid Films).
4. K.A.Vorotilov,E.V.Orlova,and V.I.Petrovsky,Thin Solid Films
209, 188 (1992).