U.S. patent application number 11/318747 was filed with the patent office on 2006-06-22 for ethyleneoxide-silane and bridged silane precursors for forming low k films.
Invention is credited to Thomas H. Baum, Steven Bilodeau, Alexander S. Borovik, Abigail Ebbing, Jeffrey F. Roeder, Daniel Vestyck, Chongying Xu.
Application Number | 20060134897 11/318747 |
Document ID | / |
Family ID | 34062640 |
Filed Date | 2006-06-22 |
United States Patent
Application |
20060134897 |
Kind Code |
A1 |
Borovik; Alexander S. ; et
al. |
June 22, 2006 |
Ethyleneoxide-silane and bridged silane precursors for forming low
k films
Abstract
An organosilicon precursor for vapor deposition, e.g., low
pressure (<100 Torr), plasma-enhanced chemical vapor deposition
(PECVD) of a low k, high strength dielectric film, wherein the
precursor includes at least one of: (i) silicon-pendant oxiranyl
functionality; and (ii) a disilyl moiety of the formula ##STR1##
wherein x is an integer having a value of from 0 to 4 inclusive.
These precursors are useful for the formation of dielectric films
having dielectric constants on the order of .about.3 and less, and
a hardness exceeding .about.1 GigaPascals.
Inventors: |
Borovik; Alexander S.; (West
Hartford, CT) ; Xu; Chongying; (New Milford, CT)
; Baum; Thomas H.; (New Fairfield, CT) ; Bilodeau;
Steven; (Oxford, CT) ; Roeder; Jeffrey F.;
(Brookfield, CT) ; Ebbing; Abigail; (Danbury,
CT) ; Vestyck; Daniel; (Danbury, CT) |
Correspondence
Address: |
INTELLECTUAL PROPERTY / TECHNOLOGY LAW
PO BOX 14329
RESEARCH TRIANGLE PARK
NC
27709
US
|
Family ID: |
34062640 |
Appl. No.: |
11/318747 |
Filed: |
December 24, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10619785 |
Jul 15, 2003 |
7022864 |
|
|
11318747 |
Dec 24, 2005 |
|
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Current U.S.
Class: |
438/584 ;
549/215 |
Current CPC
Class: |
C09D 4/00 20130101; C09D
4/00 20130101; C23C 16/401 20130101; C07F 7/0814 20130101; C08G
77/04 20130101; C07F 7/1804 20130101 |
Class at
Publication: |
438/584 ;
549/215 |
International
Class: |
H01L 21/20 20060101
H01L021/20; C07F 7/02 20060101 C07F007/02 |
Claims
1. An organosilicon precursor for vapor deposition of a low k, high
strength dielectric film, wherein the precursor comprises a disilyl
moiety of the formula ##STR24## wherein x is an integer having a
value of from 0 to 4 inclusive.
2. An organosilicon precursor according to claim 1, wherein x is
1.
3. An organosilicon precursor according to claim 1, wherein x is
2.
4. An organosilicon precursor according to claim 1, having the
formula (III):
R.sup.4R.sup.5R.sup.6Si--(CH.sub.2).sub.y--SiR.sup.7R.sup.8R.sup-
.9 (III) wherein: each of R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8 and R.sup.9 can be the same as or different from one
another and each is independently selected from the group
consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
fluoroalkyl, C.sub.1-C.sub.8 alkoxyl, C.sub.6-C.sub.10 cycloalkyl,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6
vinyl, C.sub.3-C.sub.6 allyl, and oxiranylalkylene of formula (IV)
##STR25## wherein s is 0 or 1; and y is an integer having a value
of from 0 to 4 inclusive.
5. The organosilicon precursor of claim 4, wherein x is 1.
6. The organosilicon precursor of claim 4, wherein x is 2.
7. The organosilicon precursor of claim 4, wherein x is 0.
8. An organosilicon precursor composition for vapor deposition of a
low k, high strength dielectric film, comprising an organosilicon
precursor according to claim 1.
9. The organosilicon precursor composition of claim 8, wherein the
organosilicon precursor has the formula:
R.sup.4R.sup.5R.sup.6Si--(CH.sub.2).sub.y--SiR.sup.7R.sup.8R.sup.9
(III) wherein: each of R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9 can be the same as or different from one another and
each is independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxyl, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, C.sub.3-C.sub.6
allyl, and oxiranylalkylene of formula (IV) ##STR26## wherein s is
0 or 1; and y is an integer having a value of from 0 to 4
inclusive.
10. The organosilicon precursor composition of claim 9, wherein x
is 1.
11. The organosilicon precursor composition of claim 9, wherein x
is 2.
12. The organosilicon precursor composition of claim 9, wherein x
is 0.
13. The organosilicon precursor composition according to claim 8,
further comprising TMCTS.
14. The organosilicon precursor composition according to claim 8,
further comprising a porogen.
15. The organosilicon precursor composition of claim 14, wherein
said porogen is selected from the group consisting of compounds of
the formula (X): R.sup.10R.sup.11SiR.sup.12R.sup.13 (X) wherein:
each of R.sup.10, R.sup.11, R.sup.12 and R.sup.13 can be the same
as or different from one another and each is independently selected
from the group consisting of H, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 alkoxyl, C.sub.6-C.sub.10 cycloalkyl, and
C.sub.6-C.sub.10 aryl, with the proviso that at least one of
R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is C.sub.1-C.sub.8
alkoxyl.
16. The organosilicon precursor composition of claim 14, wherein
said porogen is selected from the group consisting of:
.sup.tBu.sub.2Si(OCH.sub.3).sub.2
.sup.tBu.sub.2Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5).sub.2Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5).sub.2Si(OC.sub.2H.sub.5).sub.2 (C.sub.6H,
.sub.1).sub.2Si(OCH.sub.3).sub.2
(C.sub.6H5).sub.2Si(OC.sub.2H.sub.5).sub.2
.sup.tBuSi(OCH.sub.3).sub.2H .sup.tBuSi(OC.sub.2H.sub.5).sub.2H
(C.sub.6H.sub.5)Si(OCH.sub.3).sub.2H
(C.sub.6H.sub.5)Si(OC.sub.2H.sub.5).sub.2H
(C.sub.6H.sub.5)Si(OCH.sub.3).sub.2H
(C.sub.6H.sub.5)Si(OC.sub.2H.sub.5).sub.2H
(.sup.tBu)(CH.sub.3)Si(OCH.sub.3).sub.2
(.sup.tBu)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2 wherein
.sup.tBu is tertiary butyl.
17. A method of synthesizing a bridged disilane compound of formula
(II):
R.sup.4R.sup.5R.sup.6Si--(CH.sub.2).sub.y--SiR.sup.7R.sup.8R.sup.9
(III) wherein: each of R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9 can be the same as or different from one another and
each is independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxyl, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, C.sub.3-C.sub.6
allyl, and oxiranylalkylene of formula (IV) ##STR27## wherein s is
0 or 1; and y is an integer having a value of from 0 to 4
inclusive, said method comprising derivatization of a corresponding
bridged chlorosilane.
18. The method of claim 17, wherein said derivatization step
comprises reacting said corresponding bridged chlorosilane with
tetraalkylsodium to alkylate said corresponding bridged
chlorosilane.
19. The method of claim 17, wherein said derivatization step
comprises the reaction
MeCl.sub.2SiCH.sub.2CH.sub.2SiMeCl.sub.2+4MeONa.fwdarw.Me(MeO).sub.2SiCH.-
sub.2CH.sub.2SiMe(OMe).sub.2+4NaCl.
20. The method of claim 17, wherein said derivatization step
comprises the reaction
Me.sub.2ClSiCH.sub.2CH.sub.2SiMe.sub.2Cl+2MeONa.fwdarw.Me.sub.2(MeO)SiCH.-
sub.2CH.sub.2SiMe.sub.2(OMe)+2NaCl.
21. The method of claim 17, wherein said derivatization step
comprises the reaction
HSiCl.sub.2CH.sub.2HSiCl.sub.2+4MeONa+2MeOH.fwdarw.(MeO).sub.3SiCH.sub.2S-
i(OMe).sub.3+4NaCl+2H.sub.2.
22. A method of forming a low k, high strength dielectric film on a
substrate, comprising vapor depositing said film on the substrate
from a precursor comprising a disilyl moiety of the formula
##STR28## wherein x is an integer having a value of from 0 to 4
inclusive.
23. The method of claim 22, wherein said precursor is selected from
the group consisting of disilane compounds of formula (III):
R.sup.4R.sup.5R.sup.6Si--(CH.sub.2).sub.y--SiR.sup.7R.sup.8R.sup.9
(III) wherein: each of R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9 can be the same as or different from one another and
each is independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxyl, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, C.sub.3-C.sub.6
allyl, and oxiranylalkylene of formula (IV) ##STR29## wherein s is
0 or 1; and y is an integer having a value of from 0 to 4
inclusive.
24. The method of claim 23, wherein x is 0.
25. The method of claim 23, wherein x is 1.
26. The method of claim 23, wherein x is 2.
27. The method of claim 22, wherein said vapor depositing step
comprises use of a porogen in combination with said precursor.
28. The method of claim 27, wherein said porogen is selected from
the group consisting of compounds of the formula (X):
R.sup.10R.sup.11SiR.sup.12R.sup.13 (X) wherein: each of R.sup.10,
R.sup.11, R.sup.12 and R.sup.13 can be the same as or different
from one another and each is independently selected from the group
consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxyl,
C.sub.6-C.sub.10 cycloalkyl, and C.sub.6-C.sub.10 aryl, with the
proviso that at least one of R.sup.10, R.sup.11, R.sup.12 and
R.sup.13 is C.sub.1-C.sub.8 alkoxyl.
29. The method of claim 27, wherein said porogen is selected from
the group consisting of: .sup.tBU.sub.2Si(OCH.sub.3).sub.2
.sup.tBu.sub.2Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5).sub.2Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5).sub.2Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5).sub.2Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5).sub.2Si(OC.sub.2H.sub.5).sub.2
.sup.tBuSi(OCH.sub.3).sub.2H .sup.tBuSi(OC.sub.2H.sub.5).sub.2H
(C.sub.6H.sub.5)Si(OCH.sub.3).sub.2H
(C.sub.6H.sub.5)Si(OC.sub.2H.sub.5).sub.2H
(C.sub.6H.sub.5)Si(OCH.sub.3).sub.2H
(C.sub.6H.sub.5)Si(OC.sub.2H.sub.5).sub.2H
(.sup.tBu)(CH.sub.3)Si(OCH.sub.3).sub.2
(.sup.tBu)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OCH.sub.3).sub.2
(C.sub.6H.sub.5)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2 wherein
.sup.tBu is tertiary butyl.
30. The method of claim 22, wherein said vapor depositing step
comprises chemical vapor deposition.
31. The method of claim 22, wherein said vapor depositing step
comprises plasma-enhanced chemical vapor deposition.
32. The method of claim 22, wherein said vapor depositing step
comprises flowing said precursor to a vapor deposition locus in a
carrier gas.
33. The method of claim 32, wherein said carrier gas comprises
carbon dioxide.
34. The method of claim 22, wherein the precursor and the carrier
gas are the only potential sources of oxygen at the vapor
deposition locus.
35. The method of claim 22, wherein the precursor is selected from
the group consisting of: Me(EtO).sub.2SiCHCH.sub.2O;
Me(MeO).sub.2Si CH.sub.2CHCH.sub.2O; Me.sub.2Si
(CHCH.sub.2O).sub.2;
Me(MeO).sub.2SiCH.sub.2CH.sub.2SiMe(OMe).sub.2;
Me.sub.2(MeO)SiCH.sub.2CH.sub.2SiMe.sub.2(OMe); and
(MeO).sub.3SiCH.sub.2Si(OMe).sub.2.
36. The method of claim 22, wherein the precursor further comprises
TMCTS.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a divisional application of U.S. patent application
Ser. No. 10/619,785 filed in the name of Alexander S. Borovik on
Jul. 15, 2003 and entitled "ETHYLENEOXIDE-SILANE AND BRIDGED SILANE
PRECURSORS FOR FORMING LOW K FILMS," the disclosure of which is
hereby incorporated herein by reference, for all purposes. Priority
of said U.S. patent application Ser. No. 10/619,785 is claimed,
under the provisions of 35 USC 120.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to low dielectric constant
films, and to precursors and methods useful in making such
films.
[0004] 2. Description of the Related Art
[0005] As semiconductor devices are scaled to higher processor
speeds and smaller, denser structures, there is an increasing need
to reduce resistance-capacitance (RC) delays present in
interconnect wiring. Since the dielectric constant k is
proportional to capacitance (C), scaling relationships require
reductions in k values of the dielectric material. In addition to
the requirement of low k values, reliability issues require that
the dielectric material have a high degree of mechanical strength.
Currently available dielectric films have low mechanical strength
as k values decrease.
[0006] Among the various materials that are currently available for
forming low k films, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS)
is a widely studied precursor for deposition of low k thin films
used as interlayer dielectrics in integrated circuitry. Dielectric
films formed from TMCTS typically have k values in a range of from
about 2.6 to about 3.0, but lack sufficient hardness for
large-scale integration. For next generation very large-scale
integration (VLSI) devices, dielectrics will be required that have
a dielectric constant k below 2.5 with hardness greater than about
1 gigapascal (gPa).
[0007] Accordingly, the art continues to seek improvements in
dielectric materials, in the quest for dielectrics having both high
mechanical strength and low k value.
SUMMARY OF THE INVENTION
[0008] The present invention relates generally to low dielectric
constant films, and to precursors and methods useful in making such
films, e.g., for the manufacture of semiconductor devices and
products.
[0009] In one aspect, the invention relates to an organosilicon
precursor for vapor deposition, e.g., low pressure (<100 Torr),
plasma-enhanced chemical vapor deposition (PECVD) of a low k, high
strength dielectric film, wherein the precursor comprises at least
one of:
[0010] (i) silicon-pendant oxiranyl functionality; and
[0011] (ii) a disilyl moiety of the formula ##STR2## wherein x is
an integer having a value of from 0 to 4 inclusive.
[0012] In another aspect, the invention relates to an organosilicon
precursor composition for vapor deposition of a low k, high
strength dielectric film, wherein the composition comprises:
(A) an organosilicon precursor comprising at least one of:
[0013] (i) silicon-pendant oxiranyl functionality; and
[0014] (ii) a disilyl moiety of the formula ##STR3## wherein x is
an integer having a value of from 0 to 4 inclusive; and (B) a
porogen.
[0015] Another aspect of the invention relates to a method of
forming an oxiranylsilane compound of formula (I): ##STR4##
wherein: [0016] m is an integer having a value of 0 to 6,
inclusive; [0017] n is 0 or 1; [0018] x is an integer having a
value of 0 to 3, inclusive; and [0019] each R and R* can be the
same as or different from one another and each is independently
selected from the group consisting of H, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8 alkoxy,
C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, and
C.sub.3-C.sub.6 allyl, [0020] such method comprising oxidizing a
corresponding vinylsilane or allylsilane compound.
[0021] In one preferred aspect, the oxiranylsilane compound has the
formula (II) set out below: ##STR5## wherein: [0022] each of
R.sub.1, R.sub.2 and R.sub.3 can be the same as or different from
one another and each is independently selected from the group
consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
fluoroalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.6-C.sub.10 cycloalkyl,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6
vinyl, and C.sub.3-C.sub.6 allyl; and [0023] n is 0 or 1; [0024]
with the proviso that if n=1, then one of R.sub.1, R.sub.2 and
R.sub.3 alternatively can be an oxiranyl functionality: ##STR6##
(sometimes hereinafter referred to as ethyleneoxide
functionality).
[0025] Yet another aspect of the invention relates to a method of
synthesizing a bridged disilane compound of formula (III):
R.sup.4R.sup.5R.sup.6Si--(CH.sub.2).sub.y--SiR.sup.7R.sup.8R.sup.9
(III) wherein: [0026] each of R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8 and R.sup.9 can be the same as or different from one
another and each is independently selected from the group
consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
fluoroalkyl, C.sub.1-C.sub.8 alkoxyl, C.sub.6-C.sub.10 cycloalkyl,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6
vinyl, C.sub.3-C.sub.6 allyl, and oxiranylalkylene of formula (IV)
##STR7## [0027] wherein s is 0 or 1; and [0028] y is an integer
having a value of from 0 to 4 inclusive, [0029] such method
comprising derivatization of a corresponding bridged
chlorosilane.
[0030] In a further aspect, the invention relates to a method of
forming a low k, high strength dielectric film on a substrate,
comprising vapor depositing said film on the substrate from a
precursor comprising at least one of:
[0031] (i) silicon-pendant oxiranyl functionality; and
[0032] (ii) a disilyl moiety of the formula ##STR8## wherein x is
an integer having a value of from 0 to 4 inclusive.
[0033] Other aspects, features and advantages of the invention will
be more fully apparent from the ensuing disclosure and appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 is a graph of FTIR transmission spectra of a film
deposited from TMCTS and a film deposited from
Me(EtO.sub.2)SiCHCH.sub.2O under low oxygen activity deposition
conditions.
[0035] FIG. 2 is a plot of deposition rate, in Angstroms per
minute, as a function of measured radio frequency power, in watts,
for each of Me(EtO.sub.2)SiCHCH.sub.2O (denoted in the graph as
DEOMORS), tetramethylcyclotetrasiloxane (denoted in the graph as
TMCTS), and tetraethylorthosilicate (denoted in the graph as TEOS),
each utilized in the deposition process in combination with a same
porogen under similar conditions.
DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS
THEREOF
[0036] The present invention contemplates a new class of precursor
compounds that are useful in forming low k films having superior
mechanical strength characteristics.
[0037] The precursor compounds of the invention in a first general
category are organosilicon source reagents including
silicon-pendant oxiranyl functionality. The organosilicon source
reagents include monosilicon-containing compounds as well as
polysilicon-containing compounds, e.g., disilanes, disilylalkyl
compounds, disiloxanes and cyclosiloxanes. The number of oxiranyl
functional groups in the molecule can be selectively adjusted along
with other R and OR groups to optimize the behavior of the
precursor molecule for a specific film-forming application, e.g., a
low-pressure plasma chemical vapor deposition (CVD) process, and
the molecule can include H groups in combination with oxiranyl,
methyl, methoxide, and other functionality. Cross-linked silyl
structures (having an Si--C--Si moiety) can also be employed in the
organosilicon precursors of the invention.
[0038] One general class of compounds of the invention has the
formula (I): ##STR9## wherein: [0039] m is an integer having a
value of 0 to 6, inclusive; [0040] x is an integer having a value
of 0 to 3, inclusive; and [0041] each R and R* can be the same as
or different from one another and each is independently selected
from the group consisting of H, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8 alkoxy,
C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, and
C.sub.3-C.sub.6 allyl.
[0042] Within the foregoing general formula (I), one sub-class of
oxiranylsilane compounds of the invention has the formula (II):
##STR10## wherein: [0043] each of R.sub.1, R.sub.2 and R.sub.3 can
be the same as or different from one another and each is
independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxy, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, and
C.sub.3-C.sub.6 allyl; and [0044] n is 0 or 1; [0045] with the
proviso that if n=1, then one of R.sub.1, R.sub.2 and R.sub.3
alternatively can be ##STR11## an oxiranyl functionality.
[0046] Within the foregoing general formula (I), another sub-class
of silyloxirane compounds of the invention has the formula (V):
##STR12## wherein: each of R.sub.1, R.sub.2 and R.sub.3 is
independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxy, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, and
C.sub.3-C.sub.6 allyl.
[0047] Yet another sub-class of silyloxirane compounds within the
general formula set out below has the formula (VI): ##STR13##
wherein: each of R.sub.1 and R.sub.2 is independently selected from
the group consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
fluoroalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.6-C.sub.10 cycloalkyl,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6
vinyl, and C.sub.3-C.sub.6 allyl.
[0048] A further sub-class of silyloxirane compounds within the
general formula (I) has the formula (VII): ##STR14## wherein: each
of R.sub.1, R.sub.2 and R.sub.3 is independently selected from the
group consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
fluoroalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.6-C.sub.10 cycloalkyl,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6
vinyl, and C.sub.3-C.sub.6 allyl.
[0049] A further sub-class of compounds within the scope of broad
formula (I) comprises compounds of the formula (VIII) set out
below: ##STR15## wherein: [0050] m is an integer having a value of
from 0 to 6 inclusive; [0051] n is 0 or 1; [0052] each R.sub.1,
R.sub.2 and R* can be the same as or different from one another and
each is independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxy, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, and
C.sub.3-C.sub.6 allyl.
[0053] A further sub-class of oxiranyl compounds of the invention
has the formula (IX): ##STR16## wherein: [0054] m is an integer
having a value of from 0 to 6 inclusive; [0055] n is 0 or 1; [0056]
each of R.sub.1 and R* can be the same as or different from one
another and each is independently selected from the group
consisting of H, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8
fluoroalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.6-C.sub.10 cycloalkyl,
C.sub.6-C.sub.10 aryl, C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6
vinyl, and C.sub.3-C.sub.6 allyl.
[0057] Illustrative compounds within the broad scope of the present
invention include the compounds set out below.
Me(EtO).sub.2SiCHCH.sub.2O Formula (A), ##STR17## Me(MeO).sub.2Si
CH.sub.2CHCH.sub.2O Formula (B), ##STR18## Me.sub.2Si
(CHCH.sub.2O).sub.2 Formula (C), ##STR19## wherein Me is
methyl.
[0058] The ethyleneoxide-substituted silane compounds of the
invention are useful precursors for the formation of low k films
having dielectric constant below 2.5, by deposition methods such as
plasma-enhanced chemical vapor deposition (PECVD). The
ethyleneoxide moiety in the precursor molecule provides a
functionality with a weak carbon-oxygen bond. Under mild plasma
conditions, this bond breaks first and by absorbing the plasma
energy prevents the breakage of other silicon-carbon bonds in the
precursor molecule. The resulting incorporation of carbon in the
deposited films provides lowered k values. The formation of oxygen
and carbon radicals during the PECVD film-forming process also
facilitates cross-linking within the film to produce films of
superior hardness.
[0059] The ethyleneoxide-substituted silane precursor compounds of
the invention are readily synthesized by oxidation of either vinyl
or allyl groups on correspondingly functionalized silane compounds.
Useful oxidizing agents for such purpose include
meta-Cl(C.sub.6H.sub.4)C(O)OOH, denoted m-CPBA, .sup.tBuOOH,
wherein .sup.tBu is tertiary butyl, and Me.sub.3OOSiMe.sub.3,
wherein Me is methyl, as well as other oxidants having sufficient
oxidizing strength and inertness in relation to Si--OR fragments.
The reaction can be run in a suitable non-flammable solvent medium,
e.g., using a solvent such as dichloromethane (CH.sub.2Cl.sub.2),
chloroform (CHCl.sub.3), etc., which provides a safe environment
for the strong oxidizing agent.
[0060] An illustrative example is the synthesis of
Me(EtO).sub.2SiCHCH.sub.2O, which is obtained in 50% yield
according to Reaction (1) below. ##STR20##
[0061] Another illustrative example is the synthesis of
Me(MeO).sub.2SiCH.sub.2CHCH.sub.2O, which is obtained in almost
quantitative yield according to Reaction (2) below. ##STR21##
[0062] Reaction (2) involving the allylsilane analog was much
faster compared to Reaction (1) involving the corresponding vinyl
compound.
[0063] Me(EtO).sub.2SiCHCH.sub.2O was employed as a precursor for
PECVD formation of low k films, and yielded films having a k value
of 3.1 and a hardness of 2.3 GPa.
[0064] Very low k value films can be obtained using the
dioxiranylsilane compounds of formula (III) above, such as
Me.sub.2Si(CHCH.sub.2O).sub.2, which can be synthesized according
to Reaction (3) below. ##STR22##
[0065] The precursor compounds of the invention in a second general
category are bridged silane source reagents of the formula (III):
R.sup.4R.sup.5R.sup.6Si--(CH.sub.2).sub.y--SiR.sup.7R.sup.8R.sup.9
(III) wherein: each of R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8
and R.sup.9 can be the same as or different from one another and
each is independently selected from the group consisting of H,
C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 fluoroalkyl, C.sub.1-C.sub.8
alkoxyl, C.sub.6-C.sub.10 cycloalkyl, C.sub.6-C.sub.10 aryl,
C.sub.6-C.sub.10 fluoroaryl, C.sub.2-C.sub.6 vinyl, C.sub.3-C.sub.6
allyl, and oxiranylalkylene of formula (IV) ##STR23## [0066]
wherein s is 0 or 1; and [0067] y is an integer having a value of
from 0 to 4 inclusive.
[0068] Preferably, the number of methylene groups, i.e.,
--(CH.sub.2)-- groups, in the silane compound of formula (III) is
one or two.
[0069] The precursors of formula (III) employ bridged carbons
between silicon atoms in the molecule, to improve film hardness.
During deposition, the --(CH.sub.2).sub.x-- moieties remain in the
film's cross-linking silicon centers, to provide significantly
improved hardness, and concurrently lower k values due to the
incorporation of carbon in the deposited film, in relation to
corresponding silane precursors lacking the --(CH.sub.2).sub.x--
moieties of the formula (III) compounds.
[0070] The bridged silanes of formula (III) can be readily
synthesized by derivatization of commercially available bridged
chlorosilanes.
[0071] For example, Me(MeO).sub.2SiCH.sub.2CH.sub.2SiMe(OMe).sub.2
and Me.sub.2(MeO)SiCH.sub.2CH.sub.2SiMe.sub.2(OMe) are readily
synthesized at yields of 82% and 88%, respectively, by the
respective Reactions (4) and (5) set out below.
MeCl.sub.2SiCH.sub.2CH.sub.2SiMeCl.sub.2+4MeONa.fwdarw.Me(MeO).sub.2SiCH.-
sub.2CH.sub.2SiMe(OMe).sub.2+4NaCl Reaction (4):
Me.sub.2ClSiCH.sub.2CH.sub.2SiMe.sub.2Cl+2MeONa.fwdarw.Me.sub.2(MeO)SiCH.-
sub.2CH.sub.2SiMe.sub.2(OMe)+2NaCl Reaction (5):
[0072] (MeO).sub.3SiCH.sub.2Si(OMe).sub.3 is correspondingly
synthesized using MeONa by the reaction scheme of Reaction (6) set
out below.
HSiCl.sub.2CH.sub.2HSiCl.sub.2+4MeONa+2MeOH.fwdarw.(MeO).sub.3SiCH.sub.2S-
i(OMe).sub.3+4NaCl+2NaCl Reaction (5):
[0073] The compounds of formula (III) can be used as precursors for
formation of low k, high strength films, in vapor deposition
processes.
[0074] Such precursors of formula (III) can be employed alone or
alternatively in combination with porogen materials, such as
porogens of the formula (X): R.sup.10R.sup.11SiR.sup.12R.sup.13 (X)
wherein: each of R.sup.10, R.sup.11, R.sup.12 and R.sup.13 can be
the same as or different from one another and each is independently
selected from the group consisting of H, C.sub.1-C.sub.8 alkyl,
C.sub.1-C.sub.8 alkoxyl, C.sub.6-C.sub.10 cycloalkyl, and
C.sub.6-C.sub.10 aryl, with the proviso that at least one of
R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is C.sub.1-C.sub.8
alkoxyl.
[0075] Preferred porogens include: [0076]
.sup.tBu.sub.2Si(OCH.sub.3).sub.2 [0077]
.sup.tBu.sub.2Si(OC.sub.2H.sub.5).sub.2 [0078]
(C.sub.6H.sub.5).sub.2Si(OCH.sub.3).sub.2 [0079]
(C.sub.6H.sub.5).sub.2Si(OC.sub.2H.sub.5).sub.2 [0080]
(C.sub.6H.sub.11).sub.2Si(OCH.sub.3).sub.2 [0081]
(C.sub.6H.sub.11).sub.2Si(OC.sub.2H.sub.5).sub.2 [0082]
.sup.tBuSi(OCH.sub.3).sub.2H [0083]
.sup.tBuSi(OC.sub.2H.sub.5).sub.2H [0084]
(C.sub.6H.sub.5)Si(OCH.sub.3).sub.2H [0085]
(C.sub.6H.sub.5)Si(OC.sub.2H.sub.5).sub.2H [0086]
(C.sub.6H.sub.11)Si(OCH.sub.3).sub.2H [0087]
(C.sub.6H.sub.11)Si(OC.sub.2H.sub.5).sub.2H [0088]
(.sup.tBu)(CH.sub.3)Si(OCH.sub.3).sub.2 [0089]
(.sup.tBu)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2 [0090]
(C.sub.6H.sub.5)(CH.sub.3)Si(OCH.sub.3).sub.2 [0091]
(C.sub.6H.sub.5)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2 [0092]
(C.sub.6H.sub.11)(CH.sub.3)Si(OCH.sub.3).sub.2 [0093]
(C.sub.6H.sub.11)(CH.sub.3)Si(OC.sub.2H.sub.5).sub.2 [0094] and the
like, wherein .sup.tBu is tertiary butyl.
[0095] It is also within the purview of the present invention to
employ the organosilicon precursors of the invention, e.g., of
Formula (I) and/or Formula (III), in combination with other
organosilicon precursor compounds, such as TMCTS or other, e.g.,
cyclosiloxane, precursor(s), to provide improvement in the film
properties that would otherwise be obtained using such other
organosilicon precursor compounds in the absence of the
organosilicon precursors of the invention.
[0096] It will be appreciated that the foregoing is illustrative of
a wide variety of oxiranylsilane compounds and bridged silane
compounds that can be synthesized within the general scope of the
present invention and usefully employed to form low k, high
strength films by vapor deposition methods.
[0097] The features and advantages of the invention are more fully
shown with reference to the following non-limiting examples.
EXAMPLE 1
Synthesis of Me(EtO.sub.2)SiCHCH.sub.2O
[0098] m-CPBA (14 g, 62.47 mmol based on 77% purity) was dried in
vacuum until vacuum reached 10 mTorr. Anhydrous methylene chloride
(100 mL) was added to dissolve m-CPBA.
Me(EtO).sub.2SiCH.dbd.CH.sub.2 (10 g, 62.5 mmol) was added to the
clear solution of m-CPBA in CH.sub.2Cl.sub.2. No visual changes
immediately occurred. The white precipitate of
m-ClC.sub.6H.sub.4COOH formed within 2 hours. The reaction mixture
was reduced in volume under vacuum (about 75 mL of CH.sub.2Cl.sub.2
were removed). Pentane (50 mL) was added and then the mixture was
filtered. Low boiling point volatiles were removed in vacuum. The
mixture of unreacted Me(EtO).sub.2SiCH.dbd.CH.sub.2 (10%) and the
product (90%) was isolated under vacuum distillation. Second
distillation yielded high purity oxirane. Yield: 50%. Boiling
point: 30.degree. C. at 0.2 Torr. Mass spectrum: (EI, %): m/z 176
(M.sup.+, 1), 161 (M.sup.+-Me, 10), 133 (M.sup.+-CHCH.sub.2O, 100).
.sup.1H NMR (C.sub.6D.sub.6): .delta. 3.76-3.64 (m, 4H,
SiOCH.sub.2CH.sub.3), 2.59-2.5 (m, 2H, SiCHCH.sub.2), 2.08-2.05 (m,
1H, SiCHCH.sub.2), 1.17-1.07 (m, 6H, SiOCH.sub.2CH.sub.3), 0.07 (s,
3H, SiCH.sub.3). .sup.13C NMR: (C.sub.6D.sub.6) .delta. 59.15
(SiOCH.sub.2CH.sub.3), 44.07 (SiCHCH.sub.2), 18.91
(SiOCH.sub.2CH.sub.3), -6.25 (SiCH.sub.3).
EXAMPLE 2
Synthesis of Me(MeO).sub.2SiCH.sub.2CHCH.sub.2O
[0099] m-CPBA (7.66 g, 34.18 mmol based on 77% purity) was dried in
vacuum at room temperature until vacuum reached 10 mTorr. Anhydrous
methylene chloride (60 mL) was added to dissolve m-CPBA.
Me(MeO).sub.2SiCH.dbd.CH.sub.2 (5 g, 34.18 mmol) was added to the
solution of m-CPBA in CH.sub.2Cl.sub.2. The immediate reaction was
evidenced by moderate heat generation. White precipitate of
m-ClC.sub.6H.sub.4COOH formed within 1 hour. The reaction mixture
was left overnight. Next morning, the reaction mixture was reduced
in volume under vacuum. Pentane (50 mL) was added and then the
mixture was filtered. Low boiling point volatiles were removed in
vacuum. The product was obtained by vacuum distillation. Yield:
40%. Boiling point: 30.degree. C. at 0.2 Torr. Mass spectrum: (EI,
%): m/z 162 (M.sup.+, 1), 174 (M.sup.+-Me, 10), 105
(M.sup.+-CH.sub.2CHCH.sub.2O, 100). .sup.1H NMR (C.sub.6D.sub.6):
.delta. 3.31 (s, 3H, SiOCH.sub.3), 3.30 (s, 3H, SiOCH.sub.3),
2.9-2.82 (m, 1H, SiCH.sub.2CHCH.sub.2O), 2.44-2.41 (m, 1H,
SiCH.sub.2CHCHHO), 2.18-2.15 (m, 1H, SiCH.sub.2CHCHHO), 1.09-1.02
(m, 1H, SiCHHCHCH.sub.2O), 0.73-0.65 (m, 1H, SiCHHCHCH.sub.2O),
0.08 (s, 3H, SiCH3). .sup.3C NMR: (C.sub.6D.sub.6) .delta. 50.30
(SiOCH.sub.3), 50.28 (SiOCH.sub.3), 48.94 (SiCH.sub.2CHCH.sub.2O),
48.36 (SiCH.sub.2CHCH.sub.2O), 18.83 (SiCH.sub.2CHCH.sub.2O), -4.30
(SiCH.sub.3).
EXAMPLE 3
Synthesis of Me.sub.2Si (CHCH.sub.2O).sub.2
[0100] m-CPBA (8 g, 35.70 mmol based on 77% purity) was dried in
vacuum until vacuum reached 10 mTorr. Anhydrous methylene chloride
(100 mL) was added to dissolve m-CPBA. The solution of
Me.sub.2Si(CH.dbd.CH.sub.2).sub.2 (2 g, 17.86 mmol) in
CH.sub.2Cl.sub.2 was added to the clear solution of m-CPBA in
CH.sub.2Cl.sub.2. No visual changes occurred. The reaction mixture
was left stirring overnight. White precipitate of m-ClC.sub.6H4COOH
formed by next morning. The mixture was reduced in volume under
vacuum (about 80 mL of CH.sub.2Cl.sub.2 were removed). Pentane (50
mL) was added and then the mixture was filtered. Low boiling point
volatiles were removed in vacuum. The mixture of
Me.sub.2Si(CH.dbd.CH.sub.2)(CHCH.sub.2O) (15%) and the product
(85%) was isolated using nitrogen trap under high vacuum. Yield:
50%. Boiling point: 45.degree. C. at 0.2 Torr. Mass spectrum: (EI,
%): m/z 101 (M.sup..+-.CHCH.sub.2O, 20), 59 (Me.sub.2SiH, 100).
.sup.1H NMR (C.sub.6D.sub.6): .delta. 2.58-2.54 (m, 2H, SiCHCHHO),
2.38-2.28 (m, 2H, SiCHCHHO), 2.04-1.98 (m, 2H, SiCHCH.sub.2O),
-0.10 and -0.12 (m, 6H, SiCH.sub.3). .sup.13C NMR: (C.sub.6D.sub.6)
.delta. 44.27 and 44.19 (SiCHCH.sub.2O), 41.70 and 41.43
(SiCHCH.sub.2O), -7.36, -7.50 and -7.74 (SiCH.sub.3). The
complicated NMR spectra are consistent with four stereoisomerisms
possible for Me.sub.2Si(C*HCH.sub.2O).sub.2. Two diastereomers in
the ratio of 1:1 were separated by GC/MS.
EXAMPLE 4
Synthesis of [Me(MeO).sub.2SiCH.sub.2].sub.2
[0101] A solution of [MeCl.sub.2SiCH.sub.2].sub.2 (102.7 g, 0.4
mol) in tetrahydrofuran (THF) (500 mL) was added dropwise to 25
weight % solution of MeONa in MeOH (349 g, 1.6 mol, 1% excess) at
room temperature. White precipitate formed almost immediately. The
reaction mixture was stirred for 1 hour to ensure the complete
substitution. Upon filtration, all volatiles were removed in vacuum
to form a yellowish solution of MeONa in
[Me(MeO).sub.2SiCH.sub.2].sub.2. Pure
[Me(MeO).sub.2SiCH.sub.2].sub.2 was obtained by vacuum
distillation. Yield: 82%. Boiling point: 55.degree. C. at 0.3 Torr.
Mass spectrum: (EI, %): m/z 238 (M.sup.+, 5), 223 (M.sup.+-Me, 15).
.sup.1H NMR (C.sub.6D.sub.6): .delta. 3.37 (s, 12H, OCH.sub.3),
0.72 (s, 4H, H.sub.2C--CH.sub.2), 0.09 (s, 6H, SiCH.sub.3).
.sup.13C NMR: (C.sub.6D.sub.6) .delta. 50.30 (OCH.sub.3), 4.98
(H.sub.2C--CH.sub.2), -5.99 (SiCH.sub.3).
EXAMPLE 5
Synthesis of [Me.sub.2(MeO)SiCH.sub.2].sub.2
[0102] A solution of [Me.sub.2ClSiCH.sub.2].sub.2 (100 g, 0.465
mol) in tetrahydrofuran (THF) (500 mL) was added dropwise to 25
weight % solution of MeONa in MeOH (200.68 g, 0.929 mol) at room
temperature. White precipitate formed almost immediately. The
reaction mixture was stirred for 1 hour to ensure the complete
substitution. Upon filtration, all volatiles were removed in
vacuum. Pure [Me.sub.2(MeO)SiCH.sub.2].sub.2 was obtained by vacuum
distillation. Yield: 88%. Boiling point: 40.degree. C. at 0.3 Torr.
Mass spectrum: (EI, %): m/z 206 (M.sup.+, 5), 191 (M.sup.+-Me, 20),
89 (Me.sub.2SiOMe, 100). .sup.1H NMR (C.sub.6D.sub.6): .delta. 3.29
(s, 6H, OCH.sub.3), 0.59 (s, 4H, H.sub.2C--CH.sub.2), 0.09 (s, 6H,
SiCH.sub.3). .sup.13C NMR: (C.sub.6D.sub.6) .delta. 50.41
(OC.sub.H.sub.3), 7.92 (H.sub.2C--CH.sub.2), -2.76
(SiCH.sub.3).
EXAMPLE 6
Synthesis of [(MeO).sub.3Si].sub.2CH.sub.2
[0103] A solution of (Cl.sub.2HSi).sub.2CH.sub.2 (23.21 g, 0.108
mol) in tetrahydrofuran (THF) (120 mL) was added dropwise to 25
weight % solution of MeONa in MeOH (93.71 g, 0.434 mol) at room
temperature. White precipitate formed almost immediately. The
reaction mixture was stirred for 1 hour to ensure the complete
substitution. Upon filtration, all volatiles were removed in vacuum
and the product was obtained by vacuum distillation. Yield: 60%.
Boiling point: 53.degree. C. at 60 mTorr. Mass spectrum: (EI, %):
m/z 256 (M.sup.+, 20), 241 (M.sup.+-Me, 5), 224 [M.sup.+-OMe, 100).
.sup.1H NMR (C.sub.6D.sub.6): .delta. 3.49 (s, 18H, OCH.sub.3),
0.08 (s, 2H, CH.sub.2). .sup.13C NMR: (C.sub.6D.sub.6) .delta.
50.69 (OCH.sub.3), -9.02 (CH.sub.2).
EXAMPLE 7
Films Produced With Diethoxy Methyl Oxiranyl Silane (DEOMORS)
[0104] Me(EtO.sub.2)SiCHCH.sub.2O was synthesized as in Example
1.
[0105] The Me(EtO.sub.2)SiCHCH.sub.2O was employed to form a
deposited film on a substrate by low pressure plasma-enhanced
chemical vapor deposition, in which the deposition process was
carried out under the process conditions listed in Table 1 below.
The process was carried out in a deposition chamber to which vapor
was introduced by a showerhead injection device to the wafer
disposed on the wafer heater. TABLE-US-00001 TABLE 1 Deposition
Parameter Value Syringe setpoint, % 20 Liquid flow, milliliters per
minute 0.13 Substrate temperature, .degree. C. 370 Radio frequency
power, watts 250 Pressure, torr 6.0 Spacing (showerhead to wafer
heater distance), mils 460 Time, seconds 120 Carrier gas flow rate,
sccm/minute 200 Carrier gas carbon dioxide
[0106] The deposited film had the characteristics shown in Table 2
below. TABLE-US-00002 TABLE 2 Film property Value Dielectric
constant, k 3.1 Indentation hardness, GigaPascals (GPa) 2.3
Indentation modulus, GigaPascals (GPa) 12.4 Deposition Rate,
Angstroms/min 980
[0107] The film thus possessed an exceptional film hardness of 2.3
GPa with a dielectric constant k of 3.1. The film had less Si--H
incorporation compared to films produced using precursors with
large amounts of hydride, such as trimethylsilane and TMCTS. This
is evidenced by the results in FIG. 1, which shows FTIR
transmission spectra of a film deposited from TMCTS and a film
deposited from Me(EtO.sub.2)SiCHCH.sub.2O under low oxygen activity
deposition conditions. The presence of large amounts of Si--H in
the film is generally correlated with reduced mechanical strength
in low k films, and the low Si--H content of the film deposited
from Me(EtO.sub.2)SiCHCH.sub.2O is consistent with the improvement
achieved with the oxiranylsilane precursors of the present
invention.
[0108] Films formed from oxiranylsilane precursors also demonstrate
compatibility with low oxygen activity plasmas, which render such
precursors compatible with oxygen sensitive porogens, e.g.,
organosilicon precursors containing t-butyl functional groups. The
process conditions summarized in Table 1 reflect the fact that a
small amount of CO.sub.2 and the Me(EtO.sub.2)SiCHCH.sub.2O
precursor were the only potential sources of oxygen in the plasma.
Under conditions similar to this, many hydride-containing
precursors such as TMCTS show a severely depressed deposition rate,
and poor dielectric constant and hardness characteristics. Large
amounts of Si--H are observed in films deposited from TMCTS. Si--H
is not detected in films deposited under similar conditions using
Me(EtO.sub.2)SiCHCH.sub.2O.
[0109] FIG. 2 is a plot of deposition rate, in Angstroms per
minute, as a function of measured radio frequency power, in watts,
for each of Me(EtO.sub.2)SiCHCH.sub.2O (denoted in the graph as
DEOMORS), tetramethylcyclotetrasiloxane (denoted in the graph as
TMCTS), and tetraethylorthosilicate (denoted in the graph as TEOS),
each utilized in the deposition process in combination with a same
porogen under similar conditions.
[0110] As shown by the results of FIG. 2,
Me(EtO.sub.2)SiCHCH.sub.2O evidenced a markedly higher deposition
rate in comparison with the prior art TEOS and TMCTS precursor
materials.
[0111] Although the invention has been variously disclosed herein
with reference to illustrative embodiments and features, it will be
appreciated that the embodiments and features described hereinabove
are not intended to limit the invention, and that other variations,
modifications and other embodiments will suggest themselves to
those of ordinary skill in the art. The invention therefore is to
be broadly construed, consistent with the claims hereafter set
forth.
* * * * *