U.S. patent application number 10/735579 was filed with the patent office on 2005-01-27 for organic compositions.
Invention is credited to Apen, Paul, Lau, Kreisler, Li, Bo, Sullivan, Edward.
Application Number | 20050020702 10/735579 |
Document ID | / |
Family ID | 27558469 |
Filed Date | 2005-01-27 |
United States Patent
Application |
20050020702 |
Kind Code |
A1 |
Li, Bo ; et al. |
January 27, 2005 |
Organic compositions
Abstract
The present invention provides a composition comprising (a)
thermosetting component comprising: (1) optionally monomer of
Formula I as set forth below and (2) at least one oligomer or
polymer of Formula II as set forth below where E, Q, G, h, I, j,
and w are as set forth below and (b) porogen that bonds to
thermosetting component (a). Preferably, the porogen is selected
from the group consisting of unsubstituted polynorbornene,
substituted polynorbornene, polycaprolactone, unsubstituted
polystyrene, substituted polystyrene, polyacenaphthylene
homopolymer, and polyacenaphthylene copolymer. Preferably, the
present compositions may be used as dielectric substrate in
microchips, multichip modules, laminated circuit boards, or printed
wiring boards.
Inventors: |
Li, Bo; (San Jose, CA)
; Apen, Paul; (San Francisco, CA) ; Lau,
Kreisler; (Sunnyvale, CA) ; Sullivan, Edward;
(Daly City, CA) |
Correspondence
Address: |
Sandra Poteat THompson
Bingham McCutchen LLP
Three EmbracaderoCenter
San Francisco
CA
94111
US
|
Family ID: |
27558469 |
Appl. No.: |
10/735579 |
Filed: |
December 12, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10735579 |
Dec 12, 2003 |
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10158548 |
May 30, 2002 |
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6740685 |
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60294864 |
May 30, 2001 |
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60350187 |
Jan 15, 2002 |
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60350557 |
Jan 22, 2002 |
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60353011 |
Jan 30, 2002 |
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60376219 |
Apr 29, 2002 |
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60378424 |
May 7, 2002 |
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Current U.S.
Class: |
521/52 ;
257/E21.259; 257/E21.261; 257/E21.273; 257/E21.576; 257/E23.007;
257/E23.167 |
Current CPC
Class: |
H05K 1/0313 20130101;
C07C 17/266 20130101; H01L 21/312 20130101; H01L 21/31695 20130101;
H01L 2924/09701 20130101; C07C 25/22 20130101; H01L 2924/00
20130101; H01L 21/02126 20130101; H05K 1/024 20130101; C07C 23/46
20130101; C07C 17/10 20130101; H01L 21/02203 20130101; C08G 61/02
20130101; H01L 21/02282 20130101; H01L 23/145 20130101; C07C 17/10
20130101; H01L 21/02118 20130101; H01L 2924/0002 20130101; H05K
3/4676 20130101; H01L 2924/0002 20130101; C08L 65/00 20130101; H01L
2924/12044 20130101; C07C 25/22 20130101; H01L 21/3122 20130101;
C07C 25/24 20130101; C07C 17/266 20130101 |
Class at
Publication: |
521/052 |
International
Class: |
C08J 009/38 |
Claims
What is claimed is:
1. A composition comprising: (a) thermosetting component
comprising: (1) optionally monomer of Formula I 29and (2) at least
one oligomer or polymer of Formula II 30where said E is a cage
compound; each of said Q is the same or different and selected from
aryl, branched aryl, and substituted aryl wherein said substituents
include hydrogen, halogen, alkyl, aryl, substituted aryl,
heteroaryl, aryl ether, alkenyl, alkynyl, alkoxyl, hydroxyalkyl,
hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl;
said G is aryl or substituted aryl where substituents include
halogen and alkyl; said h is from 0 to 10; said i is from 0 to 10;
said j is from 0 to 10; and said w is 0 or 1; (b) porogen that
bonds to said thermosetting component (a).
2. The composition of claim 1 wherein said thermosetting component
(a) is functionalized.
3. The composition of claim 2 wherein said functionality is
selected from the group consisting of acetylene; 4-ethynylaniline;
3-hydroxyphenylacetylene; 4-fluorophenylacetylene; and
1-ethylcyclohexylamine.
4. The composition of claim 1 wherein said porogen comprises a
material having a decomposition temperature less than the glass
transition temperature of said thermosetting component (a) and
greater than the curing temperature of said thermosetting component
(a).
5. The composition of claim 4 wherein said porogen is selected from
the group consisting of unsubstituted polynorbornene, substituted
polynorbornene, polycaprolactone, unsubstituted polystyrene,
substituted polystyrene, polyacenaphthylene homopolymer, and
polyacenaphthylene copolymer.
6. The composition of claim 5 wherein said porogen is
functionalized.
7. The composition of claim 6 wherein said functionality is
selected from the group consisting of epoxy, hydroxy, carboxylic
acid, amino, and ethynyl.
8. The composition of claim 1 wherein said porogen is covalently
bonded to said thermosetting component (a).
9. The composition of claim 8 wherein said porogen is covalently
bonded to said thermosetting component (a) through an ethynyl
containing group.
10. The composition of claim 9 wherein said ethynyl containing
group is acetylene.
11. The composition of claim 8 wherein said thermosetting component
(a) comprises (1) adamantane monomer of Formula III 31and (2)
adamantane oligomer or polymer of Formula IV 3233or (1) diamantane
monomer of Formula V 34and (2) diamantane oligomer or polymer of
Formula VI 3536where said h is from 0 to 10; said i is from 0 to
10; said j is from 0 to 10; each of said R.sub.1 is the same or
different and selected from hydrogen, halogen, alkyl, aryl,
substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,
alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,
hydroxyl, or carboxyl; and each of said Y is same or different and
is selected from hydrogen, alkyl, aryl, substituted aryl, or
halogen.
12. The composition of claim 11 wherein said monomer is
present.
13. The composition of claim 11 or 12 wherein said R.sub.1 is aryl
or substituted aryl and said Y is hydrogen, phenyl, or
biphenyl.
14. The composition of claim 13 wherein said (2) adamantane
oligomer or polymer is dimer of Formula IX 37or said (2) diamantane
oligomer or polymer is dimer of Formula X 38
15. The composition of claim 13 wherein said (2) adamantane
oligomer or polymer is trimer of Formula XI 39or said (2)
diamantane oligomer or polymer is trimer of Formula XII 40
16. The composition of claim 13 where in said thermosetting
component (a), said oligomer or polymer (2) comprises a mixture of
adamantane dimer of Formula IX 41and adamantane trimer of Formula
XI 42or diamantane dimer of Formula X 43and diamantane trimer of
Formula XII 44
17. The composition of claim 16 where in said thermosetting
component (a), said monomer (1) and said oligomer or polymer (2)
are adamantane based monomers.
18. The composition of claim 17 wherein at least two of said
R.sub.1C.ident.C groups on said phenyl groups are two different
isomers and at least one of said phenyl groups between two
bridgehead carbons of said adamantane monomers exists as two
different isomers.
19. The composition of claim 18 wherein said at least two isomers
are meta- and para-isomers.
20. The composition of claim 13 additionally comprising (c)
adhesion promoter comprising compound having at least
bifunctionality wherein the bifunctionality may be the same or
different and at least one of said bifunctionality is capable of
interacting with said thermosetting component (a).
21. The composition of claim 20 wherein said adhesion promoter is
selected from the group consisting of: silanes of the Formula XXIV:
(R.sub.2).sub.k(R.sub.3).sub.lSi(R.sub.4).sub.m(R.sub.5).sub.n
wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently
represents hydrogen, hydroxyl, unsaturated or saturated alkyl,
substituted or unsubstituted alkyl where the substituent is amino
or epoxy, unsaturated or saturated alkoxyl, unsaturated or
saturated carboxylic acid radical, or aryl, at least two of said
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 represent hydrogen,
hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or
unsaturated carboxylic acid radical, and k+l+m+n.ltoreq.4;
polycarbosilane of the Formula XXV: 45in which R.sub.8, R.sub.14,
and R.sub.17 each independently represents substituted or
unsubstituted alkylene, cycloalkylene, vinylene, allylene, or
arylene; R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.15, and
R.sub.16 each independently represents hydrogen atom, alkyl,
alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be
linear or branched, R.sub.13 represents organosilicon, silanyl,
siloxyl, or organo group, and p, q, r, and s satisfy the conditions
of [4.ltoreq.p+q+r+s.ltoreq.100,000- ], and q and r and s may
collectively or independently be zero; glycidyl ethers, or esters
of unsaturated carboxylic acids containing at least one carboxylic
acid group; vinyl cyclic oligomers or polymers where the cyclic
group is vinyl, aromatic, or heteroaromatic; and
phenol-formaldehyde resins or oligomers of the Formula XXVI:
--[R.sub.18C.sub.6H.sub.2(OH)(R.sub.19)].sub.t-- where R.sub.18 is
substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl,
or aryl, R.sub.19 is alkyl, alkylene, vinylene, cycloalkylene,
allylene, or aryl, and t=3-100.
22. The composition of claim 21 wherein said adhesion promoter (c)
is said phenol-formaldehyde resin or oligomer.
23. An oligomer comprising said composition of claim 20.
24. A spin-on precursor comprising said oligomer of claim 23 and
solvent.
25. A thermosetting matrix made from said spin-on precursor of
claim 24.
26. A layer comprising said thermosetting matrix of claim 25.
27. The layer of claim 26 wherein said thermosetting matrix is
cured.
28. The layer of claim 26 wherein said layer has a dielectric
constant of less than 2.7, preferably less than 2.5, preferably
less than 2.2, and preferably less than 2.0.
29. The layer of claim 26 wherein said layer has an average pore
size diameter of less than 20 nanometers.
30. A substrate having thereon at least one of said layer of claim
26.
31. A microchip comprising said substrate of claim 30.
32. A method of lowering the dielectric constant of a composition
comprising (a) thermosetting component comprising: (1) optionally
monomer of Formula I 46and (2) at least one oligomer or polymer of
Formula II 47where said E is a cage compound; each of said Q is the
same or different and selected from aryl, branched aryl, and
substituted aryl wherein said substituents include hydrogen,
halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether,
alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl,
hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl; said G is
aryl or substituted aryl where substituents include halogen and
alkyl; said h is from 0 to 10; said i is from 0 to 10; said j is
from 0 to 10; and said w is 0 or 1; (b) adhesion promoter
comprising compound having at least bifunctionality wherein the
bifunctionality may be the same or different and the first
functionality is capable of interacting with said thermosetting
component (a) and the second functionality is capable of
interacting with a substrate when said composition is applied to
said substrate comprising the steps of: bonding porogen to said
thermosetting component; decomposing said bonded porogen; and
volatilizing said porogen whereby pores form in said
composition.
33. The method of claim 32 wherein said thermosetting component (a)
is functionalized.
34. The method of claim 33 wherein said thermosetting component
functionality is selected from the group consisting of acetylene;
4-ethynylaniline; 3-hydroxyphenylacetylene;
4-fluorophenylacetylene; and 1-ethylcyclohexylamine.
35. The method of claim 32 wherein said porogen comprises a
material having a decomposition temperature less than the glass
transition temperature of said thermosetting component (a) and
greater than the curing temperature of said thermosetting component
(a).
36. The method of claim 35 wherein said porogen is selected from
the group consisting of unsubstituted polynorbornene, substituted
polynorbornene, polycaprolactone, unsubstituted polystyrene,
substituted polystyrene, polyacenaphthylene homopolymer, and
polyacenaphthylene copolymer.
37. The method of claim 36 wherein said porogen is
functionalized.
38. The method of claim 37 wherein said porogen functionality is
selected from the group consisting of epoxy, hydroxy, carboxylic
acid, amino, and ethynyl.
39. The method of claim 32 wherein said porogen is covalently
bonded to said thermosetting component (a).
40. The method of claim 39 wherein said porogen is covalently
bonded to said thermosetting component (a) through an ethynyl
containing group.
41. The method of claim 40 wherein said ethynyl containing group is
acetylene.
42. The method of claim 39 wherein said thermosetting component (a)
comprises (1) adamantane monomer of Formula III 48and (2)
adamantane oligomer or polymer of Formula IV 4950or (1) diamantane
monomer of Formula V 51and (2) diamantane oligomer or polymer of
Formula VI 5253where said h is from 0 to 10; said i is from 0 to
10; said j is from 0 to 10; each of said R.sub.1 is the same or
different and selected from hydrogen, halogen, alkyl, aryl,
substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,
alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,
hydroxyl, or carboxyl; and each of said Y is same or different and
is selected from hydrogen, alkyl, aryl, substituted aryl, or
halogen.
43. The method of claim 42 wherein said monomer is present.
44. The method of claim 42 or 43 wherein said decomposing said
porogen step comprises curing by furnace, hot plate, electron beam
radiation, microwave radiation, or ultraviolet radiation.
45. The method of claim 44 wherein said R.sub.1 is aryl or
substituted aryl and said Y is hydrogen, phenyl, or biphenyl.
46. The method of claim 45 wherein said (2) adamantane oligomer or
polymer is dimer of Formula IX 54or said (2) diamantane oligomer or
polymer is dimer of Formula X 55
47. The method of claim 45 wherein said (2) adamantane oligomer or
polymer is trimer of Formula XI 56or said (2) diamantane oligomer
or polymer is trimer of Formula XII 57
48. The method of claim 45 where in said thermosetting component
(a), said oligomer or polymer (2) comprises a mixture of adamantane
dimer of Formula IX 58and adamantane trimer of Formula XI 59or
diamantane dimer of Formula X 60and diamantane trimer of Formula
XII 61
49. The method of claim 48 where in said thermosetting component
(a), said monomer (1) and said oligomer or polymer (2) are
adamantane based monomers.
50. The method of claim 49 wherein at least two of said
R.sub.1C.ident.C groups on said phenyl groups are two different
isomers and at least one of said phenyl groups between two
bridgehead carbons of said adamantane monomers exists as two
different isomers.
51. The method of claim 50 wherein said at least two isomers are
meta- and para-isomers.
52. The method of claim 44 wherein at least one of said first
functionality and said second functionality of said adhesion
promoter (b) is selected from the group consisting of Si containing
groups; N containing groups; C bonded to O containing groups;
hydroxyl groups; and C double bonded to C containing groups.
53. The method of claim 52 wherein said Si containing group is
selected from silanes of the Formula XXIV:
(R.sub.2).sub.k(R.sub.3).sub.lSi(R.sub.- 4).sub.m(R.sub.5).sub.n
wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently
represents hydrogen, hydroxyl, unsaturated or saturated alkyl,
substituted or unsubstituted alkyl where the substituent is amino
or epoxy, unsaturated or saturated alkoxyl, unsaturated or
saturated carboxylic acid radical, or aryl, at least two of said
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 represent hydrogen,
hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or
unsaturated carboxylic acid radical, and k+l+m+n.ltoreq.4; or
polycarbosilane of the Formula XXV: 62in which R.sub.8, R.sub.14,
and R.sub.17 each independently represents substituted or
unsubstituted alkylene, cycloalkylene, vinylene, allylene, or
arylene; R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.15, and
R.sub.16 each independently represents hydrogen atom, alkyl,
alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be
linear or branched, R.sub.13 represents organosilicon, silanyl,
siloxyl, or organo group, and p, q, r, and s satisfy the conditions
of [4.ltoreq.p+q+r+s.ltoreq.100,000- ], and q and r and s may
collectively or independently be zero; said C bonded to O
containing groups are selected from glycidyl ethers, or esters of
unsaturated carboxylic acids containing at least one carboxylic
acid group; said C double bonded to C containing groups is vinyl
cyclic oligomers or polymers where the cyclic group is vinyl,
aromatic, or heteroaromatic; and said hydroxyl group is
phenol-formaldehyde resins or oligomers of the Formula XXVI:
--[R.sub.18C.sub.6H.sub.2(OH)(R.sub.19)].s- ub.t-- where R.sub.18
is substituted or unsubstituted alkylene, cycloalkylene, vinyl,
allyl, or aryl, R.sub.19 is alkyl, alkylene, vinylene,
cycloalkylene, allylene, or aryl, and t=3-100.
54. The method of claim 53 wherein said adhesion promoter (c) is
said phenol-formaldehyde resin or oligomer. and at least one
oligomer or polymer, wherein the at least one oligomer or polymer
comprises at least one cage compound in the backbone of the at
least one oligomer or polymer and further comprises at least one
aryl, substituted aryl or branched aryl; and a porogen that bonds
to the thermosetting component.
56. The composition of claim 55, wherein the cage compound
comprises an adamantane or a diamantane compound.
57. The composition of claim 56, wherein the cage compound
comprises an adamantane compound.
58. The composition of claim 55, wherein the at least one oligomer
or polymer comprises the structure of Formula II: 63where said E is
the cage compound; each of said Q is the same or different and
selected from aryl, branched aryl, and substituted aryl wherein
said substituents include hydrogen, halogen, alkyl, aryl,
substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,
alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,
hydroxyl, or carboxyl; said G is aryl or substituted aryl where
substituents include halogen and alkyl; said h is from 0 to 10;
said i is from 0 to 10; said j is from 0 to 10; and said w is 0 or
1.
59. The composition of claim 55, further comprising an adhesion
promoter.
60. The composition of claim 55, wherein the thermosetting
component comprises the adamantane monomer of formula III: 64or
polymer of Formula IV: 65the diamantane monomer of Formula V: 66or
the diamantane oligomer or polymer of Formula VI 67where h is from
0 to 10; i is from 0 to 10; j is from 0 to 10; each of R.sub.1 is
the same or different and selected from hydrogen, halogen, alkyl,
aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,
alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,
hydroxyl, or carboxyl; and each of said Y is same or different and
is selected from hydrogen, alkyl, aryl, substituted aryl, or
halogen.
61. The composition of claim 55, wherein the thermosetting
composition is functionalized.
62. The composition of claim 61, wherein the functionality
comprises acetylene; 4-ethynylaniline; 3-hydroxyphenylacetylene;
4-fluorophenylacetylene or 1-ethylcyclohexylamine.
63. The composition of claim 55, wherein the porogen comprises a
material having a decomposition temperature less than the glass
transition temperature of the thermosetting component.
64. The composition of either of claims 55 or 63, wherein the
porogen comprises a material having a decomposition temperature
greater than the curing temperature of the thermosetting
component.
65. The composition of claim 55, wherein the porogen comprises an
unsubstituted polynorbornene, substituted polynorbornene,
polycaprolactone, unsubstituted polystyrene, substituted
polystyrene, polyacenaphthylene homopolymer or polyacenaphthylene
copolymer.
66. The composition of either of claims 55 or 65, wherein the
porogen is functionalized.
67. The composition of claim 66, wherein the functionality
comprises epoxy, hydroxy, carboxylic acid, amino or ethynyl.
68. The composition of claim 55, wherein the porogen is covalently
bonded to the thermosetting component.
69. The composition of claim 68, wherein the porogen is covalently
bonded to the thermosetting component through an ethynyl-containing
group.
70. The composition of claim 69, wherein the ethynyl-containing
group is acetylene.
71. The composition of claim 55, wherein the monomer is present in
the thermosetting composition.
72. The composition of claim 60, wherein said R.sub.1 is aryl or
substituted aryl and said Y is hydrogen, phenyl, or biphenyl.
73. The composition of claim 55, wherein the at least one oligomer
or polymer comprises the structure of Formula IX 68or the structure
of Formula X: 69
74. The composition of claim 55, wherein the at least one oligomer
or polymer comprises the structure of Formula XI: 70or the
structure of Formula XII: 71
75. The composition of claim 55, wherein the thermosetting
component comprises a mixture of the compound of Formula IX 72and
Formula XI 73or Formula X 74and Formula XII 75
76. The composition of claim 75, wherein the thermosetting
component, the monomer and the at least one oligomer or polymer
comprise adamantane-based monomers.
77. The composition of claim 76, wherein at least two of the
R.sub.1C.ident.C groups on the phenyl groups are two different
isomers and at least one of the phenyl groups between two
bridgehead carbons of the adamantane-based monomers exists as two
different isomers.
78. The composition of claim 77, wherein the at least two isomers
are meta- and para-isomers.
79. The composition of claim 59, wherein the adhesion promoter
comprises a compound having at least bifunctionality wherein the
bifunctionality may be the same or different and at least one of
said bifunctionality is capable of interacting with said
thermosetting component.
80. The composition of claim 79 wherein said adhesion promoter
comprises at least one of the following: silanes of the Formula
XXIV:
(R.sub.2).sub.k(R.sub.3).sub.lSi(R.sub.4).sub.m(R.sub.5).sub.n
wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently
represents hydrogen, hydroxyl, unsaturated or saturated alkyl,
substituted or unsubstituted alkyl where the substituent is amino
or epoxy, unsaturated or saturated alkoxyl, unsaturated or
saturated carboxylic acid radical, or aryl, at least two of said
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 represent hydrogen,
hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or
unsaturated carboxylic acid radical, and k+l+m+n<4;
polycarbosilane of the Formula XXV: 76in which R.sub.8, R.sub.14,
and R.sub.17 each independently represents substituted or
unsubstituted alkylene, cycloalkylene, vinylene, allylene, or
arylene; R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.15, and
R.sub.16 each independently represents hydrogen atom, alkyl,
alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be
linear or branched, R.sub.13 represents organosilicon, silanyl,
siloxyl, or organo group, and p, q, r, and s satisfy the conditions
of [4<p+q+r+s.ltoreq.100,000], and q and r and s may
collectively or independently be zero; glycidyl ethers, or esters
of unsaturated carboxylic acids containing at least one carboxylic
acid group; vinyl cyclic oligomers or polymers where the cyclic
group is vinyl, aromatic, or heteroaromatic; and
phenol-formaldehyde resins or oligomers of the Formula XXVI:
--[R.sub.18C.sub.6H.sub.2(OH)(R.sub.19)].sub.t-- where R.sub.18 is
substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl,
or aryl, R.sub.19 is alkyl, alkylene, vinylene, cycloalkylene,
allylene, or aryl, and t=3-100.
81. The composition of claim 80, wherein the adhesion promoter is
said phenol-formaldehyde resin or oligomer.
82. An oligomer comprising the composition of claim 79.
83. A spin-on precursor comprising the oligomer of claim 82 and
solvent.
84. A thermosetting matrix made from the spin-on precursor of claim
83.
85. A layer comprising the thermosetting matrix of claim 84.
86. The layer of claim 85, wherein the thermosetting matrix is
cured.
87. The layer of claim 85, wherein the layer has a dielectric
constant of less than 2.7.
88. The layer of claim 87, wherein the layer has a dielectric
constant of less than about 2.2.
89. The layer of claim 85, wherein the layer has an average pore
size diameter of less than about 20 nanometers.
Description
BENEFIT OF PENDING APPLICATIONS
[0001] This application claims the benefit of pending commonly
assigned provisional patent applications 60/294864 filed May 30,
2001; 60/350187 filed Jan. 15, 2002; 60/350557 filed Jan. 22, 2002;
60/353011 filed Jan. 30, 2002; 60/376219 filed Apr. 29, 2002, and
60/378424 filed May 7, 2002, incorporated herein in their
entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to semiconductor devices, and
in particular, to semiconductor devices having an organic low
dielectric constant material and processes for the manufacture
thereof.
BACKGROUND OF THE INVENTION
[0003] In an effort to increase the performance and speed of
semiconductor devices, semiconductor device manufacturers have
sought to reduce the linewidth and spacing of interconnects while
minimizing the transmission losses and reducing the capacitative
coupling of the interconnects. One way to diminish power
consumption and reduce capacitance is by decreasing the dielectric
constant (also referred to as "k") of the insulating material, or
dielectric, that separates the interconnects. Insulator materials
having low dielectric constants are especially desirable, because
they typically allow faster signal propagation, reduce capacitance
and cross talk between conductor lines, and lower voltages required
to drive integrated circuits.
[0004] Since air has a dielectric constant of 1.0, a major goal is
to reduce the dielectric constant of insulator materials down to a
theoretical limit of 1.0, and several methods are known in the art
for reducing the dielectric constant of insulating materials. These
techniques include adding elements such as fluorine to the
composition to reduce the dielectric constant of the bulk material.
Other methods to reduce k include use of alternative dielectric
material matrices. Another approach is to introduce pores into the
matrix.
[0005] Therefore, as interconnect linewidths decrease, concomitant
decreases in the dielectric constant of the insulating material are
required to achieve the improved performance and speed desired of
future semiconductor devices. For example, devices having
interconnect linewidths of 0.13 or 0.10 micron and below seek an
insulating material having a dielectric constant (k)<3.
[0006] Currently silicon dioxide (SiO.sub.2) and modified versions
of SiO.sub.2, such as fluorinated silicon dioxide or fluorinated
silicon glass (hereinafter FSG) are used. These oxides, which have
a dielectric constant ranging from about 3.5-4.0, are commonly used
as the dielectric in semiconductor devices. While SiO.sub.2 and FSG
have the mechanical and thermal stability needed to withstand the
thermal cycling and processing steps of semiconductor device
manufacturing, materials having a lower dielectric constant are
desired in the industry.
[0007] Methods used to deposit dielectric materials may be divided
into two categories: spin-on deposition (hereinafter SOD) and
chemical vapor deposition (hereinafter CVD). Several efforts to
develop lower dielectric constant materials include altering the
chemical composition (organic, inorganic, blend of
organic/inorganic) or changing the dielectric matrix (porous,
non-porous). Table I summarizes the development of several
materials having dielectric constants ranging from 2.0 to 3.5.
(PE=plasma enhanced; HDP=high-density plasma) However, the
dielectric materials and matrices disclosed in the publications
shown in Table 1 fail to exhibit many of the combined physical and
chemical properties desirable and even necessary for effective
dielectric materials, such as higher mechanical stability, high
thermal stability, high glass transition temperature, high modulus
or hardness, while at the same time still being able to be
solvated, spun, or deposited on to a substrate, wafer, or other
surface. Therefore, it may be useful to investigate other compounds
and materials that may be used as dielectric materials and layers,
even though these compounds or materials may not be currently
contemplated as dielectric materials in their present form.
1TABLE 1 DEPOSITION DIELECTRIC MATERIAL METHOD CONSTANT (k)
REFERENCE Fluorinated silicon oxide PE-CVD; 3.3-3.5 U.S. Pat. No.
No. 6,278,174 (SiOF) HDP-CVD Hydrogen SOD 2.0-2.5 U.S. patents
4,756,977; 5,370,903; and Silsesquioxane (HSQ) 5,486,564;
International Patent Publication WO 00/40637; E.S. Moyer et at.,
"Ultra Low k Silsesquioxane Based Resins", Concepts and Needs for
Low Dielectric Constant <0.15 .mu.m Interconnect Materials: Now
and the Next Millennium, Sponsored by the American Chemical
Society, pages 128-146 (November 14-17, 1999) Methyl Silsesquioxane
SOD 2.4-2.7 U.S. Pat. No. 6,143,855 (MSQ) Polyorganosilicon SOD
2.5-2.6 U.S. Pat. No. 6,225,238 Fluorinated Amorphous HDP-CVD 2.3
U.S. Pat. No. 5,900,290 Carbon (a-C:F) Benzocyclobutene SOD 2.4-2.7
U.S. Pat. No. 5,225,586 (BCB) Polyarylene Ether (PAE) SOD 2.4 U.S.
patents 5,986,045; 5,874,516; and 5,658,994 Parylene (N and F) CVD
2.4 U.S. Pat. No. 5,268,202 Polyphenylenes SOD 2.6 U.S. patents
5,965,679 and 6,288,188B1; and Waeterloos et al., "Integration
Feasibility of Porous SiLK Semiconductor Dielectric", Proc. Of the
2001 International Interconnect Tech. Conf., pp. 253-254 (2001).
Thermosettable SOD 2.3 International Patent Publication WO
benzocyclobutenes, 00/31183 polyarylenes, thermosettable
perfluoroethylene monomer Poly(phenylquinoxaline), SOD 2.3-3.0 U.S.
patents 5,776,990; 5,895,263; organic polysilica 6,107,357; and
6,342,454; and US Patent Publication 2001/0040294 Organic
polysilica SOD Not reported U.S. Pat. No. 6,271,273 Organic and
inorganic SOD 2.0-2.5 U.S. Pat. No. 6,156,812 Materials Organic and
inorganic SOD 2.0-2.3 U.S. Pat. No. 6,171,687 Materials Organic
materials SOD Not reported U.S. Pat. No. 6,172,128 Organic SOD 2.12
U.S. Pat. No. 6,214,746 Organosilsesquioxane CVD, SOD <3.9 WO
01/29052 Fluorosilsesquioxane CVD, SOD <3.9 WO 01/29141
[0008] Unfortunately, numerous organic SOD systems under
development with a dielectric constant between 2.0 and 3.5 suffer
from certain drawbacks in terms 5 of mechanical and thermal
properties as described above; therefore a need exists in,the
industry to develop improved processing and performance for
dielectric films in this dielectric constant range. In addition,
industry demands materials having demonstrated low dielectric
constant extendibility, i.e. capable of being reduced to an even
lower dielectric constant, e.g., from 2.7 to 2.5 to 2.2 to 2.0 and
below.
[0009] Reichert and Mathias describe compounds and monomers that
comprise adamantane molecules, which are in the class of cage-based
molecules and are taught to be useful as diamond substitutes.
(Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1993, Vol. 34
(1), pp. 495-6; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.),
1992, Vol. 33 (2), pp. 144-5; Chem. Mater., 1993, Vol. 5 (1), pp.
4-5; Macromolecules, 1994, Vol. 27 (24), pp. 7030-7034;
Macromolecules, 1994, Vol. 27 (24), pp. 7015-7023; Polym, Prepr.
(Am. Chem. Soc., Div. Polym. Chem.), 1995, Vol. 36 (1), pp.
741-742; 205.sup.th ACS National Meeting, Conference Program, 1993,
pp. 312; Macromolecules, 1994, Vol. 27 (24), pp. 7024-9;
Macromolecules, 1992, Vol. 25 (9), pp. 2294-306; Macromolecules,
1991, Vol. 24 (18), pp. 5232-3; Veronica R. Reichert, PhD
Dissertation, 1994, Vol. 55-06B; ACS Symp. Ser.: Step-Growth
Polymers for High-Performance Materials, 1996, Vol. 624, pp.
197-207; Macromolecules, 2000, Vol. 33 (10), pp. 3855-3859; Polym,
Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1999, Vol. 40 (2), pp.
620-621; Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1999,
Vol. 40 (2), pp. 577-78; Macromolecules, 1997, Vol. 30 (19), pp.
5970-5975; J. Polym. Sci, Part A: Polymer Chemistry, 1997, Vol. 35
(9), pp. 1743-1751; Polym, Prepr. (Am. Chem. Soc., Div. Polym.
Chem.), 1996, Vol. 37 (2), pp. 243-244; Polym, Prepr. (Am. Chem.
Soc., Div. Polym. Chem.), 1996, Vol. 37 (1), pp. 551-552; J. Polym.
Sci., Part A: Polymer Chemistry, 1996, Vol. 34 (3), pp. 397-402;
Polym, Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1995, Vol. 36
(2), pp. 140-141; Polym, Prepr. (Am. Chem. Soc., Div. Polym.
Chem.), 1992, Vol. 33 (2), pp. 146-147; J. Appl. Polym. Sci., 1998,
Vol. 68 (3), pp. 475-482). The adamantane-based compounds and
monomers described by Reichert and Mathias are preferably used to
form polymers with adamantane molecules at the core of a thermoset.
The compounds disclosed by Reichert and Mathias in their studies,
however, comprise only one isomer of the adamantane-based compound
by design choice. Structure A shows this symmetrical para- isomer
1,3,5,7-tetrakis[4'-(phenylethynyl)phenyl]adamantane: 1
[0010] Structure A
[0011] In other words, Reichert and Mathias in their individual and
joint work contemplated a useful polymer comprising only one isomer
form of the target adamantane-based monomer. A significant problem
exists, however, when forming and processing polymers from the
single isomer form (symmetrical "all-para" isomer)
1,3,5,7-tetrakis[4'-(phenylethynyl)phenyl- ]adamantane of the
adamantane-based monomer. According to the Reichert dissertation
(supra) and Macromolecules, vol. 27, (pp. 7015-7034) (supra), the
symmetrical all-para isomer 1,3,5,7-tetrakis[4'-(phenylethyn-
yl)phenyl]adamantane "was found to be soluble enough in chloroform
that a .sup.1H NMR spectrum could be obtained. However, acquisition
times were found to be impractical for obtaining a solution
.sup.13C NMR spectrum." indicating that the all para isomer has low
solubility. Thus, the Reichert symmetrical "all-para" isomer
1,3,5,7-tetrakis[4'-(phenylethynyl- )phenyl]adamantane is insoluble
in standard organic solvents and therefore, would not be useful in
any application requiring solubility or solvent-based processing,
such as flow coating, spin coating, or dip coating.
[0012] In our commonly assigned pending patent application
PCT/US01/22204 filed Oct. 17, 2001 (claiming the benefit of our
commonly assigned pending patent applications U.S. Ser. No.
09/545058 filed Apr. 7, 2000; U.S. Ser. No. 09/618945 filed Jul.
19, 2000; U.S. Ser. No. 09/897936 filed Jul. 5, 2001; and U.S. Ser.
No. 09/902924 filed Jul. 10, 2001; and International Publication WO
01/78110 published Oct. 18, 2001), we discovered a composition
comprising an isomeric thermosetting monomer or dimer mixture,
wherein the mixture comprises at least one monomer or dimer having
the structure correspondingly 2
[0013] wherein Z is selected from cage compound and silicon atom;
R'.sub.1, R'.sub.2, R'.sub.3, R'.sub.4, R'.sub.5, and R'.sub.6 are
independently selected from aryl, branched aryl, and arylene ether;
at least one of the aryl, the branched aryl, and the arylene ether
has an ethynyl group; and R'.sub.7 is aryl or substituted aryl. We
also disclose methods for formation of these thermosetting
mixtures. This novel isomeric thermosetting monomer or dimer
mixture is useful as a dielectric material in microelectronics
applications and soluble in many solvents such as cyclohexanone.
These desirable properties make this isomeric thermosetting monomer
or dimer mixture ideal for film formation at thicknesses of about
0.1 .mu.m to about 1.0 .mu.m.
[0014] We filed a patent application Serial No. 60/______ on even
date herewith that claims a porous version of the preceding
isomeric mixture.
[0015] Our International Patent Publication WO 01/78110 published
Oct. 18, 2001 teaches in its background section that methods for
introducing nanosized voids include physical blending or chemical
grafting of thermostable or thermolabile portions. This
publication's invention is that nanosized voids may be introduced
into dielectric materials by using cage structures such as
adamantane or diamantane to achieve low dielectric constant
material and defines low dielectric constant materials as having a
dielectric constant of less than 3.0. However, this publication
does not report any dielectric constant for its examples.
[0016] International Patent Publication WO 00/31183 teaches in its
background section that although known porous thermoplastic
materials had acceptable dielectric constants, the pores tended to
collapse during subsequent high temperature processing and thus,
the art teaches away from adding porosity to the cage structure
that introduced nanosized voids in International Patent Publication
WO 01/78110 published Oct. 18, 2001. In addition, U.S. Pat. Nos.
5,776,990; 5,895,263; 6,107,357; and 6,342,454 and US Publication
2001/0040294 teach that although dielectric constants of 2.3-2.4
had been achieved at porosity levels less than about 20%, the pore
content could not be further increased without comprising the small
domain sizes and/or the non-interconnectivity of the pore
structure. Similarly, U.S. Pat. Nos. 6,271,273; 6,156,812;
6,171,687; and 6,172,128 teach that the amount of the thermally
labile monomer unit is limited to amounts less than about 30% by
volume because if more than about 30% by volume of the thermally
labile monomer is used, the resulting dielectric material has
cylindrical or lamellar domains, instead of pores or voids, which
lead to interconnected or collapsed structures upon removal, i.e.,
heating to degrade the thermally labile monomer units.
[0017] Although various methods are known in the art to lower the
dielectric constant of a material, these methods have
disadvantages. Thus, there is still a need in the semiconductor
industry to a) provide improved compositions and methods to lower
the dielectric constant of dielectric layers; b) provide dielectric
materials with improved properties, such as thermal stability,
glass transition temperature (T.sub.g), modulus, and hardness; c)
produce thermosetting compounds and dielectric materials that are
capable of being solvated and spun-on to a wafer or layered
material; and d) provide materials with demonstrated
extendibility.
[0018] The present invention advantageously provides demonstrated
extendibility so that semiconductor device manufacturers can use
the present compositions for numerous generations of microchips.
Also, the present invention provides for bonding of a porogen to a
thermosetting component and thus, porogen movement is minimized and
the possibility of pore aggregation is reduced.
SUMMARY OF THE INVENTION
[0019] In response to the need in the art and proceeding contrary
to the wisdom in the art, we developed a composition
comprising:
[0020] (a) thermosetting component comprising: (1) optionally
monomer of Formula I 3
[0021] and (2) at least one oligomer or polymer of Formula II 4
[0022] where E is a cage compound; each of Q is the same or
different and selected from aryl, branched aryl, and substituted
aryl wherein said substituents include hydrogen, halogen, alkyl,
aryl, substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,
alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,
hydroxyl, or carboxyl; G is aryl or substituted aryl where
substituents include halogen and alkyl; h is from 0 to 10; i is
from 0 to 10; j is from 0 to 10; and w is 0 or 1;
[0023] (b) porogen that bonds to the thermosetting component
(a).
[0024] We also discovered a method of lowering the dielectric
constant of a composition comprising: (a) thermosetting component
comprising: (1 ) optionally monomer of Formula I above and (2) at
least one oligomer or polymer of Formula II above where E, Q, G, h,
I, and j are defined as above; and
[0025] (b) adhesion promoter comprising compound having at least
bifunctionality wherein the bifunctionality may be the same or
different and the first functionality is capable of interacting
with the thermosetting component (a) and the second functionality
is capable of interacting with a substrate when the composition is
applied to the substrate
[0026] comprising the steps of:
[0027] bonding porogen to the thermosetting component;
[0028] decomposing the bonded porogen; and
[0029] volatilizing the decomposed porogen whereby pores form in
the composition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIGS. 1A through 1F illustrates how to make adamantane based
compositions useful as the thermosetting component in the present
compositions.
[0031] FIG. 2 illustrates one method for making diamantane based
compositions useful as the thermosetting component in the present
compositions.
[0032] FIGS. 3A through 3F illustrate another method for making
diamantane based compositions useful as the thermosetting component
in the present compositions.
[0033] FIGS. 4 through 11 illustrate reaction schemes for
covalently bonding the thermosetting component to the porogen in
the present compositions.
[0034] FIG. 12 illustrates the reaction scheme of Inventive Example
1.
[0035] FIG. 13 shows scanning electron microscopy pictures for the
cross section and surface of the film of Inventive Example 1.
[0036] FIG. 14 illustrates the reaction scheme of Inventive Example
2.
[0037] FIG. 15 shows scanning electron microscopy pictures for the
cross section and surface of the film of Inventive Example 2.
[0038] FIG. 16 illustrates the reaction scheme of Inventive Example
3.
DETAILED DESCRIPTION OF THE INVENTION
[0039] We filed a patent application 10/______ on even date
herewith that claims a composition of a thermosetting component and
a porogen wherein the porogen does not have to bond to the
thermosetting component.
[0040] Thermosetting Component:
[0041] The phrases "cage structure", "cage molecule", and "cage
compound" as used herein are intended to be used interchangeably
and refer to a molecule having at least eight atoms arranged such
that at least one bridge covalently connects two or more atoms of a
ring system. In other words, a cage structure, cage molecule, or
cage compound comprises a plurality of rings formed by covalently
bound atoms, wherein the structure, molecule, or compound defines a
volume, such that a point located within the volume cannot leave
the volume without passing through the ring. The bridge and/or the
ring system may comprise one or more heteroatoms, and may contain
aromatic groups, partially cyclic or acyclic saturated hydrocarbon
groups, or cyclic or acyclic unsaturated hydrocarbon groups.
Further contemplated cage structures include fullerenes, and crown
ethers having at least one bridge. For example, an adamantane or
diamantane is considered a cage structure, while a naphthalene or
an aromatic spirocompound are not considered a cage structure under
the scope of this definition, because a naphthalene or an aromatic
spirocompound do not have one, or more than one bridge and thus, do
not fall within the description of the cage compound above. Cage
compounds are preferably adamantane and diamantane and more
preferably adamantane.
[0042] The phrase "bridgehead carbon" as used herein refers to any
cage structure carbon bound to three other carbons. Thus, for
example, adamantane has four bridgehead carbons while diamantane
has eight bridgehead carbons.
[0043] Preferred dielectric material is thermosetting component
disclosed and claimed in our commonly assigned pending patent
application 60/347195 filed Jan. 8, 2002 and 60/______ filed on
even date herewith, which are incorporated herein by reference in
their entirety.
[0044] Preferably, the thermosetting component (a) comprises: (1)
adamantane monomer of Formula III 5
[0045] and (2) adamantane oligomer or polymer of Formula IV 67
[0046] or (1) diamantane monomer of Formula V 8
[0047] and (2) diamantane oligomer or polymer of Formula VI 910
[0048] wherein h is from 0 to 10; i is from 0 to 10; j is from 0 to
10; each R.sub.1 in Formulae III, IV, V, and VI is the same or
different and selected from hydrogen, halogen, alkyl, aryl,
substituted aryl, heteroaryl, aryl ether, alkenyl, alkynyl,
alkoxyl, hydroxyalkyl, hydroxyaryl, hydroxyalkenyl, hydroxyalkynyl,
hydroxyl, or carboxyl; and each Y in Formulae III, IV, V, and VI is
the same or different and selected from hydrogen, alkyl, aryl,
substituted aryl, or halogen.
[0049] Formulae II, IV, and VI represent random or irregular
structures in that any one of the units h, i, and j may or may not
repeat numerous times before another unit is present. Thus, the
sequence of units in Formulae II, IV, and VI above is random or
irregular.
[0050] In the one embodiment, preferably the thermosetting
component comprises adamantane monomer of Formula III above and at
least one adamantane oligomer or polymer of Formula IV above where
at least one of h, i, and j is at least 1. Preferably, the
thermosetting component comprises diamantane monomer of Formula V
above and at least one diamantane oligomer or polymer of Formula VI
above where at least one of h, i, and j is at least 1.
[0051] Preferably, the thermosetting component comprises adamantane
monomer of Formula III above and adamantane oligomer or polymer of
Formula VII below. 11
[0052] Preferably, the thermosetting component comprises diamantane
monomer of Formula V above and diamantane oligomer or polymer of
Formula VIII below. 12
[0053] Preferably, the thermosetting component comprises adamantane
monomer of Formula III above and adamantane dimer of Formula IX
below. 13
[0054] Preferably, the thermosetting component comprises diamantane
monomer of Formula V above and diamantane dimer of Formula X below.
14
[0055] Preferably, the thermosetting component comprises adamantane
monomer of Formula III above and adamantane trimer of Formula XI
below. 15
[0056] Preferably, the thermosetting component comprises diamantane
monomer of Formula V above and diamantane trimer of Formula XII
below. 16
[0057] Preferably, the thermosetting component comprises adamantane
monomer of Formula III above, adamantane dimer of Formula IX above,
and at least one adamantane oligomer or polymer of Formula IV above
where at least one of h, i, and j is at least 1. Preferably, the
thermosetting component comprises diamantane monomer of Formula IV
above, diamantane dimer of Formula X above, and at least one
diamantane oligomer or polymer of Formula VI above where at least
one of h, i, and j is at least 1.
[0058] Preferably, the thermosetting component comprises adamantane
monomer of Formula 11 above, adamantane dimer of Formula IX above,
adamantane trimer of Formula XI above, and at least one adamantane
oligomer or polymer of Formula IV above where at least one of i and
j is at least 1. Preferably, the thermosetting component comprises
diamantane monomer of Formula V above, diamantane dimer of Formula
X above, diamantane trimer of Formula XII above, and at least one
diamantane oligomer or polymer of Formula VI above where at least
one of i and j is at least 1.
[0059] The thermosetting component comprises adamantane monomer of
Formula III that is a tetrasubstituted adamantane or a diamantane
monomer of Formula V that is a tetrasubstituted diamantane. The
preferred monomer is the adamantane monomer of Formula III. The
adamantane framework carries a substituted aryl radical in each of
positions 1, 3, 5, and 7. The compound with the Formula IV is an
oligomer or polymer, linked via unsubstituted and/or substituted
aryl units, of the adamantane monomer of Formula III. The compound
with the Formula VI is an oligomer or polymer, linked via
unsubstituted and/or substituted aryl units, of the diamantane
monomer of Formula V. Generally, h, i, and j are whole numbers from
0 to 10, preferably 0 to 5, and more preferably 0 to 2. The
simplest adamantane oligomer is thus the dimer (h is 0, i is 0, and
j is 0 in Formula IV) as shown in Formula IX above, in which two
adamantane frameworks are linked via an unsubstituted or
substituted aryl unit. The simplest diamantane oligomer is thus the
dimer (h is 0, i is 0, and j is 0 in Formula VI) as shown in
Formula X above, in which two diamantane frameworks are linked via
an unsubstituted or substituted aryl unit.
[0060] In another embodiment, preferably the present thermosetting
component comprises at least one adamantane oligomer or polymer of
Formula IV above where h is from 0 to 10, i is from 0 to 10, and j
is from 0 to 10. Preferably, the present thermosetting component
comprises at least one diamantane oligomer or polymer of Formula VI
above where h is from 0 to 10, i is from 0 to 10, and j is from 0
to 10.
[0061] Preferably, the present thermosetting component comprises at
least one adamantane oligomer or polymer of Formula IV above where
h is 0 or 1, i is 0, and j is 0. This adamantane structure is shown
as Formula VII above.
[0062] Preferably, the present thermosetting component comprises at
least one diamantane oligomer or polymer of Formula VI above where
h is 0 or 1, i is 0, and j is 0. This diamantane structure is shown
as Formula VIII above.
[0063] Preferably, the thermosetting component comprises at least
one adamantane oligomer or polymer of Formula IV above where h is
0, i is 0, and j is 0. This adamantane dimer is shown as Formula IX
above.
[0064] Preferably, the thermosetting component comprises at least
one diamantane oligomer or polymer of Formula VI above where h is
0, i is 0, and j is 0. This diamantane dimer is shown as Formula X
above.
[0065] Preferably, the thermosetting component comprises at least
one adamantane oligomer or polymer of Formula IV above where h is
1, i is 0, and j is 0. This adamantane trimer is as shown in
Formula XI abpve.
[0066] Preferably, the thermosetting component (a) comprises at
least one diamantane oligomer or polymer of Formula VI above where
h is 1, i is 0, and j is 0. This diamantane trimer is as shown in
Formula XII above.
[0067] Preferably, the thermosetting component comprises a mixture
of at least one adamantane oligomer or polymer of Formula IV above
where h is 2, i is 0, and j is 0 (linear oligomer or polymer) and h
is 0, i is 1, and j is 0 (branched oligomer or polymer). Thus, this
composition comprises a mixture of an adamantane linear tetramer as
shown in Formula XIII below 17
[0068] and adamantane branched tetramer as shown Formula XIV below
18
[0069] Preferably, the thermosetting component comprises at least
one diamantane oligomer or polymer of Formula VI above where h is
2, i is 0, and j is 0 (linear oligomer or polymer) and h is 0, i is
1, and j is 0 (branched oligomer or polymer). Thus, the present
composition comprises diamantane linear tetramer as shown in
Formula XV below 19
[0070] and diamantane branched tetramer as shown Formula XVI below
20
[0071] Preferably, the thermosetting component comprises adamantane
dimer of Formula IX above and adamantane trimer of Formula XI
above. Preferably, the thermosetting component comprises diamantane
dimer of Formula X above and diamantane trimer of Formula XII
above.
[0072] Preferably, the thermosetting component comprises adamantane
dimer of Formula IX above and at least one adamantane oligomer or
polymer of Formula IV above where h is 0, i is at least 1, and j is
0. Preferably, the thermosetting component comprises diamantane
dimer of Formula X above and at least one diamantane oligomer or
polymer of Formula VI above where h is 0, i is at least 1, and j is
0.
[0073] In both embodiments, for Formulae I and II above, preferred
Q groups include aryl and aryl substituted with alkenyl and alkynyl
groups and more preferred Q groups include (phenylethynyl)phenyl,
phenylethynyl(phenylethynyl)phenyl, and (phenylethynyl)phenylphenyl
moiety. Preferred aryls for G include phenyl, biphenyl, and
terphenyl. The more preferred G group is phenyl.
[0074] The individual radicals R.sub.1 of the substituted ethynyl
radical on the phenyl ring attached to the adamantane or diamantane
ring of the type R.sub.1.ident.C-- are in each case the same or
different in Formulae III, IV, V, VI, VII, VIII, IX, X, XI, XII,
XIII, XIV, XV, and XVI above. R.sub.1 is selected from hydrogen,
halogen, alkyl, aryl, substituted aryl, heteroaryl, aryl ether,
alkenyl, alkynyl, alkoxyl, hydroxyalkyl, hydroxyaryl,
hydroxyalkenyl, hydroxyalkynyl, hydroxyl, or carboxyl. Each R.sub.1
may be unbranched or branched and unsubstituted or substituted and
the substituents may be unbranched or branched. It is preferred
that the radicals alkyl, alkenyl, alkynyl, alkoxyl, hydroxyalkyl,
hydroxyalkenyl, and hydroxyalkynyl contain from about 2 to about 10
carbon atoms and the radicals aryl, aryl ether, and hydroxyaryl
contain from about 6 to about 18 carbon atoms. If R.sub.1 stands
for aryl, R.sub.1 is preferably phenyl. Preferably, at least two of
the R,C.ident.C groups on the phenyl groups are two different
isomers. Examples of at least two different isomers include meta-,
para-, and ortho-isomers. Preferably, the at least two different
isomers are meta- and para-isomers. In the preferred monomer,
1,3,5,7-tetrakis[3'/4'-phenylethy- nyl)phenyl]adamantane (shown in
FIG. 1D), five isomers form: (1) para-, para-, para-, para-; (2)
para-, para-, para-, meta-; (3) para-, para-, meta-, meta-; (4)
para-, meta-, meta-, meta-; and (5) meta-, meta-, meta-, meta-.
[0075] Each Y of the phenyl rings in the Formulae III, IV, V, VI,
VII, VIII, IX, X, XI, XII, XIII, XIV, XV, and XVI above is in each
case the same or different and selected from hydrogen, alkyl, aryl,
substituted aryl, or halogen. When Y is aryl, examples of aryl
groups include phenyl or biphenyl. Y is selected from preferably
hydrogen, phenyl, and biphenyl and more preferably hydrogen.
Preferably, at least one of the phenyl groups between two
bridgehead carbons of adamantane or diamantane exists as at least
two different isomers. Examples of at least two different isomers
include meta-, para-, and ortho-isomers. Preferably, the at least
two isomers are meta- and para-isomers. In the most preferred dimer
1,3/4-bis{1',3',5'-tris[3"/4"-(phenylethynyl)phenyl]adamant-7'-yl}benzene
(shown in FIG. 1F), 14 isomers form as follows. Preferably, the
phenyl group located between the two bridgehead carbons of the
adamantane exists as meta- and para-isomers. For each of the two
preceding isomers, seven isomers of the R.sub.1C.ident.C groups on
the phenyl groups exist as follows: (1) para-, para-, para-, para-,
para-, para-; (2) para-, para-, para-, para-, para-, meta-; (3)
para-, para-, para-, para-, meta-, meta-; (4) para-, para-, para-,
meta-, meta-, meta-; (5) para-, para-, meta-, meta-, meta-, meta-;
(6) para-, meta-, meta-, meta-, meta-, meta-; and (7) meta-, meta-,
meta-, meta-, meta-, meta-.
[0076] In addition to the branched adamantane structure of Formula
XIV above, it should be understood that Formula IV above when h is
0, i is 0, and j is 1 represents further branching as shown in
Formula XVII below. It should be understood that branching may
occur beyond that of the Formula XVII structure because further
branching of the pending adamantane units of the Formula XVII
structure may also occur. 21
[0077] In addition to the branched diamantane structure of Formula
XVI above, it should be understood that Formula VI above when h is
0, i is 0, and j is 1 represents further branching as shown in
Formula XVIII below. It should be understood that branching may
occur beyond that of the Formula XVIII structure because further
branching of the pending diamantane units of the Formula XVIII
structure may also occur. 22
[0078] In thermosetting component, the monomer and oligomer or
polymer contents are determined by the gel permeation
chromatography techniques set forth below in the Analytical Test
Methods section. The present composition comprises the adamantane
or diamantane monomer in a quantity of about 30 to about 70 area-%,
more preferably about 40 to about 60 area-% and even more
preferably about 45 to about 55 area-% and the oligomer or polymer
in a quantity of about 70 to about 30 area-%, more preferably about
60 to about 40 area-%, and even more preferably about 55 to about
45 area-%. Most preferably, the present composition comprises the
monomer (1) in a quantity of approximately 50 area-% and the
oligomer or polymer (2) in a quantity of approximately 50
area-%.
[0079] The Analytical Test Methods section sets forth two Gel
Permeation Chromatography Methods. Both provide similar results.
One skilled in the art may elect to use the second method in that
it yields additional detail on the dimer and trimer.
[0080] In general, the quantity ratio of the adamantane or
diamantane monomer (1) to oligomer or polymer (2) can be set in a
desired manner, e.g. by altering the molar ratio of the starting
components during the preparation of the composition according to
the invention, by adjusting reaction conditions, and by altering
the ratio of nonsolvent to solvent during precipitation/isolation
steps.
[0081] A preferred process for preparing the thermosetting
component (a) comprises the following steps.
[0082] In step (A), adamantane or diamantane is reacted with
halogeno benzene compound of Formula XIX 23
[0083] where W is halogen,
[0084] to form a mixture which if adamantane is used, comprises at
least one monomer of Formula XX 24
[0085] and at least one oligomer or polymer of Formula XXI where h
is from 0 to 10, i is from 0 to 10, and j is from 0 to 10 25
[0086] or if diamantane is used, comprises at least one monomer of
Formula XXII 26
[0087] and at least one oligomer or polymer of Formula XXIII where
h is from 0 to 10, i is from 0 to 10, and j is from 0 to 10 27
[0088] It should be understood to those skilled in the art that
reaction may occur on diamantane at bridgehead carbons other than
those indicated in Formulae XXII and XXIII above.
[0089] In step (B), the mixture resulting from step (A) is reacted
with terminal alkyne of the formula R.sub.1C.ident.CH. Preferably,
the present process forms compositions of Formulae III and IV or V
and VI above.
[0090] In step (A), adamantane or diamantane is reacted with
halogeno benzene compound with the Formula XIX. In addition to the
halogen radical W and the previously described radical Y, the
halogeno benzene compound can also contain further
substituents.
[0091] The halogeno benzene compound is preferably selected from
bromobenzene, dibromobenzene, and iodobenzene. Bromobenzene and/or
dibromobenzene are preferred, bromobenzene being even more
preferred.
[0092] The reaction of adamantane or diamantane with the halogeno
benzene compound (step (A)) takes place preferably through
Friedel-Crafts reaction in the presence of a Lewis acid catalyst.
Although all customary Lewis acid catalysts may be used, it is
preferred that the Lewis acid catalyst contains at least one
compound selected from aluminum(III) chloride (AlCl.sub.3),
aluminum(III) bromide (AlBr.sub.3), and aluminum (III) iodide
(AlI.sub.3). Aluminum(III) chloride (AlCl.sub.3) is most preferred.
Despite the greater Lewis acidity of aluminum(III) bromide, its use
is generally less preferred, because it has a low sublimation point
of only 90.degree. C. and is thus much more difficult to handle on
an industrial scale than e.g. aluminum(III) chloride.
[0093] In a further preferred version, the Friedel-Crafts reaction
is carried out in the presence of a second catalyst component. The
second catalyst component preferably contains at least one compound
selected from tertiary halogen alkane with 4 to 20 carbon atoms,
tertiary alkanol with 4 to 20 carbon atoms, secondary and tertiary
olefin with 4 to 20 carbon atoms and tertiary halogen alkyl aryl
compound. In particular, the second catalyst component contains at
least one compound selected from 2-bromo-2-methylpropane
(tert.-butyl bromide), 2-chloro-2-methylpropane (tert.-butyl
chloride), 2-methyl-2-propanol (tert.-butyl alcohol), isobutene,
2-bromopropane, and tert.-butylbromobenzene, with
2-bromo-2-methylpropane (tert.-butyl bromide) being most preferred.
Overall, compounds whose alkyl groups include 5 or more carbon
atoms are less suitable, as solid constituents precipitate out of
the reaction solution at the end of the reaction.
[0094] It is most preferred that the Lewis acid catalyst is
aluminum(III) chloride (AlCl.sub.3) and the second catalyst
component is 2-bromo-2-methylpropane (tert.-butyl bromide) or
tert.-butylbromobenzene.
[0095] The preferable procedure for carrying out the Friedel-Crafts
reaction is that adamantane or diamantane, halogeno benzene
compound (e.g. bromobenzene), and Lewis acid catalyst (e.g.
aluminium chloride) are mixed and heated at a temperature of
30.degree. C. to 50.degree. C., preferably 35.degree. C. to
45.degree. C. and in particular 40.degree. C. At temperatures lower
than 30.degree. C., the reaction is not completed, i.e. a higher
proportion of tri-substituted adamantane forms for example. In
principle it is conceivable to use even higher temperatures than
those given above (e.g. 60.degree. C.), but this leads in an
undesirable manner to a higher proportion of non-halogenated
aromatic material (e.g. benzene) in the reaction mixture of step
(A). The second component of the catalyst system, say tert.-butyl
bromide, is then added to the above reaction solution generally
over a period of 5 to 10 hours, preferably 6 to 7 hours and after
the addition has ended, mixed into the reaction mixture in the
temperature range named above customarily for a further 5 to 10
hours, preferably 7 hours.
[0096] Surprisingly, in addition to the monomeric tetraphenylated
compound, e.g. 1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane,
oligomers or polymers thereof were also found in the mixture
obtained after step (A). It was wholly unexpected that the quantity
ratio of adamantane monomer of Formula XX to adamantane oligomer or
polymer of Formula XXI or diamantane monomer of Formula XXII to
diamantane oligomer or polymer of Formula XXIII was controllable
through the quantities of adamantane or diamantane, halogeno
benzene compound (e.g. bromobenzene), and second catalyst component
(e.g. tert.-butyl bromide) used. The molar ratio of adamantane or
diamantane to halogeno benzene compound to second catalyst
component in the reaction mixture of step (A) is preferably
1:(5-15):(2-10) and even more preferably 1:(8-12):(4-8).
[0097] In the compounds with the Formulae XX, XXI, XXII, and XXIII,
the position of the halogen substituent W is undefined. Preferably,
the mixtures comprise meta- and para-isomers which, unlike all
para-isomers, advantageously produce improved solubility and good
film properties. In the reaction mixture of step (A), in addition
to monomers and oligomers or polymers, starting components and
by-products, such as not wholly phenylated adamantanes, can also
occur.
[0098] The mixture resulting from step (A) is optionally worked up
using methods known to those skilled in the art. For example, it
may be necessary to remove non-reacted halogen phenyl compound, say
bromobenzene, from the mixture in order to obtain a product, usable
for further reaction, with a high proportion of compounds of
Formulae XX, XXI, XXII, and XXIII. Any solvent or solvent mixture
which is miscible with the halogeno benzene compound, say
bromobenzene, and is suitable for the precipitation of the
compounds of Formulae XX, XXI, XXII, and XXIII may be used for the
isolation of such a product. It is preferred to introduce the
mixture resulting from step (A) into a nonpolar solvent or solvent
mixture, e.g. by dropping in, with preference being given to the
use of aliphatic hydrocarbons with 7 to 20 carbon atoms or mixtures
thereof and in particular at least one component selected from
heptane fraction (boiling point 93-99.degree. C.), octane fraction
(boiling point 98-110.degree. C.) and alkane mixture currently
commercially available from Honeywell International Inc. under the
tradename Spezial Benzin 80-110.degree. C. (petroleum ether with
boiling point of 80-110.degree. C.). Spezial Benzin 80-110.degree.
C. (petroleum ether with boiling point of 80-110.degree. C.) is
most preferred. The weight ratio of organic mixture to nonpolar
solvent is preferably about 1:2 to about 1:20, more preferably
about 1:5 to about 1:13, and even more preferably about 1:7 to
about 1:11. Alternatively, a polar solvent or solvent mixture (e.g.
methanol or ethanol) can be used for the working-up of the mixture
obtained after step (A), but it is less preferred, as the product
mixture then precipitates out as a rubbery composition.
[0099] We have found that the peak ratio of monomer resulting from
step (A) above to its dimer and trimer and oligomer in the reaction
mixture shifts dramatically if the step (A) mixture is precipitated
into certain solvents. This discovery advantageously allows one
skilled in the art to adjust process conditions in order to achieve
a targeted ratio of monomer to dimer and trimer and oligomer. To
reduce this ratio, preferably, a solvent is used in which the
monomer and oligomer or polymer have different solubilities.
[0100] Preferred solvents for achieving this monomer to dimer and
trimer ratio shift include Spezial Benzin 80-110.degree. C.
(petroleum ether with boiling point of 80.degree. C.-110.degree.
C.), ligroine (boiling point 90-110.degree. C.), and heptane
(boiling point 98.degree. C.). The more preferred solvent is
Spezial Benzin. More specifically, to achieve a shift from about
3:1 monomer:dimer+trimer+oligomer to about 1:1, the step (A)
mixture is precipitated into Spezial Benzin or to attain a shift
from about 3:1 monomer:dimer+trimer+oligomer to about 1.7-2.0:1.0,
the step (A) reaction mixture is precipitated into ligroine and
heptane. We know that these substantial changes in peak
distribution at precipitation are explained by the loss of monomer
in the precipitation filtrates: 2/3 loss in Spezial Benzin and
.gtoreq.1/3 loss in ligroine and heptane, which correspond to
monomer yield losses of 50 and 25-33%. In order for the ratio
monomer:dimer+trimer+oligomer 3:1 to remain unchanged, the step (A)
reaction mixture is precipitated into methanol where no yield
losses are observed. This is corroborated by determination of yield
losses of the filtrates and GPC analysis of the filtrates.
[0101] Like the synthesis described by Ortiz, the Friedel-Crafts
reaction which is carried out according to a preferred version in
step (A) of the present process starts direct from adamantane which
is coupled with the halogeno benzene compound. Compared with
previous syntheses of e.g.
1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane by Reichert et al.,
the present process is particularly advantageous because it is no
longer necessary to produce tetrabrominated adamantanes first,
which saves a reaction step. Also, less unwanted benzene forms.
[0102] It is known to those skilled in the art that the halogen
radical W in the compounds of Formulae XX, XXI, XXII, and XXIII
above can also be introduced, apart from a direct reaction of
adamantane with halogen phenyl compound (e.g. with the help of a
Friedel-Crafts reaction), by a multi-stage synthesis, for example,
by coupling adamantane with a phenyl compound (i.e. without halogen
radical W) followed by introduction of the radical W say through
addition with W.sub.2 (e.g. Br.sub.2) although this is not
preferred.
[0103] In step (B) of the preferred process, the (optionally
worked-up) mixture obtained after step (A) is reacted with terminal
alkyne of the formula R.sub.1C.ident.CH where R.sub.1 is as
previously defined.
[0104] In the formula R.sub.1C.ident.CH, R.sub.1 is identical with
the previously described radical R.sub.1 of the adamantane product
of Formulae III and IV and the diamantane product of Formulae V and
VI. Accordingly it is most preferred to use ethynyl benzene
(phenylacetylene) as terminal alkyne for the reaction in step
(B).
[0105] In order, in step (B), to couple the terminal alkyne to the
halogeno benzene radicals located at the adamantane system, all
conventional coupling methods suitable for this purpose may be
used, as described for example in Diederich, F., and Stang, P. J.,
(Eds.) "Metal-Catalyzed Cross-Coupling Reactions", Wiley-VCH 1998
and March, J., "Advanced Organic Chemistry", 4th Edition, John
Wiley & Sons 1992, pages 717/718.
[0106] When Y on the phenyl groups is attached to two cage
structure bridgehead carbons in Formula XXI above or in Formula
XXIII above, Y may react with phenylacetylene to generate terminal
alkyne groups.
[0107] In a preferred version of the process according to the
invention, the reaction of the (optionally worked-up) mixture
obtained after step (A) with terminal alkyne is carried out in the
presence of a catalyst system as used in the so-called Sonogashira
coupling (cf. Sonogashira; Tohda; Hagihara; Tetrahedron Lett. 1975,
page 4467). It is even more preferred to use a catalyst system
which in each case contains at least one palladium-triarylphosphine
complex with the formula [Ar.sub.3P].sub.2PdX.sub.2 (where Ar=aryl
and X=halogen), a copper halide (e.g. Cul), a base (e.g. a
trialkylamine), a triarylphosphine and a co-solvent. According to
the invention, this preferred catalyst system can equally well
consist of the named components. The co-solvent preferably contains
at least one component selected from toluene, xylene,
chlorobenzene, N,N-dimethylformamide and 1-methyl-2-pyrrolidone
(N-methylpyrrolidone (NMP)). A catalyst system which contains the
components bis-(triphenylphosphine)palladium(II)dichloride (i.e.
[Ph.sub.3P].sub.2-PdCl.sub.2), triphenylphosphine (i.e.
[Ph.sub.3P]), copper(I)-iodide, triethylamine and toluene as
co-solvent is most preferred.
[0108] The preferred procedure for the reaction of the mixture
obtained from step (A) (and optionally worked-up) with terminal
alkyne is that the mixture is first mixed with the base (e.g.
triethylamine) and the co-solvent (e.g. toluene) and this mixture
is stirred for some minutes at room temperature. The
palladium-triphenylphosphine complex (e.g.
Pd(PPh.sub.3).sub.2Cl.sub.2), triphenylphosphine (PPh.sub.3) and
copper halide (e.g. copper(I)-iodide) are then added, and this
mixture is heated in a temperature range of 50.degree. C. to
90.degree. C. (more preferably 80.degree. C. to 85.degree. C.).
Terminal alkyne is then added in the named temperature range within
1 to 20 hours (more preferably 3 hours). After the ending of the
addition, the mixture is heated for at least 5 to 20 hours (more
preferably 12 hours) at a temperature of 75.degree. C. to
85.degree. C. (more preferably 80.degree. C.). Solvent is then
added to the reaction solution and distilled off under reduced
pressure. Preferably, after filtration, the reaction solution is
then cooled to a temperature of 20.degree. C. to 30.degree. C.
(more preferably 25.degree. C.). Finally, the reaction mixture of
step (B), in particular for the removal of metal traces (e.g. Pd),
is worked up with conventional methods which are known to those
skilled in the art.
[0109] The peak ratio of monomer resulting from step (B) above to
its dimer and trimer and oligomer in the reaction mixture shifts if
the step (B) mixture is precipitated into certain solvents.
[0110] Surprisingly, it transpired that the reaction sequence
starting direct from adamantane leads to an oligomeric or polymeric
content in the reaction product of step (A) which can be controlled
via the use ratio of adamantane, halogeno benzene compound and the
second catalyst component, say tert.-butyl bromide. In
corresponding manner, the benzene content in the reaction mixture
of step (A) is also successfully regulated via this use ratio,
which, because of the toxicity of benzene in industrial-scale
syntheses, is of great importance. The oligomeric or polymeric
content permits the same secondary chemistry as the monomer (e.g.
1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane, i.e. the oligomer or
polymer is just as accessible as the monomer for the reaction with
the terminal alkyne in step (B)).
[0111] Adhesion Promoter:
[0112] The phrase "adhesion promoter" as used herein means any
component that when added to thermosetting component, improves the
adhesion thereof to substrates compared with thermosetting
component alone.
[0113] The phrase "compound having at least bifunctionality" as
used herein means any compound having at least two functional
groups capable of interacting or reacting, or forming bonds as
follows. The functional groups may react in numerous ways including
addition reactions, nucleophilic and electrophilic substitutions or
eliminations, radical reactions, etc. Further alternative reactions
may also include the formation of non-covalent bonds, such as Van
der Waals, electrostatic bonds, ionic bonds, and hydrogen
bonds.
[0114] Adhesion promoter is disclosed in our commonly assigned
pending patent application 60/350187 filed Jan. 15, 2002 which is
incorporated herein by reference in its entirety.
[0115] In the adhesion promoter, preferably at least one of the
first functionality and the second functionality is selected from
Si containing groups; N containing groups; C bonded to O containing
groups; hydroxyl groups; and C double bonded to C containing
groups. Preferably, the Si containing groups are selected from
Si--H, Si--O, and Si--N; the N containing groups are selected from
such as C--NH.sub.2 or other secondary and tertiary amines, imines,
amides, and imides; the C bonded to O containing groups are
selected from .dbd.CO, carbonyl groups such as ketones and
aldehydes, esters, --COOH, alkoxyls having 1 to 5 carbon atoms,
ethers, glycidyl ethers; and epoxies; the hydroxyl group is phenol;
and the C double bonded to C containing groups are selected from
allyl and vinyl groups. For semiconductor applications, the more
preferred functional groups include the Si containing groups; C
bonded to O containing groups; hydroxyl groups; and vinyl
groups.
[0116] An example of a preferred adhesion promoter having Si
containing groups is silanes of the Formula XXIV:
(R.sub.2).sub.k(R.sub.3).sub.lSi(R- .sub.4).sub.m(R.sub.5).sub.n
wherein R.sub.2, R.sub.3, R.sub.4, and R.sub.5 each independently
represents hydrogen, hydroxyl, unsaturated or saturated alkyl,
substituted or unsubstituted alkyl where the substituent is amino
or epoxy, saturated or unsaturated alkoxyl, unsaturated or
saturated carboxylic acid radical, or aryl; at least two of
R.sub.2, R.sub.3, R.sub.4, and R.sub.5 represent hydrogen,
hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or
unsaturated carboxylic acid radical; and k+l+m+n.ltoreq.4. Examples
include vinylsilanes such as H.sub.2C.dbd.CHSi(CH.sub.3).sub.2H and
H.sub.2C.dbd.CHSi(R.sub.6).sub.3 where R.sub.6 is CH.sub.3O,
C.sub.2H.sub.5O, AcO, H.sub.2C.dbd.CH, or
H.sub.2C.dbd.C(CH.sub.3)O--, or vinylphenylmethylsilane;
allylsilanes of the formula
H.sub.2C.dbd.CHCH.sub.2--Si(OC.sub.2H.sub.5).sub.3 and
H.sub.2C.dbd.CHCH.sub.2--Si(H)(OCH.sub.3).sub.2
glycidoxypropylsilanes such as
(3-glycidoxypropyl)methyldiethoxysilane and
(3-glycidoxypropyl)trimethoxysilane; methacryloxypropylsilanes of
the formula
H.sub.2C.dbd.(CH.sub.3)COO(CH.sub.2).sub.3--Si(OR.sub.7).sub.3
where R.sub.7 is an alkyl, preferably methyl or ethyl;
aminopropylsilane derivatives including
H.sub.2N(CH.sub.2).sub.3Si(OCH.sub.2CH.sub.3).sub.3- ,
H.sub.2N(CH.sub.2).sub.3Si(OH).sub.3, or
H.sub.2N(CH.sub.2).sub.3OC(CH.s-
ub.3).sub.2CH.dbd.CHSi(OCH.sub.3).sub.3. The aforememtioned silanes
are commercially available from Gelest.
[0117] An example of a preferred adhesion promoter having C bonded
to O containing groups is glycidyl ethers including but not limited
to 1,1,1-tris-(hydroxyphenyl)ethane tri-glycidyl ether which is
commercially available from TriQuest.
[0118] An example of a preferred adhesion promoter having C bonded
to O containing groups is esters of unsaturated carboxylic acids
containing at least one carboxylic acid group. Examples include
trifunctional methacrylate ester, trifunctional acrylate ester,
trimethylolpropane triacrylate, dipentaerythritol pentaacrylate,
and glycidyl methacrylate. The foregoing are all commercially
available from Sartomer.
[0119] An example of a preferred adhesion promoter having vinyl
groups is vinyl cyclic pyridine oligomers or polymers wherein the
cyclic group is pyridine, aromatic, or heteroaromatic. Useful
examples include but not limited to 2-vinylpyridine and
4-vinylpyridine, commercially available from Reilly; vinyl
aromatics; and vinyl heteroaromatics including but not limited to
vinyl quinoline, vinyl carbazole, vinyl imidazole, and vinyl
oxazole.
[0120] An example of a preferred adhesion promoter having Si
containing groups is the polycarbosilane disclosed in commonly
assigned copending allowed U.S. patent application Ser. No.
09/471299 filed Dec. 23, 1999 incorporated herein by reference in
its entirety. The polycarbosilane is of the Formula XXV: 28
[0121] in which R.sub.8, R.sub.14, and R.sub.17 each independently
represents substituted or unsubsalltituted alkylene, cycloalkylene,
vinylene, allylene, or arylene; R.sub.9, R.sub.10, R.sub.11,
R.sub.10, R.sub.15, and R.sub.16 each independently represents
hydrogen atom or organo group comprising alkyl, alkylene, vinyl,
cycloalkyl, allyl, or aryl and may be linear or branched; R.sub.13
represents organosilicon, silanyl, siloxyl, or organo group; and p,
q, r, and s satisfy the conditions of
[4.ltoreq.p+q+r+s.ltoreq.100,000], and q and r and s may
collectively or independently be zero. The organo groups may
contain up to 18 carbon atoms but generally contain from about 1 to
about 10 carbon atoms. Useful alkyl groups include --CH.sub.2-- and
--(CH.sub.2).sub.t-- where t>1.
[0122] Preferred polycarbosilanes of the present invention include
dihydrido polycarbosilanes in which R.sub.8 is a substituted or
unsubstituted alkylene or phenyl, R.sub.9 group is a hydrogen atom
and there are no appendent radicals in the polycarbosilane chain;
that is, q, r, and s are all zero. Another preferred group of
polycarbosilanes are those in which the R.sub.9, R.sub.10,
R.sub.11, R.sub.12, R.sub.15, and R.sub.16 groups of Formula XXV
are substituted or unsubstituted alkenyl groups having from 2 to 10
carbon atoms. The alkenyl group may be ethenyl, propenyl, allyl,
butenyl or any other unsaturated organic backbone radical having up
to 10 carbon atoms. The alkenyl group may be dienyl in nature and
includes unsaturated alkenyl radicals appended or substituted on an
otherwise alkyl or unsaturated organic polymer backbone. Examples
of these preferred polycarbosilanes include dihydrido or alkenyl
substituted polycarbosilanes such as polydihydridocarbosilane,
polyallylhydrididocarbosilane and random copolymers of
polydihydridocarbosilane and polyallylhydridocarbosilane.
[0123] In the more preferred polycarbosilanes, the R.sub.9 group of
Formula XXV is a hydrogen atom and R.sub.8 is methylene and the
appendent radicals q, r, and s are zero. Other preferred
polycarbosilane compounds of the invention are polycarbosilanes of
Formula XXV in which R.sub.9 and R.sub.15 are hydrogen, R.sub.8 and
R.sub.17 are methylene, and R.sub.16 is an alkenyl, and appendent
radicals q and r are zero. The polycarbosilanes may be prepared
from well known prior art processes or provided by manufacturers of
polycarbosilane compositions. In the most preferred
polycarbosilanes, the R.sub.9 group of Formula XXV is a hydrogen
atom; R.sub.8 is --CH.sub.2--; q, r, and s are zero and p is from 5
to 25. These most preferred polycarbosilanes may be obtained from
Starfire Systems, Inc. Specific examples of these most preferred
polycarbosilanes follow:
2 Peak Weight Average Molecular Molecular Weight Weight
Polycarbosilane (Mw) Polydispersity (Mp) 1 400-1,400 2-2.5 330-500
2 330 1.14 320 3 10,000-14,000 10.4-16 1160 (with 10% allyl groups)
4 2,400 3.7 410 (with 75% allyl groups)
[0124] As can be observed in Formula XXV, the polycarbosilanes
utilized in the subject invention may contain oxidized radicals in
the form of siloxyl groups when r>0. Accordingly, R.sub.13
represents organosilicon, silanyl, siloxyl, or organo group when
r>0. It is to be appreciated that the oxidized versions of the
polycarbosilanes (r>0) operate very effectively in, and are well
within the purview of the present invention. As is equally
apparent, r can be zero independently of p, q, and s the only
conditions being that the radicals p, q, r, and s of the Formula
XXV polycarbosilanes must satisfy the conditions of
[4<p+q+r+s<100,000], and q and r can collectively or
independently be zero.
[0125] The polycarbosilane may be produced from starting materials
that are presently commercially available from many manufacturers
and by using conventional polymerization processes. As an example
of synthesis of the polycarbosilanes, the starting materials may be
produced from common organo silane compounds or from polysilane as
a starting material by heating an admixture of polysilane with
polyborosiloxane in an inert atmosphere to thereby produce the
corresponding polymer or by heating an admixture of polysilane with
a low molecular weight carbosilane in an inert atmosphere to
thereby produce the corresponding polymer or by heating an
admixture of polysilane with a low molecular carbosilane in an
inert atmosphere and in the presence of a catalyst such as
polyborodiphenylsiloxane to thereby produce the corresponding
polymer. Polycarbosilanes may also be synthesized by Grignard
Reaction reported in U.S. Pat. No. 5,153,295 hereby incorporated by
reference.
[0126] An example of a preferred adhesion promoter having hydroxyl
groups is phenol-formaldehyde resins or oligomers of the Formula
XXVI: --[R.sub.18C.sub.6H.sub.2(OH)(R.sub.19)].sub.u-- where
R.sub.18 is substituted or unsubstituted alkylene, cycloalkylene,
vinyl, allyl, or aryl; R.sub.19 is alkyl, alkylene, vinylene,
cycloalkylene, allylene, or aryl; and u=3-100. Examples of useful
alkyl groups include --CH.sub.2-- and --(CH.sub.2).sub.v-- where
v>1. A particularly useful phenol-formaldehyde resin oligomer
has a molecular weight of 1500 and is commercially available from
Schenectady International Inc.
[0127] The present adhesion promoter is preferably added in small,
effective amounts from about 0.5% to up to 20% based on the weight
of the present thermosetting composition and amounts up to about
5.0% by weight of the composition are generally more preferred.
[0128] By combining the adhesion promoter with the thermosetting
component and subjecting the composition to thermal or a high
energy source, the resulting compositions have superior adhesion
characteristics throughout the entire polymer so as to ensure
affinity to any contacted surface of the coating. The present
adhesion promoters also improve striation control, viscosity, and
film uniformity. Visual inspection confirms the presence of
improved striation control.
[0129] The present compositions may also comprise additional
components such as additional adhesion promoters, antifoam agents,
detergents, flame retardants, pigments, plasticizers, stabilizers,
and surfactants.
[0130] Porogen:
[0131] The term "pore" as used herein includes void and cells in a
material and any other term meaning space occupied by gas in the
material. Appropriate gases include relatively pure gases and
mixtures thereof. Air, which is predominantly a mixture of N.sub.2
and O.sub.2, is commonly distributed in the pores but pure gases
such as nitrogen, helium, argon, CO.sub.2, or CO are also
contemplated. Pores are typically spherical but may alternatively
or additionally include tubular, lamellar, discoidal, voids having
other shapes, or a combination of the preceding shapes and may be
open or closed. The term "porogen" as used herein means a
decomposable material that is radiation, thermally, chemically, or
moisture decomposable, degradable, depolymerizable, or otherwise
capable of breaking down and includes solid, liquid, or gaseous
material. The decomposed porogen is removable from or can
volatilize or diffuse through a partially or fully cross-linked
matrix to create pores in a subsequently fully cured matrix and
thus, lower the matrix's dielectric constant and includes
sacrificial polymers. Supercritical materials such as CO.sub.2 may
be used to remove porogen and decomposed porogen fragments.
Preferably, for a thermally decomposable porogen, the porogen
comprises a material having a decomposition temperature less than
the glass transition temperature (Tg) of a material combined with
it and greater than the curing temperature of the material combined
with it. Preferably, the present porogens have a degradation or
decomposition temperature of about 350.degree. C. or greater.
Preferably, the degraded or decomposed porogens volatilize at a
temperature greater than the cure temperature of the material with
which the porogen is combined and less than the Tg of the material.
Preferably, the degraded or decomposed porogens volatilize at a
temperature of about 96.degree. C. or greater.
[0132] The phrase "porogen bonds to the thermosetting component"
covers addition reactions, nucleophilic and electrophilic
substitutions or eliminations, radical reactions, etc. Further
alternative reactions may also include the formation of
non-covalent bonds, such as Van der Waals, electrostatic bonds,
ionic bonds, and hydrogen bonds.
[0133] Although International Patent Publication WO 00/31183
teaches that a porogen may be added to thermosettable
benzocyclobutene, polyarylene, or thermosettable perfluoroethylene
monomer to increase porosity thereof and thus, lower the dielectric
constant of that resin, the reference teaches that a porogen that
is known to function well with a first matrix system will not
necessarily function well with another matrix system.
[0134] The present porogens preferably comprise unsubstituted
polynorbornene, substituted polynorbornene, polycaprolactone,
unsubstituted polystyrene, substituted polystyrene,
polyacenaphthylene homopolymer, and polyacenaphthylene copolymer.
The more preferred porogen is substituted polynorbornene.
Preferably, the porogen has functional groups selected from the
group consisting of epoxy, hydroxy, carboxylic acid groups, amino,
and ethynyl. Preferably, the porogen has a functional group on at
least one of its ends.
[0135] Preferably, the porogen is bonded to the thermosetting
component through an ethynyl containing group. In one embodiment,
the ethynyl containing group is first reacted with the porogen as
shown in FIGS. 5, 7, 9, and 11. In a preferred embodiment, the
ethynyl containing group is first reacted with the thermosetting
component as shown in FIGS. 4, 6, 8, and 10. In FIGS. 4 though 11,
although only 1,3/4-bis[1',3',5'-tris(3"/4"-
-bromophenyl)adamant-7'-yl]benzene is shown, it is understood that
similar reaction occur for other useful thermosetting components
including 1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane and
1,3-bis{3'/4'-[1",3",5"-
-tris(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,7-bis{3"",4""-bromopheny-
l)adamantane. Useful ethynyl containing groups include fluorine;
amine; or hydroxy; and preferably, are acetylene; 4-ethynylaniline;
3-hydroxyphenylacetylene; 4-fluorophenylacetylene; and
1-ethylcyclohexylamine. Preferably, a covalent bond forms between
the porogen and the thermosetting component through the ethynyl
containing group.
[0136] Useful polyacenaphthylene homopolymers may have weight
average molecular weights ranging from preferably about 300 to
about 20,000; more preferably about 300 to about 10,000; and most
preferably about 300 to about 7,000.
[0137] The amount of thermosetting component used is about 50 to
about 90 weight percent while the amount of porogen used is about
10 to about 50 weight percent. Preferably, an adhesion promoter as
described above is added to the porogen bonded to the thermosetting
component. Based on a composition comprising the adhesion promoter
and the porogen bonded to the thermosetting component, about 0.1 to
about 15 weight percent of adhesion promoter is used and about 5 to
about 50 weight percent porogen bonded to the thermosetting
component is used.
[0138] Pore Generation:
[0139] The term "degrade" as used herein refers to the breaking of
covalent bonds. Such breaking of bonds may occur in numerous ways
including heterolytic and homolytic breakage. The breaking of bonds
need not be complete, i.e., not all breakable bonds must be
cleaved. Furthermore, the breaking of bonds may occur in some bonds
faster than in others. Ester bonds, for example, are generally less
stable than amide bonds, and therefore, are cleaved at a faster
rate. Breakage of bonds may also result in the release of fragments
differing from one another, depending on the chemical composition
of the degraded portion.
[0140] In the pore generation process, for thermally degradable
porogens, thermal energy is applied to the porogen bonded to the
thermosetting component to substantially degrade or decompose the
porogen into its starting components or monomers. As used herein,
"substantially degrade" preferably means at least 80 weight percent
of the porogen degrades or decomposes. For the preferred
thermosetting components of Formulae I and II above, the Tg is from
about 400.degree. C. to about 450.degree. C. so the present
porogens which have a degradation or decomposition temperature of
about 350.degree. C. or greater are particularly useful with this
thermosetting component.
[0141] Thermal energy is also applied to volatilize the
substantially degraded or decomposed porogen out of the
thermosetting component matrix. Preferably, the same thermal energy
is used for both the degradation and volatilization steps. As the
amount of volatilized degraded porogen increases, the resulting
porosity of the thermosetting component increases. For the
preferred thermosetting components of Formulae I and II above, the
Tg is from about 400.degree. C. to about 450.degree. C. so the
present substantially degraded porogens which have a volatilization
temperature of about 96.degree. C. or greater are particularly
useful with said thermosetting component.
[0142] Preferably, the cure temperature used for cross-linking the
thermosetting component will also substantially degrade the porogen
and volatilize it out of the thermosetting matrix. Typical cure
temperature and conditions will be described in the Utility section
below.
[0143] The resulting pores may be uniformly or randomly dispersed
throughout the matrix. Preferably, the pores are uniformly
dispersed throughout the matrix.
[0144] Alternatively, other procedures or conditions which at least
partially remove the porogen without adversely affecting the
thermosetting component may be used. Preferably, the porogen is
substantially removed. Typical removal methods include, but are not
limited to, exposure to radiation, such as but not limited to,
electromagnetic radiation such as ultraviolet, x-ray, laser, or
infrared radiation; mechanical energy such as sonication or
physical pressure; or particle radiation such as gamma ray, alpha
particles, neutron beam, or electron beam.
[0145] Utility:
[0146] The term "layer" as used herein includes film and
coating.
[0147] The term "low dielectric constant polymer" as used herein
refers to an organic, organometallic, or inorganic polymer with a
dielectric constant of approximately 3.0, or lower. The low
dielectric material is typically manufactured in the form of a thin
layer having a thickness from 100 to 25,000 Angstroms but also may
be used as thick films, blocks, cylinders, spheres etc.
[0148] The present composition of thermosetting component, adhesion
promoter, and porogen is useful in lowering the dielectric constant
of a material. Preferably, the dielectric material has a dielectric
constant k of less than or equal to about 3.0 and more preferably,
from about 1.9 to 3.0. The dielectric material has a glass
transition temperature of preferably at least about 350.degree.
C.
[0149] Layers of the instant compositions of thermosetting
component, adhesion promoter, and porogen may be formed by solution
techniques such as spraying, rolling, dipping, spin coating, flow
coating, or casting, with spin coating being preferred for
microelectronics. Preferably, the present composition is dissolved
in a solvent. Suitable solvents for use in such solutions of the
present compositions include any suitable pure or mixture of
organic, organometallic, or inorganic molecules that are volatized
at a desired temperature. Suitable solvents include aprotic
solvents, for example, cyclic ketones such as cyclopentanone,
cyclohexanone, cycloheptanone, and cyclooctanone; cyclic amides
such as N-alkylpyrrolidinone wherein the alkyl has from about 1 to
4 carbon atoms; and N-cyclohexylpyrrolidinone and mixtures thereof.
A wide variety of other organic solvents may be used herein insofar
as they are able to aid dissolution of the adhesion promoter and at
the same time effectively control the viscosity of the resulting
solution as a coating solution. Various facilitating measures such
as stirring and/or heating may be used to aid in the dissolution.
Other suitable solvents include methyethylketone,
methylisobutylketone, dibutyl ether, cyclic dimethylpolysiloxanes,
butyrolactone, .gamma.-butyrolactone, 2-heptanone, ethyl
3-ethoxypropionate, polyethylene glycol [dilmethyl ether, propylene
glycol methyl ether acetate (PGMEA), and anisole, and hydrocarbon
solvents such as mesitylene, xylenes, benzene, and toluene.
Preferred solvent is cyclohexanone. Typically, layer thicknesses
are between 0.1 to about 15 microns. As a dielectric interlayer for
microelectronics, the layer thickness is generally less than 2
microns.
[0150] The present composition may be used in electrical devices
and more specifically, as an interlayer dielectric in an
interconnect associated with a single integrated circuit ("IC")
chip. An integrated circuit chip typically has on its surface a
plurality of layers of the present composition and multiple layers
of metal conductors. It may also include regions of the present
composition between discrete metal conductors or regions of
conductor in the same layer or level of an integrated circuit.
[0151] In application of the instant polymers to ICs, a solution of
the present composition is applied to a semiconductor wafer using
conventional wet coating processes such as, for example, spin
coating; other well known coating techniques such as spray coating,
flow coating, or dip coating may be employed in specific cases. As
an illustration, a cyclohexanone solution of the present
composition is spin-coated onto a substrate having electrically
conductive components fabricated therein and the coated substrate
is then subjected to thermal processing. An exemplary formulation
of the instant composition is prepared by dissolving the present
composition in cyclohexanone solvent under ambient conditions with
strict adherence to a clean-handling protocol to prevent trace
metal contamination in any conventional apparatus having a
non-metallic lining. The resulting solution comprises based on the
total solution weight, from preferably about 2 to about 30 weight
percent of thermosetting component, adhesion promoter, and porogen,
and about 70 to about 98 weight percent solvent and more preferably
about 5 to about 25 weight percent of thermosetting component,
adhesion promoter, and porogen, and about 75 to about 95 weight
percent solvent.
[0152] An illustration of the use of the present invention follows.
Application of the instant compositions to form a layer onto planar
or topographical surfaces or substrates may be carried out by using
any conventional apparatus, preferably a spin coater, because the
compositions used herein have a controlled viscosity suitable for
such a coater. Evaporation of the solvent by any suitable means,
such as simple air drying during spin coating, by exposure to an
ambient environment, or by heating on a hot plate up to 350.degree.
C., may be employed. The substrate may have on it at least one
layer of the present preferred composition of thermosetting
component, adhesion promoter, and porogen.
[0153] Substrates contemplated herein may comprise any desirable
substantially solid material. Particularly desirable substrate
layers comprise films, glass, ceramic, plastic, metal or coated
metal, or composite material. In preferred embodiments, the
substrate comprises a silicon or gallium arsenide die or wafer
surface, a packaging surface such as found in a copper, silver,
nickel or gold plated leadframe, a copper surface such as found in
a circuit board or package interconnect trace, a via-wall or
stiffener interface ("copper" includes considerations of bare
copper and its oxides), a polymer-based packaging or board
interface such as found in a polyimide-based flex package, lead or
other metal alloy solder ball surface, glass and polymers. Useful
substrates include silicon, silicon nitride, silicon oxide, silicon
oxycarbide, silicon dioxide, silicon carbide, silicon oxynitride,
titanium nitride, tantalum nitride, tungsten nitride, aluminum,
copper, tantalum, organosiloxanes, organo silicon glass, and
fluorinated silicon glass. In other embodiments, the substrate
comprises a material common in the packaging and circuit board
industries such as silicon, copper, glass, and polymers. The
present compositions may also be used as a dielectric substrate
material in microchips, multichip modules, laminated circuit
boards, or printed wiring boards. The circuit board made up of the
present composition will have mounted on its surface patterns for
various electrical conductor circuits. The circuit board may
include various reinforcements, such as woven non-conducting fibers
or glass cloth. Such circuit boards may be single sided, as well as
double sided.
[0154] Layers made from the present compositions possess a low
dielectric constant, high thermal stability, high mechanical
strength, and excellent adhesion to electronic substrate surfaces.
Because the adhesion promoter is molecularly dispersed, these
layers demonstrate excellent adhesion to all affixed surfaces
including underlying substrates and overlaid capping or masking
layers, such as SiO.sub.2 and Si.sub.3N.sub.4 capping layers. The
use of these layers eliminates the need for an additional process
step in the form of at least one primer coating application to
achieve adhesion of the film to a substrate and/or overlaid
surface.
[0155] After application of the present composition to an
electronic topographical substrate, the coated structure is
subjected to a bake and cure thermal process at increasing
temperatures ranging from about 50.degree. C. up to about
450.degree. C. to polymerize the coating. The curing temperature is
at least about 300.degree. C. because a lower temperature is
insufficient to complete the reaction herein. Generally, it is
preferred that curing is carried out at temperatures of from about
375.degree. C. to about 425.degree. C. Curing may be carried out in
a conventional curing chamber such as an electric furnace, hot
plate, and the like and is generally performed in an inert
(non-oxidizing) atmosphere (nitrogen) in the curing chamber. In
addition to furnace or hot plate curing, the present compositions
may also be cured by exposure to ultraviolet radiation, microwave
radiation, or electron beam radiation as taught by commonly
assigned patent publication PCT/US96/08678 and U.S. Pat. Nos.
6,042,994; 6,080,526; 6,177,143; and 6,235,353, which are
incorporated herein by reference in their entireties. Any non
oxidizing or reducing atmospheres (e.g., argon, helium, hydrogen,
and nitrogen processing gases) may be used in the practice of the
present invention, if they are effective to conduct curing of the
present adhesion promoter-modified thermosetting component to
achieve the low k dielectric layer herein.
[0156] While not to be construed as limiting, it is observed that
the processing used to prepare the present low dielectric constant
composition results in a homogeneous solution of thermosetting
component, adhesion promoter, and porogen. The preferred silane
adhesion promoter advantageously serves multiple functions in the
low dielectric constant composition. For example, the processing of
the present composition enables the preferred polycarbosilane
adhesion promoter to interact with both the porogen and the
unsaturated structures of thermosetting component. It is believed
that the silane portions of the preferred polycarbosilane interact
with the porogen and thermosetting component. It is speculated that
the polycarbosilane acts as a surfactant or emulsification agent to
uniformly disperse the porogen within the thermosetting component
in the low dielectric composition. This is critical to producing a
composition that gives a homogeneous film (or layer) with uniformly
dispersed pores of very small dimension. The silane portion of the
polycarbosilane also reacts with the substrate surfaces, thereby
creating a chemically bonded adherent interface for the dominant
thermosetting monomer precursor. It has been proposed that
silylene/silyl radicals being available throughout the composition
act as attachment sources to fasten and secure any interface
surface of contact by chemical bonding therewith. The interactions
between the various components and the reactions of the silane
portion may occur during formulation and treatment prior to layer
formation. As indicated, the dispersion of silane functionality
with the porogen and thermosetting component throughout the
composition accounts for the uniform porosity in the resulting
layers. The dispersion of the silane functionality also leads to
reactive radicals as well as the superb adhesion of the instant
layers to both underlying substrate surfaces as well as overlayered
surface structures such as cap or masking layers. Crucial to the
materials discovered herein are the findings that the preferred
Formula XXV polycarbosilane adhesion promoters have a hydrido
substituted silicon in the backbone structure of the
polycarbosilane. This feature of the polycarbosilane enables it to:
(1) mix uniformly with the porogen to form a homogeneous
composition, (2) be reactive with thermosetting component; (3)
uniformly blend and disperse the porogen within the thermosetting
component providing a uniform composition leading to uniform
distribution of small pores in the final porous layer, and (4)
generate a polycarbosilane-modified thermosetting composition and
porous layer that possesses improved adhesion performance.
[0157] As indicated earlier, the present adhesion promoter-modified
thermosetting component (a) coating may act as an interlayer and be
covered by other coatings, such as other dielectric (SiO.sub.2)
coatings, SiO.sub.2 modified ceramic oxide layers, silicon
containing coatings, silicon carbon containing coatings, silicon
nitrogen containing coatings, silicon-nitrogen-carbon containing
coatings, diamond like carbon coatings, titanium nitride coatings,
tantalum nitride coatings, tungsten nitride coatings, aluminum
coatings, copper coatings, tantalum coatings, organosiloxane
coatings, organo silicon glass coatings, and fluorinated silicon
glass coatings. Such multilayer coatings are taught in U.S. Pat.
No. 4,973,526, which is incorporated herein by reference. And, as
amply demonstrated, the present polycarbosilane-modified
thermosetting component (a) prepared in the instant process may be
readily formed as interlined dielectric layers between adjacent
conductor paths on fabricated electronic or semiconductor
substrates.
[0158] The present films may be used in dual damascene (such as
copper) processing and substractive metal (such as aluminum or
aluminum/tungsten) processing for integrated circuit manufacturing.
The present compositions may be used as an etch stop, hardmask, air
bridge, or passive coating for enveloping a completed wafer. The
present composition may be used in a desirable all spin-on stacked
film as taught by Michael E. Thomas, "Spin-On Stacked Films for Low
k.sub.eff Dielectrics", Solid State Technology (July 2001),
incorporated herein in its entirety by reference. The present
layers may be used in stacks with other layers comprising
organosiloxanes such as taught by commonly assigned U.S. Pat. No.
6,143,855 and pending U.S. Ser. No. 10/078919 filed Feb. 19, 2002;
Honeywell International Inc.'s commercially available HOSP.RTM.
product; nanoporous silica such as taught by commonly assigned U.S.
Pat. No. 6,372,666; Honeywell International Inc.'s commercially
available NANOGLASS.RTM. E product; organosilsesquioxanes taught by
commonly assigned WO 01/29052; and fluorosilsesquioxanes taught by
commonly assigned WO 01/29141, incorporated herein in their
entirety.
[0159] Analytical Test Methods:
[0160] Proton NMR: A 2-5 mg sample of the material to be analyzed
was put into an NMR tube. About 0.7 ml deuterated chloroform was
added. The mixture was shaken by hand to dissolve the material. The
sample was then analyzed using a Varian 400 MHz NMR.
[0161] High Performance Liquid Chromatography (HPLC): A HPLC with a
Phenomenex luna Phenyl-Hexyl 250.times.4.6 mm 5 micron column was
used. The column temperature was set at 40.degree. C. Water and
acetonitrile were used to improve peak separation.
3 TIME WATER ACETONITRILE Initial 20% 80% 10 minutes 0% 100% 30
minutes 0% 100%
[0162] The following experimental conditions were used:
4 INJECTION VOLUME 10 microliters DETECTION UV at 200 nm STOP TIME
30 minutes POST TIME 5 minutes
[0163] The samples were prepared as follows.
[0164] For a mixture of the halogenated intermediate such as the
mixture of 1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane and
1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl]adamant-7'-yl]benzene of
Preparation 1 below, the reaction mixture (0.5-1 milliliter) was
shaken with approximately 4% HCl (several milliliters). The organic
layer was shaken with water. An organic layer sample (twenty
microliters) was taken and added to acetonitrile (one
milliliter).
[0165] For a mixture of the final product such as the mixture of
1,3,5,7-tetrakis[3'/4'-(phenylethynyl)phenyl]adamantane and
1,3/4-bis{1',3',5'-tris[3"/4"-(phenylethynyl)phenyl]adamant-7'-yl}benzene
of Preparation 1 below, the reaction mixture (0.5 gram) was mixed
with chloroform (five milliliters) and 3-5% HCl (5 milliliters) and
shaken. The organic layer was washed by water. An organic layer
sample (100 microliters) was added to tetrahydrofuran (0.9
milliliter).
[0166] Gel Permeation Chromatography (GPC 1): The GPC analysis was
done with Waters liquid chromatography system composed from Water
717 plus Autosampler, Waters in-line degasser, Waters 515 HPLC
pump, Waters 410 Differential Refractometer (RI detector), and two
columns: HP PI gel 5 .mu. MIXED D. The analysis conditions
were:
5 Mobile Phase Tetrahydrofuran (THF) Column flow (milliliters/min)
1.0 Column temperature (.degree. C.) 40.0 Detection Refractive
Index, Polarity positive Analysis run time 25 min Injection
quantity (.mu.L) 50
[0167] The solid product sample (10 milligrams) was prepared by
dissolving in tetrahydrofuran (one milliliter).
[0168] Gel Permeation Chromatography (GPC 2): This method may be
used to provide additional detail about the dimer and trimer peaks.
The following conditions are used:
6 Analysis Apparatus Shimadzu LC10 Separation Column Plgel 5
.mu.pre-column Plgel 5 .mu.1000 .ANG., 300 .times. 7.5 nm Plgel 5
.mu.500 .ANG., 300 .times. 7.5 nm Plgel 5 .mu.100 .ANG., 300
.times. 7.5 nm Mobile Phase Eluent A: toluene Column Flow
(milliliters/minute) 1.0 Column Temperature (.degree. C.) 40
Detection Refractive Index, Polarity Positive Analysis Run Time
(minutes) 32 Trial Solution 10 milligrams/milliliter toluene
Injection Quantity (.mu.) 50
[0169] To calculate the contents, in other words area-%, the peak
area belonging to the monomer or the peak area belonging to the
oligomer or polymer is related to the total of all the peak areas
in the chromatogram.
[0170] Gel Permeation Chromatography (GPC 3): Separation was
performed with a Waters 2690 separation module with Waters 996
diode array and Waters 410 differential refractometer detectors.
The separation was performed on two PLgel 3 .mu.m Mixed-E
300.times.7.5 mm columns with chloroform flowing at 1 ml/min.
Injection volumes of 25 .mu.l of solutions of about 1 mg/ml
concentration were run in duplicate. Good reproducibility was
observed.
[0171] The column was calibrated with relatively monodisperse
polystyrene standards between 20,000 and 500 molecular weight. With
the lower molecular weight standards nine distinct components could
be resolved corresponding to butyl terminated styrene monomer
through oligomers with nine styrenes. The logs of the peak
molecular weight of the standards were fit with a third order
polynomial of the elution time. The instrumental broadening was
evaluated from the ratio of the full width at half maximum to the
mean elution time of toluene.
[0172] The absorbance for Preparations 1 and 2 below was a maximum
at about 284 nm. The chromatograms had similar shapes at absorbance
at wavelengths below about 300 nm. The results presented here
correspond to 254 nm absorbance. The peaks were identified by the
molecular weight of the polystyrene that would be eluting at the
same time. These values should not be considered as measurements of
molecular weight of the Preparation 1 and 2 oligomers. The
sequential elution of higher oligomers, trimers, dimers, oligomers,
and incomplete oligomers at increasing times can be
quantitated.
[0173] Each component was broader than that which would be observed
for a monodisperse species. This width was analyzed from the full
width in minutes at half maximum of the peak. To roughly account
for the instrumental broadening, we calculated
width.sub.corrected=[width.sub.observed.sup.2-width.sub.instrument.sup.2].-
sup.1/2
[0174] where width.sub.instrument is the observed width of toluene
corrected by the ratio of the elution times of the peak to that for
toluene. The peak width was converted to a molecular weight width
through the calibration curve and ratioed to the peak molecular
width. Since the molecular weight of styrene oligomers was
proportional to the square of their size, the relative molecular
weight width can be converted to a relative oligomer size width by
dividing by 2. This procedure accounted for the difference in
molecular configuration of the two species.
[0175] Liquid Chromatography-Mass Spectroscopy (LC-MS): This
analysis was performed on a Finnigan/MAT TSQ7000 triple stage
quadrupole mass spectrometer system, with an Atmospheric Pressure
Ionization (API) interface unit, using a Hewlett-Packard Series
1050 HPLC system as the chromatographic inlet. Both mass spectral
ion current and variable single wavelength UV data were acquired
for time-intensity chromatograms.
[0176] Chromatography was conducted on a Phenomenex Luna 5-micron
pheny-hexyl column (250.times.4.6 mm). Sample auto-injections were
generally between 5 and 20 microliters of concentrated solutions,
both in tetrahydrofuran and without tetrahydrofuran. The preferred
preparation of concentrated sample solutions for analysis was
dissolution in tetrahydrofuran, of about 5 milligrams solid product
per milliliter, for 10 microliter injections. The mobile phase flow
through the column was 1.0 milliliter/minute of acetonitrile/water,
initially 70/30 for 1 minute then gradient programmed to 100%
acetonitrile at 10 minutes and held until 40 minutes.
[0177] Atmospheric Pressure Chemical Ionization (APCI) mass spectra
were recorded in both positive and negative ionization, in separate
experiments. Positive APCI was more informative of molecular
structure for these final products, providing protonated
pseudomolecular ions including adducts with acetonitrile matrix.
The APCI corona discharge was 5 microamps, about 5 kV for positive
ionization, and about 4 kV for negative ionization. The heated
capillary line was maintained at 200.degree. C. and the vaporizer
cell at 400.degree. C. The ion detection system after quadrupole
mass analysis was set at 15 kV conversion dynode and 1500V electron
multiplier voltage. Mass spectra were typically recorded at 1.0
second/scan from about m/z 50 to 2000 a.m.u. for negative
ionization, and from about m/z 150 a.m.u. up for positive
ionization. In separate positive ion experiments, the mass range
was scanned up both to 2000 a.m.u. in low mass tune/calibration
mode and to 4000 a.m.u. in high mass tune/calibration mode.
[0178] Differential Scanning Calorimetry (DSC): DSC measurements
were performed using a TA Instruments 2920 Differential Scanning
Calorimeter in conjunction with a controller and associated
software. A standard DSC cell with temperature ranges from
250.degree. C. to 725.degree. C. (inert atmosphere: 50 ml/min of
nitrogen) was used for the analysis. Liquid nitrogen was used as a
cooling gas source. A small amount of sample (10-12 mg) was
carefully weighed into an Auto DSC aluminum sample pan (Part #
990999-901) using a Mettler Toledo Analytical balance with an
accuracy of .+-.0.0001 grams. Sample was encapsulated by covering
the pan with the lid that was previously punctured in the center to
allow for outgasing. Sample was heated under nitrogen from
0.degree. C. to 450.degree. C. at a rate of 100.degree. C./minute
(cycle 1), then cooled to 0.degree. C. at a rate of 100.degree.
C./minute. A second cycle was run immediately from 0.degree. C. to
450.degree. C. at a rate of 100.degree. C./minute (repeat of cycle
1). The cross-linking temperature was determined from the first
cycle.
[0179] FTIR analysis: FTIR spectra were taken using a Nicolet Magna
550 FTIR spectrometer in transmission mode. Substrate background
spectra were taken on uncoated substrates. Film spectra were taken
using the substrate as background. Film spectra were then analyzed
for change in peak location and intensity.
[0180] Dielectric Constant: The dielectric constant was determined
by coating a thin film of aluminum on the cured layer and then
doing a capacitance-voltage measurement at 1 MHz and calculating
the k value based on the layer thickness.
[0181] Glass Transition Temperature (Tg): The glass transition
temperature of a thin film was determined by measuring the thin
film stress as a function of temperature. The thin film stress
measurement was performed on a KLA 3220 Flexus. Before the film
measurement, the uncoated wafer was annealed at 500.degree. C. for
60 minutes to avoid any errors due to stress relaxation in the
wafer itself. The wafer was then deposited with the material to be
tested and processed through all required process steps. The wafer
was then placed in the stress gauge, which measured the wafer bow
as function of temperature. The instrument calculated the stress
versus temperature graph, provided that the wafer thickness and the
film thickness were known. The result was displayed in graphic
form. To determine the Tg value, a horizontal tangent line was
drawn (a slope value of zero on the stress vs. temperature graph).
Tg value was where the graph and the horizontal tangent line
intersect.
[0182] It should be reported if the Tg was determined after the
first temperature cycle or a subsequent cycle where the maximum
temperature was used because the measurement process itself may
influence Tg.
[0183] Isothermal Gravimetric Analysis (ITGA) Weight Loss: Total
weight loss was determined on the TA Instruments 2950
Thermogravimetric Analyzer (TGA) used in conjunction with a TA
Instruments thermal analysis controller and associated software. A
Platinel II Thermocouple and a Standard Furnace with a temperature
range of 25.degree. C. to 1000.degree. C. and heating rate of
0.1.degree. C. to 100.degree. C./min were used. A small amount of
sample (7 to 12 mg) was weighed on the TGA's balance (resolution:
0.1 g; accuracy: to .+-.0.1%)and heated on a platinum pan. Samples
were heated under nitrogen with a purge rate of 100 ml/min (60
ml/min going to the furnace and 40 ml/min to the balance). Sample
was equilibrated under nitrogen at 20.degree. C. for 20 minutes,
then temperature was raised to 200.degree. C. at a rate of
10.degree. C./minute and held at 200.degree. C. for 10 minutes.
Temperature was then ramped to 425.degree. C. at a rate of
10.degree. C./minute and held at 425.degree. C. for 4 hours. The
weight loss at 425.degree. C. for the 4 hour period was
calculated.
[0184] Shrinkage: Film shrinkage was measured by determining the
film thickness before and after the process. Shrinkage was
expressed in percent of the original film thickness. Shrinkage was
positive if the film thickness decreased. The actual thickness
measurements were performed optically using a J. A. Woollam M-88
spectroscopic ellipsometer. A Cauchy model was used to calculate
the best fit for Psi and Delta (details on Ellipsometry can be
found in e.g. "Spectroscopic Ellipsometry and Reflectometry" by H.
G. Thompkins and William A. McGahan, John Wiley and Sons, Inc.,
1999).
[0185] Refractive Index: The refractive index measurements were
performed together with the thickness measurements using a J. A.
Woollam M-88 spectroscopic ellipsometer. A Cauchy model was used to
calculate the best fit for Psi and Delta. Unless noted otherwise,
the refractive index was reported at a wavelenth of 633 nm (details
on Ellipsometry can be found in e.g. "Spectroscopic Ellipsometry
and Reflectometry" by H. G. Thompkins and William A. McGahan, John
Wiley and Sons, Inc., 1999).
[0186] Modulus and Hardness: Modulus and hardness were measured
using instrumented indentation testing. The measurements were
performed using a MTS Nanoindenter XP (MTS Systems Corp., Oak
Ridge, Tenn.). Specifically, the continuous stiffness measurement
method was used, which enabled the accurate and continuous
determination of modulus and hardness rather than measurement of a
discrete value from the unloading curves. The system was calibrated
using fused silica with a nominal modulus of 72+-3.5 GPa. The
modulus for fused silica was obtained from average value between
500 to 1000 nm indentation depth. For the thin films, the modulus
and hardness values were obtained from the minimum of the modulus
versus depth curve, which is typically between 5 to 15% of the film
thickness.
[0187] Tape Test: The tape test was performed following the
guidelines given in ASTM D3359-95. A grid was scribed into the
dielectric layer according to the following. A tape test was
performed across the grid marking in the following manner: (1) a
piece of adhesive tape, preferably Scotch brand #3
m600-1/2.times.1296, was placed on the present layer, and pressed
down firmly to make good contact; and (2) the tape was then pulled
off rapidly and evenly at an angle of 180.degree. to the layer
surface. The sample was considered to pass if the layer remained
intact on the wafer, or to have failed if part or all of the film
pulled up with the tape.
[0188] Stud Pull Test: Epoxy-coated studs were attached to the
surface of a wafer containing the layers of the present invention.
A ceramic backing plate was applied to the back side of the wafer
to prevent substrate bending and undue stress concentration at the
edges of the stud. The studs were then pulled in a direction normal
to the wafer surface by a testing apparatus employing standard pull
protocol steps. The stress applied at the point of failure and the
interface location were then recorded.
[0189] Compatibility with Solvents: Compatibility with solvents was
determined by measuring film thickness, refractive index, FTIR
spectra, and dielectric constant before and after solvent
treatment. For a compatible solvent, no significant change should
be observed.
[0190] Average Pore Size Diameter: The N.sub.2 isotherms of porous
samples was measured on a Micromeretics ASAP 2000 automatic
isothermal N.sub.2 sorption instrument using UHP (ultra high purity
industrial gas) N.sub.2, with the sample immersed in a sample tube
in a liquid N.sub.2 bath at 77.degree. K.
[0191] For sample preparation, the material was first deposited on
silicon wafers using standard processing conditions. For each
sample, three wafers were prepared with a film thickness of
approximately 6000 Angstroms. The films were then removed from the
wafers by scraping with a razor blade to generate powder samples.
These powder samples were pre-dried at 180.degree. C. in an oven
before weighing them, carefully pouring the powder into a 10 mm
inner diameter sample tube, then degassing at 180.degree. C. at
0.01 Torr for >3 hours.
[0192] The adsorption and desorption N.sub.2 sorption was then
measured automatically using a 5 second equilibration interval,
unless analysis showed that a longer time was required. The time
required to measure the isotherm was proportional to the mass of
the sample, the pore volume of the sample, the number of data
points measured, the equilibration interval, and the P/Po
tolerance. (P is actual pressure of the sample in the sample tube.
Po is the ambient pressure outside the instrument.) The instrument
measures the N.sub.2 isotherm and plots N.sub.2 versus P/Po.
[0193] The apparent BET (Brunauer, Emmett, Teller method for
multi-layer gas absorption on a solid surface disclosed in S.
Brunauer, P. H. Emmett, E. Teller; J. Am. Chem. Soc., 60, 309-319
(1938)) surface area was calculated from the lower P/Po region of
the N2 adsorption isotherm using the BET theory, using the linear
section of the BET equation that gives an R.sup.2 fit
>0.9999.
[0194] The pore volume was calculated from the volume of N.sub.2
adsorbed at the relative pressure P/Po value, usually P/Po
.about.0.95, which is in the flat region of the isotherm where
condensation is complete, assuming that the density of the adsorbed
N.sub.2 is the same as liquid N.sub.2 and that all the pores are
filled with condensed N.sub.2 at this P/Po.
[0195] The pore size distribution was calculated from the
adsorption arm of the N.sub.2 isotherm using the BJH (E. P. Barret,
L. G. Joyner, P. P. Halenda; J. Am. Chem. Soc., 73, 373-380 (1951))
pore size distribution from the N2 isotherm using the Kelvin
equation) theory. This uses the Kelvin equation, which relates
curvature to suppression of vapor pressure, and the Halsey
equation, which describes the thickness of the adsorbed N.sub.2
monolayer versus P/Po, to convert the volume of condensed N.sub.2
versus P/Po to the pore volume in a particular range of pore
sizes.
[0196] The average cylindrical pore diameter D was the diameter of
a cylinder that has the same apparent BET surface area Sa
(m.sup.2/g) and pore volume Vp (cc/g) as the sample, so D(nm)=4000
Vp/Sa.
[0197] Thermal Desorption Mass Spectroscopy: Thermal Desorption
Mass Spectroscopy (TDMS) is used to measure the thermal stability
of a material by analyzing the desorbing species while the material
is subjected to a thermal treatment.
[0198] The TDMS measurement was performed in a high vacuum system
equipped with a wafer heater and a mass spectrometer, which was
located close to the front surface of the wafer. The wafer was
heated using heating lamps, which heat the wafer from the backside.
The wafer temperature was measured by a thermocouple, which was in
contact with the front surface of the wafer. Heater lamps and
thermocouple were connected to a programmable temperature
controller, which allowed several temperature ramp and soak cycles.
The mass spectrometer was a Hiden Analytical HAL IV RC RGA 301.
Both mass spectrometer and the temperature controller were
connected to a computer, which read and recorded the mass
spectrometer and the temperature signal versus time.
[0199] To perform TDMS analysis, the material was first deposited
as a thin film onto an 8 inch wafer using standard processing
methods. The wafer was then placed in the TDMS vacuum system and
the system was pumped down to a pressure below 1e-7 torr. The
temperature ramp was then starting using the temperature
controller. The temperature and the mass spectrometer signal were
recorded using the computer. For a typical measurement with a ramp
rate of about 10 degree C. per minute, one complete mass scan and
one temperature measurement are recorded every 20 seconds. The mass
spectrum at a given time and temperature at a given time can be
analyzed after the measurement is competed.
EXAMPLES
Comparative A
[0200] We measured the dielectric constant of a composition similar
to Example 5 of our International Patent Publication WO 01/78110
and the dielectric constant was 2.7.
Preparations
[0201] Preparation 1--Preparation of Thermosetting Component
(referred to herein as "P1")
[0202] Step (a): Preparation of Mixture of
1,3,5,7-tetrakis(3'/4'-bromophe- nyl)adamantane (shown in FIG. 1A);
1,3/4-bis[1',3',5'-tris(3"/4"-bromophen- yl)adamant-7'-yl]benzene
(shown in FIG. 1C); and at least
1,3-bis{3'/4'-[1",3",5"-tris(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,-
7-bis(3""/4""-bromophenyl)adamantane (shown in FIG. 1C)
(collectively "P1 Step (a) Product")
[0203] A first reaction vessel was loaded with adamantane (200
grams), bromobenzene (1550 milliliters), and aluminum trichloride
(50 grams). The reaction mixture was heated to 40.degree. C. by a
thermostatted water bath. Tert-butyl bromide (1206 grams) was added
slowly over a period of 4-6 hours to the reaction mixture. The
reaction mixture at 40.degree. C. was stirred overnight.
[0204] A second reaction vessel was loaded with 1000 milliliters of
aqueous hydrogen chloride (5% w/w). The contents of the first
reaction vessel were gradually discharged into the second reaction
vessel while maintaining the reaction mixture at 25-35.degree. C.
by an external ice bath. An organic phase (dark brown lower phase)
was separated and washed with water (1000 milliliters). About 1700
milliliters of the organic phase remained.
[0205] A third reaction vessel was loaded with 20.4 liters of
petroleum ether (mainly isooctane with a boiling range of
80.degree. C.-110.degree. C.). The contents of the second reaction
vessel were slowly added over a period of one hour to the third
reaction vessel. The resulting mixture was stirred for at least one
hour. The precipitate was filtered off and the filter cake was
washed twice with 300 milliliters per wash of the aforementioned
petroleum ether. The washed filter cake was dried overnight at
45.degree. C. at 40 mbar. The P1 Step (a) Product yield was 407
grams dry weight. This reaction is shown in FIGS. 1A through 1C as
follows. FIG. 1A shows the resulting monomer. FIG. 1B shows the
resulting generic dimer and higher products while FIG. 1C shows the
resulting specific dimer and trimer covered by the FIG. 1B
structure.
[0206] Analytical techniques including GPC, HPLC, and NMR were used
to identify the product. GPC analysis showed:
1,3,5,7-tetrakis(3'/4'-bromoph- enyl)adamantane (shown in FIG. 1A)
had a peak molecular weight of 430;
1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl)adamant-7'-yl]benzene
(shown in FIG. 1C) had a peak molecular weight of 820;
1,3-bis{3'/4'-[1",3",5"-tris-
(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,7-bis(3""/4""-bromophenyl)ada-
mantane (shown in FIG. 1C) had a peak molecular weight of about
1150 (shoulder).
[0207] Step (b): Preparation of Mixture of
1,3,5,7-tetrakis[3',4'-(phenyle- thynyl)phenyl]adamantane (shown in
FIG. 1D); 1,3/4-bis{1',3',5'-tris[3"/4"-
-(phenylethynyl)phenyl]adamant-7'-yl}benzene (shown in FIG. 1F);
and at least
1,3-bis{3'/4'-[1",3",5"-tris[3'"/4'"-(phenylethynyl)phenyl]adamant--
7"-yl]phenyl}-5,7-bis[3""/4""-(phenylethynyl)phenyl]adamantane
(shown in FIG. 1F) (collectively "P1 Step (b) Product")
[0208] A first reactor under nitrogen was loaded with toluene (1500
milliliters), triethylamine (4000 milliliters), and the P1 Step (a)
Product prepared above (1000 grams dry). The mixture was heated to
80.degree. C. and bis-(triphenyl-phosphine)palladium(II)dichloride
(i.e., [Ph.sub.3P].sub.2PdCl.sub.2) (7.5 grams) and
tri-phenylphosphine (i.e. [Ph.sub.3P]) (15 grams) were added. After
ten minutes, copper(I)iodide (7.5 grams) was added.
[0209] Over a period of three hours, a solution of phenylacetylene
(750 grams) was added to the first reactor. The reaction mixture at
80.degree. C. was stirred for 12 hours to ensure that the reaction
was complete. Toluene (4750 milliliters) was added. The solvent was
then distilled off under reduced pressure and a maximum sump
temperature and the reaction mixture was cooled down to about
50.degree. C. The triethylammonium bromide (about 1600 milliliters)
was filtered off. The filter cake was washed three times with 500
milliliters per wash of toluene. The organic phase was washed with
1750 milliliters of HCl (10 w/w %) and then washed with water (2000
milliliters).
[0210] To the washed organic phase, water (1000 milliliters),
ethylene diamine tetraacetic acid (EDTA) (100 grams), and
dimethylglyoxime (20 grams) were added. About 150 milliliters of
NH.sub.4OH (25 w/w %) were added to achieve a pH of 9. The reaction
mixture was stirred for one hour. The organic phase was separated
and washed with water (1000 milliliters). With a Dean-Stark trap,
azeotropic drying occurred until water evolution ceased. Filtering
agent dolomite (100 grams) (tradename Tonsil) was added. The
mixture was heated to 100.degree. C. for 30 minutes. Dolomite was
filtered off with a cloth filter having fine pores and the
remainder was washed with toluene (200 milliliters). Silica (100
grams) was added. The reaction mixture was stirred for 30 minutes.
The silica was filtered off with a cloth filter having fine pores
and the remainder was washed with toluene (200 milliliters).
Aqueous NH.sub.3 (20 w/w %), in an amount of 2500 milliliters, and
12.5 g of N-acetylcysteine were added. The phases were separated.
The organic phase was washed with 1000 milliliters of HCl (10% w/w)
and then washed two times with 1000 milliliters per wash of water.
The toluene was distilled off under a reduced pressure of about 120
mbar. The pot temperature did not exceed about 70.degree. C. A dark
brown viscous oil (1500-1700 milliliters) remained. To the hot mass
in the pot, iso-butyl acetate (2500 milliliters) was added and a
dark brown solution formed (4250 milliliters).
[0211] A second reactor was loaded with 17000 milliliters of
petroleum ether (mainly isooctane with a boiling range of
80.degree. C.-110.degree. C.). The contents of the first reactor
were added over a period of one hour to the second reactor and
stirred overnight. The precipitate was filtered and washed four
times with 500 milliliters per wash of the aforedescribed petroleum
ether. The product was dried under reduced pressure for four hours
at 45.degree. C. and five hours at 80.degree. C. The P1 Step (B)
Product yield was 850-900 grams. This reaction is shown in FIGS. 1D
through 1F as follows. FIG. 1D shows the resulting monomer. FIG. 1E
shows the resulting generic dimer and higher products while FIG. 1F
shows the resulting specific dimer and trimer covered by the FIG.
1F structure.
[0212] Analytical techniques including GPC, HPLC, NMR, and FTIR
were used to identify the product. GPC analysis showed:
1,3,5,7-tetrakis[3',4'-(phe- nylethynyl)phenyl]adamantane (shown in
FIG. 1D) had a peak molecular weight of about 900;
1,3/4-bis{1',3',5'-tris[3"/4"-(phenylethynyl)phenyl]-
adamant-7'-yl}benzene (shown in FIG. 1F) had a peak molecular
weight of about 1500;
1,3-bis{3'/4'-[1",3",5"-tris[3'"/4'"(phenylethynyl)phenyl]ada-
mant-7"-yl]phenyl}-5,7-bis[3""/4""-(phenylethynyl)phenyl]adamantane
(shown in FIG. 1F) had a peak molecular weight of about 2100
(shoulder).
[0213] The melting point was 164-167.degree. C. From NMR, a
multiplet occurred at 6,9-8 ppm 2,8+-0,2 H (aromatic part) and
1,7-2,7 ppm 1H+-0,2H (cage portion). From GPC, the ratio of the
monomeric and small molecules to oligomeric compounds was 50.+-.5%.
FTIR showed the following:
7 PEAKS IN CENTIMETERS.sup.-1 (PEAK INTENSITY) STRUCTURE 3050
(weak) Aromatic C--H 2930 (weak) Aliphatic C--H on adamantane 2200
(very weak) Acetylene 1600 (very strong) Aromatic C.dbd.C 1500
(strong) 1450 (medium) 1350 (medium) LC-MS study showed the
presence of peaks: of main monomeric product m/z 840, of its
derivatives, m/z 640, 740, 940; 706, 606, 806; 762, 662, 862; 938,
838, 1038 of dimeric products, m/z 1402, 1302, 1502; 1326, 1226,
1426.
[0214] The GPC 3 results follow.
8 Amount Peak Molecular Weight (Weight %) (Relative to PS) Inc Hi
Inc .DELTA.R/R Mnmr Mnmr Dmr Trmr Olgmr Mnmr Mnmr Dmr Trmr Mnmr
w/mnmr 49.3 30.9 10.1 9.7 744 1304 1676 0.10
Preparation 2--Preparation of Thermosetting Component (Referred to
Herein as "P2")
[0215] Step (a): Preparation of Mixture of
1,3,5,7-tetrakis(3'/4'-bromophe- nyl)adamantane (shown in FIG. 1A);
1,3/4-bis[1',3',5'-tris(3"/4"-bromophen- yl)adamant-7'-yl] benzene
(shown in FIG. 1C); and at least
1,3-bis{3'/4'-[1",3",5"-tris(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,-
7-bis(3""/4""-bromophenyl)adamantane(shown in FIG. 1C)(collectively
"P2 Step (a) Product")
[0216] A first reaction vessel was loaded with 1,4-dibromobenzene
(587.4 grams) and aluminum trichloride (27.7 grams). This reaction
mixture was heated to 90.degree. C. by a thermostatted water bath
and maintained at this temperature for one hour without stirring
and for an additional one hour with stirring. The reaction mixture
was cooled down to 50.degree. C. Adamantane (113.1 grams) was added
to the cooled reaction mixture. Over a period of four hours,
t-butyl-bromobenzene (796.3 grams) was added to the reaction
mixture. The reaction mixture was stirred for an additional 12
hours.
[0217] A second reaction vessel was loaded with HCl (566
milliliters, 10% aqueous w/w). The contents of the first reaction
vessel at 50.degree. C. were discharged into the second reaction
vessel while maintaining the mixture at 25-35.degree. C. by an
external ice bath. The reaction mass was a light brown suspension.
The organic phase was a dark brown lower phase and separated from
the reaction mixture. The separated organic phase was washed with
water (380 milliliters). After this washing, about 800 milliliters
of organic phase remained.
[0218] A third reaction vessel was loaded with heptane (5600
milliliters). Slowly over a period of one hour, the contents of the
second reaction vessel were added to the third reaction vessel. The
suspension was stirred for at least four hours and the precipitate
was filtered off. The filter cake was washed twice with 300
milliliters per wash of heptane. The P2 Step (a) Product yield was
526.9 grams (wet) and 470.1 grams (dry).
[0219] Analytical techniques including GPC, HPLC, and NMR were used
to identify the product. GPC analysis showed:
1,3,5,7-tetrakis(3'/4'-bromoph- enyl)adamantane (shown in FIG. 1A)
had a peak molecular weight of about 430;
1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl)adamant-7'-yl] benzene
(shown in FIG. 1C) had a peak molecular weight of about 820;
1,3-bis{3'/4'-[1",3",5"-tris(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,-
7-bis(3""/4""-bromophenyl)adamantane (shown in FIG. 1C) had a peak
molecular weight of about 1150 (shoulder).
[0220] Step (b): Preparation of Mixture of
1,3,5,7-tetrakis[3',4'-(phenyle- thynyl)phenyl]adamantane (shown in
FIG. 1D); 1,3/4-bis{1',3',5'-tris[3"/4"-
-(phenylethynyl)phenyl]adamant-7'-yl}benzene (shown in FIG. 1F);
and at least
1,3-bis{3'/4'-[1",3",5"-tris[3'"/4'"-(phenylethynyl)phenyl]adamant--
7"-yl]phenyl}-5,7-bis[3""/4""-(phenylethynyl)phenyl]adamantane
(shown in FIG. 1F)(collectively "P2 Step (b) Product")
[0221] A first reaction pot under nitrogen was loaded with toluene
(698 milliliters), triethylamine (1860 milliliters), and the P2
Step (a) Product prepared above (465 grams dry). The mixture was
heated to 80.degree. C. Palladium-triphenylphosphine complex (i.e.
[Ph(PPh.sub.3).sub.2Cl.sub.2)(4.2 grams) was added to the reaction
mixture. After waiting ten minutes, triphenylphosphine (i.e.,
PPh.sub.3)(8.4 grams) was added to the reaction mixture. After
waiting another ten minutes, copper(I)-iodide (4.2 grams) was added
to the reaction mixture.
[0222] Over a period of three hours, a solution of phenylacetylene
(348.8 grams) was added to the reaction mixture. The reaction
mixture at 80.degree. C. was stirred for 12 hours to ensure that
the reaction was complete. Toluene (2209 milliliters) was added to
the reaction mixture and then distilled off under reduced pressure
and a maximum sump temperature. The reaction mixture was cooled
down to about 50.degree. C. and the triethylammonium bromide was
filtered off. The filter cake was washed twice with 250 milliliters
per wash of toluene. The organic phase was washed with HCl (10 w/w
%)(500 milliliters) and water (500 milliliters).
[0223] To the organic phase, water (500 milliliters), EDTA (18.6
grams), and dimethylglyoxime (3.7 grams) were added. NH.sub.4OH (25
w/w %)(about 93 milliliters) was added to keep the pH=9. The
reaction mixture was stirred for one hour. The organic phase was
separated from the insoluble material and the emulsion containing
the palladium-complex. The separated organic phase was washed with
water (500 milliliters). With a Dean-Stark trap, azeotropic drying
of the washed organic phase occurred until water evolution ceased.
Filtering agent dolomite (tradename Tonsil)(50 grams) was added and
the reaction mixture was heated to 100.degree. C. for 30 minutes.
The dolomite was filtered off with a cloth filter having fine pores
and the organic material was washed with toluene (200 milliliters).
Silica (50 grams) was added and the reaction mixture was stirred
for 30 minutes. The silica was filtered off with a cloth filter
having fine pores and the organic material was washed with toluene
(200 milliliters). Aqueous NH.sub.3 (20% w/w)(250 milliliters) and
N-acetylcysteine (12.5 grams) were added. The phases were
separated. The organic phase was washed with HCl(10% w/w)(500
milliliters). The organic material was washed twice with 500
milliliters per wash of water. The toluene was distilled off under
reduced pressure of about 120 mbar. The pot temperature did not
exceed 70.degree. C. A dark brown viscous oil (about 500-700
milliliters) remained. To the hot mass in the pot, iso-butyl
acetate (1162 milliliters) was added. A dark brown solution (about
1780 milliliters) formed.
[0224] A second reaction pot was loaded with heptane (7120
milliliters). Over a period of one hour, the contents of the first
reaction pot were added to the second reaction pot. The precipitate
was stirred for at least three hours and filtered off. The product
was washed four times with 250 milliliters per wash of heptane. The
product was dried under reduced pressure of 40 mbar at 80.degree.
C. The P2 Step (b) Product yield was 700 grams wet or 419 grams
dry.
[0225] Analytical techniques including GPC, HPLC, and NMR were used
to identify the product. GPC analysis showed:
1,3,5,7-tetrakis[3',4'-(phenyl- ethynyl)phenyl]adamantane (shown in
FIG. 1D) had a peak molecular weight of about 900;
1,3/4-bis{1',3',5'-tris[3"/4"-(phenylethynyl)phenyl]adamant-
-7'-yl}benzene (shown in FIG. 1F) had a peak molecular weight of
about 1500;
1,3-bis{3'/4'-[1",3",5"-tris[3'"/4'"-(phenylethynyl)phenyl]adamant--
7"-yl]phenyl}-5,7-bis[3""/4""-(phenylethynyl)phenyl]adamantane
(shown in FIG. 1F) had a peak molecular weight of about 2100
(shoulder).
[0226] The melting point was 164-167.degree. C. From NMR, a
multiplet occurred at 6,9-8 ppm 2,8+-0,2H (aromatic part) and
1,7-2,7 ppm 1H+-0,2H (cage portion). From GPC, the ratio of the
monomeric and small molecules to oligomeric compounds was 50.+-.5%.
FTIR showed the following:
9 PEAKS IN CENTIMETERS.sup.-1 (PEAK INTENSITY) STRUCTURE 3050
(weak) Aromatic C--H 2930 (weak) Aliphatic C--H on adamantane 2200
(very weak) Acetylene 1600 (very strong) Aromatic C.dbd.C 1500
(strong) 1450 (medium) 1350 (medium) LC-MS study showed the
presence of peaks: of main monomeric product m/z 840, of its
derivatives, m/z 640, 740, 940; 706, 606, 806; 762, 662, 862; 938,
838, 1038 of dimeric products, m/z 1402, 1302, 1502; 1326, 1226,
1426.
[0227] GPC 3 results follow.
10 Amount Peak Molecular Weight (Weight %) (Relative to PS) Inc Hi
Inc .DELTA.R/R Mnmr Mnmr Dmr Trmr Olgmr Mnmr Mnmr Dmr Trmr Mnmr 7.7
36.4 26.8 12.3 16.8 546 763 1328 1672 0.14
[0228] Preparation 3
[0229] Impact of Solvent on ratio of
1,3,5,7-tetrakis[3',4'-(phenylethynyl- )phenyl]adamantane (shown in
FIG. 1D) to 1,3/4-bis{1',3',5'-tris[3"/4"-phe-
nylethynyl)phenyl]adamant-7'-yl}benzene (shown in FIG. 1F) and at
least
1,3-bis{3'/4'-[1",3",5"-tris[3'"/4'"-(phenylethynyl)phenyl]adamant-7"-yl]-
phenyl}-5,7-bis[3""/4""-(phenylethynyl) phenyl]adamantane (shown in
FIG. 1F)
[0230] 850 milliliters of P1 Step (a) Product was divided into four
equal parts, and subjected to precipitation in petroleum ether,
ligroine, heptane, and methanol. Each part was precipitated into
2520 ml of the solvent, vacuum filtered (Buchner funnel diam. 185
mm), washed on filter twice by 150 ml of the solvent, then dried in
a vacuum oven for two hours at about 20.degree. C., overnight at
40.degree. C., and at 70-80.degree. C. to constant weight.
[0231] Precipitation into hydrocarbons resulted in very dispersed
light beige powders that dried without complications. Precipitation
into methanol gave heavy, brownish granular solid (particles size
approximately 1 mm), which formed tar when dried at 20.degree. C.
This product was dried further.
[0232] Reaction mixtures were analyzed by GPC during the reaction
and before precipitation. All filtrates and final solids were
analyzed by GPC and the results are in Table 4. In Table 4, PPT
stands for precipitation, monomer is
1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane (shown in FIG. 1A);
dimer is
1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl)adamant-7'-yl]ben- zene
(shown in FIG. 1C); and trimer is
1,3-bis{3'/4'-[1",3",5"-tris(3'"/4'-
"-bromophenyl)adamant-7"-yl]phenyl}-5,7-bis(3""/4""-bromophenyl)adamantane
(shown in FIG. 1C).
11TABLE 4 Peak Ratio [monomer to Peak Ratio [monomer to (dimer +
trimer)] (dimer + trimer)] before PPT Solvent For PPT after PPT
75.0:25.0 Petroleum Ether 52.5:47.4 75.0:25.0 Ligroine 64.0:36.0
75.0:25.0 Heptane 66.2:33.8 75.0:25.0 Methanol 75.0:25.0
[0233] To summarize these results, the peak ratio of monomer to
(dimer+trimer) in the reaction mixture was about 3:1. The product
lost in hydrocarbons precipitation filtrates was mostly (>90%)
monomer while losses in washing filtrates were negligible. There is
no product in methanol precipitation filtrates. The monomer to
(dimer+trimer) ratio after precipitation increases
(1:1.fwdarw.3:1), and monomer losses in the filtrates decrease
(56.fwdarw.0%) in the sequence: petroleum ether, ligroine, heptane,
and methanol.
[0234] Preparation 4--Preparation of Thermosetting Component
[0235] The
1,3/4-bis{1',3',5'-tris[3"/4"-(phenylethynyl)phenyl]adamant-7'--
yl}benzene (shown in FIG. 1F) in the Preparation 1 product mixture
is separated using preparative liquid chromatography (PLC). PLC is
similar to the HPLC method described above but uses larger columns
to separate larger quantities of the mixture (from several grams to
several hundred grams).
[0236] Preparation 5--Preparation of Thermosetting Component
[0237] The
1,3-bis{3'/4'-[1",3",5"-tris[3'"/4'"-(phenylethynyl)phenyl]adam-
ant-7"-yl]phenyl}-5,7-bis[3""/4""-(phenylethynyl)phenyl]adamantane
(shown in FIG. 1F) in the Preparation 1 product mixture is
separated using preparative liquid chromatography (PLC).
[0238] Preparation 6--Preparation of Thermosetting Component
[0239] The diamantane monomer of Formula V and oligomer or polymer
of diamantane monomer of Formulae VI, VIII, X, XII, XV, XVI, and
XVIII are prepared using the following method. As shown in FIG. 2,
diamantane is converted using bromine and a Lewis Acid catalyst to
brominated diamantane product. The brominated diamantane product is
then reacted with bromobenzene in the presence of a Lewis Acid
catalyst to form bromophenylated diamantane. The bromophenylated
diamantane is then reacted with a terminal alkyne in the presence
of a catalyst system as used in the so-called Sonogashira coupling
reaction. The product at each step is worked up as described in our
pending patent application PCT/US01/22204 filed Oct. 17, 2001.
[0240] Preparation 7--Preparation of Thermosetting Component
(a)
[0241] The diamantane monomer of Formula V and oligomer or polymer
of diamantane monomer of Formulae VI, VIII, X, XII, XV, XVI, and
XVIII are prepared using the following method. As shown in FIGS. 1A
through 1F, diamantane is converted to the bromophenylated
compositions of diamantane using similar synthetic procedures as
described in Preparations 1 and 2. In FIGS. 1A through 1C,
diamantane is reacted with a substituted halogen phenyl compound in
the presence of a Lewis Acid catalyst as described in Preparations
1 and 2, and/or a second catalyst component as described in
Preparation 2. A mixture of monomers, dimers, trimers, and higher
oligomers is obtained after work-up of the reaction mixtures. In
FIGS. 1D through 1F, the bromophenylated diamantane mixture is then
reacted with a terminal alkyne in the presence of catalyst to
produce the alkyne-substituted diamantane compositions of the
present invention.
Inventive Example 1
[0242] In this example, the ethynyl containing group is first
reacted with the thermosetting component.
[0243] To a 500-mL, 3 neck flask equipped with a condenser, a
mechanical stirrer and a nitrogen inlet-outlet were added
thermosetting component similar to Preparation 1 or 2 above
(amount=20.00 grams (20.19 millimoles));
dichlorobis(triphenylphosphine)palladium(II)(amount=1.134 grams
(1.62 millimoles)); triphenylphosphine (amount=0.848 gram (3.23
millimoles)); copper(I) iodide (amount=0.308 gram (1.62
millimoles)); triethylamine (amount=70 milliliters); and toluene
(amount=80 milliliters). The mixture was heated to 80.degree. C.
and 4-ethynylaniline (amount=0.63 gram (5.2 millimoles)) in 20
milliliters of triethylamine were added to the reaction mixture
dropwise. The reaction mixture was heated at 80.degree. C. for 8
hours and then phenylacetylene (amount=16.50 grams (161.6
millimoles)) and triethylamine (amount=20 milliliters) were added
to the reaction mixture dropwise. The solution was heated at
80.degree. C. for 8 hours.
[0244] The reaction mixture was cooled to room temperature and
transferred to a 1 liter, 3 neck flask equipped with a condenser, a
mechanical stirrer and a nitrogen inlet-outlet and toluene (100
milliliters) was added. The solution was then neutralized with 6N
HCl. The resulting water was removed. The toluene solution was then
stirred with 100 mL of 6N HCl at 60.degree. C. for 30 minutes. The
mixture was filtered through celite.RTM. naturally occurring
inorganic material. The aqueous solution was then removed. The HCl
extraction was repeated for two more times. The toluene solution
was then washed with 100 mL of deionized water twice. The solution
was stirred with 100 mL of 0.1M of N-acetyl-cysteine in ammonia
solution at 60.degree. C. for 30 min. The aqueous solution was then
removed. The ammonia extraction was repeated for five more times.
The toluene was then removed by rotary evaporator and the resulting
solid was dried under vacuum overnight to yield 17.10 grams
(85.05%) of reddish solid (called Solid A).
[0245] To a 100-mL, 3 neck flask equipped with a condenser, a
magnetic stirrer and a nitrogen inlet-outlet were added 20.70 mg
(60% dispersion in mineral oil, which corresponds to 0.5176 mmol)
of sodium hydride, and 20 ml of hexane. The mixture was stirred at
room temperature for 5 minutes and upper hexane layer was decanted.
To the above mixture were added tetrahydrofuran (amount=20
millilters)(THF) and 1.00 g of the above Solid A. The mixture was
stirred at room temperature for 30 minutes and then epoxy
functionalized polynorbornene (amount=0.6540 gram) was added. The
solution was then heated at 65.degree. C. for 12 hours. THF was
then removed by rotary evaporator and the resulting mixture was
dissolve in 15 ml of xylene (called Solution B). This solution was
washed by de-ionized water for 3 times. The preceding reaction
scheme is shown in FIG. 12 where although only
1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl)adamant-7'-- yl]benzene
is shown, it is understood that similar reactions occur for
1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane and
1,3-bis{3'/4'-[1",3",5"-
-tris(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,7-bis{3""/4""-bromopheny-
l)adamantane.
[0246] To a 65-mL plastic bottle was added the above Solution B and
ortho-cresol novolac (amount=0.030 gram; molecular weight of 1760;
supplied by Schenectady International Inc.). The solution was
stirred at room temperature for 1 hour. The solution was then
filtered through a 0.1 .mu.m teflon filter.
[0247] The composition was applied to a substrate using typical
coating conditions known to those skilled in the art. The resulting
spun-on composition was baked for one minute under N.sub.2 (<50
ppm 02) at each of the following temperatures: 125.degree. C.,
250.degree. C., and 300.degree. C. The furnace cure condition was
400.degree. C. for 60 minutes in N.sub.2 (26 liters/minute) with
ramping up from 250.degree. C. at 5.degree. K per minute. The cure
temperature range was from 350.degree. C. to 450.degree. C. In each
composition, the porogen decomposed and the decomposed porogen
volatilized whereby pores formed in the composition. The layer had
a refractive index of 1.433 and a thickness of 2414 Angstroms. FIG.
13 shows the Scanning Electronic Microscope results.
Inventive Example 2
[0248] In this example, the ethynyl containing group is first
reacted with the porogen.
[0249] To a 500-milliliter, 3 neck flask equipped with a condenser,
a magnetic stirrer and a nitrogen inlet-outlet were added sodium
hydride (amount=0.262 gram (60% dispersion in mineral oil, which
corresponds to 6.54 millimoles)), and hexane (amount=60
milliliters). The mixture was stirred at room temperature for 5
minutes and the upper hexane layer was decanted. To the above
mixture were added 4-ethynylaniline (amount=0.695 gram (5.93
millimoles)) and tetrahydrofuran (THF, amount=144 grams). The
solution was stirred at room temperature for 1 hour and epoxy
functionalized polynorbornene (amount=15 grams) was added. The
reaction mixture was heated at 60.degree. C. for 12 hours. THF was
then removed by rotary evaporator and the resulting mixture was
dissolve in 50 ml of toluene to form a solution (referred to below
as Solution A).
[0250] To a 500-milliliter, 3 neck flask equipped with a condenser,
a mechanical stirrer and a nitrogen inlet-outlet were added
thermosetting component similar to Preparation 1 or 2 above
(amount=25.75 grams (26.00 millimoles)),
dichlorobis(triphenylphosphine)palladium(II) (amount=1.461
grams(2.081 millimoles)), triphenylphosphine (amount=1.092
gram(4.162 millimoles)), copper(I) iodide (amount=0.3963 gram(2.081
millimoles)), triethylamine (amount=160 milliliters), and toluene
(amount=80 milliliters). The mixture was heated to 80.degree. C.
and the above Solution A was added to the reaction mixture
dropwise. The reaction mixture was heated at 80.degree. C. for 12
hours and then phenylacetylene (amount=21.3 grams (208.1
millimoles)) and toluene (amount=30 milliliters) were added to the
reaction mixture dropwise. The solution was heated at 80.degree. C.
for 4 hours.
[0251] The reaction mixture was cooled to room temperature and
transferred to a 1 liter, 3 neck flask equipped with a condenser, a
mechanical stirrer and a nitrogen inlet-outlet and toluene
(amount=100 milliliters) was added. The solution was then
neutralized with 6N HCl. The resulting water was removed. The
toluene solution was then stirred with 100 mL of 6N HCl at
60.degree. C. for 30 min. The mixture was filtered through
celite.RTM. naturally occurring inorganic material. The aqueous
solution was then removed. The HCl extraction was repeated for two
more times. The toluene solution was then washed with 100 mL of
deionized water twice. The solution was stirred with 100 mL of 0.1M
of N-acetyl-cysteine in ammonia solution at 60.degree. C. for 30
min. The aqueous solution was then removed. The ammonia extraction
was repeated for five more times. The toluene was then removed by
rotary evaporator and the resulting solid was dried under vacuum
overnight. The preceding reaction scheme is shown in FIG. 14 where
although only 1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl)-
adamant-7'-yl]benzene is shown, it is understood that similar
reactions occur for 1,3,5,7-tetrakis(3'/4'-bromophenyl)adamantane
and
1,3-bis{3'/4'-[1",3",5"-tris(3'"/4'"-bromophenyl)adamant-7"-yl]phenyl}-5,-
7-bis{3""/4""-bromophenyl)adamantane.
[0252] To a 125-milliliter plastic bottle were added 4.48 g of the
above solid, 0.047 g of ortho-cresol novolac (amount=0.047 gram;
molecular weight of 1760; supplied by Schenectady International
Inc.) and xylenes (40.74 grams). The solution was stirred at room
temperature for 1 hour. The solution was then filtered through a
0.1 .mu.m teflon filter.
[0253] The composition was applied to a substrate using typical
coating conditions known to those skilled in the art. The resulting
spun-on composition was baked for one minute under N.sub.2 (<50
ppm O.sub.2) at each of the following temperatures: 125.degree. C.,
250.degree. C., and 300.degree. C. The furnace cure condition was
400.degree. C. for 60 minutes in N.sub.2 (26 liters/minute) with
ramping up from 250.degree. C. at 5.degree. K per minute. The cure
temperature range was from 350.degree. C. to 450.degree. C. In each
composition, the porogen decomposed and the decomposed porogen
volatilized whereby pores formed in the composition. After bake,
the layer had a refractive index of 1.636 and a thickness of 1255
Angstroms. After cure, the layer had a refractive index of 1.398
and a thickness of 1056 Angstroms. FIG. 15 shows Scanning Electron
Microscope results.
Inventive Example 3
[0254] In this example, the ethynyl containing group is first
reacted with the porogen.
[0255] To a 300-milliliter, 3 neck flask equipped with a condenser,
a magnetic stirrer and a nitrogen inlet-outlet were added
triphenylphosphine (amount=9.76 grams (37.2 millimoles)), diethyl
azodicarboxylate (amount=6.49 grams (37.2 millimoles)),
3-hydroxyphenylacetylene (amount=4.00 grams (33.9 millimoles)), and
tetrahydrofuran (THF; amount=90 milliliters). A clear solution was
obtained after the mixture was stirred at room temperature for 5
minutes. To this solution was then added 10.76 g of
polycaprolactone in 40 ml of THF solution dropwise at room
temperature. The solution was stirred at room temperature for 12
hours. THF was then partially removed by rotary evaporator to make
a 40 ml viscous solution and ethyl ether (amount=50 milliliters)
was added to the mixture and put into refrigerator for 30 min. The
precipitate that formed was removed by filtration. Ethyl ether in
the filtrate was then removed by rotary evaporator. To this viscous
solution was added methylene chloride (50 milliliters) and put into
refrigerator overnight. The precipitation that formed was removed
by filtration. The solvent was then removed by rotary evaporator to
yield a viscous liquid (referred to belows as Liquid A).
[0256] To a 500-mL, 3 neck flask equipped with a condenser, a
mechanical stirrer and a nitrogen inlet-outlet were added
thermosetting component similar to Preparation 1 or 2 above
(amount=13.34 grams (13.47 millimoles)),
dichlorobis(triphenylphosphine)palladium(II)
(amount=0.7566gram(1.078 millimoles)), triphenylphosphine
(amount=0.5655gram(2.156 millimoles), copper(I) iodide
(amount=0.2053gram(1.078 millimoles), triethylamine (amount=110
milliliters). The mixture was heated to 80.degree. C. and 12.30 g
of the above Liquid A with toluene (amount=40 milliliters) was
added to the reaction mixture dropwise. The reaction mixture was
heated at 80.degree. C. for 12 hours and then 10.32 g (101.1 mmol)
of phenylacetylene and toluene (amount=30 milliliters) were added
to the reaction mixture dropwise. The solution was heated at
80.degree. C. for 4 hours.
[0257] The reaction mixture was cooled to room temperature and
transferred to a 1 liter, 3 neck flask equipped with a condenser, a
mechanical stirrer and a nitrogen inlet-outlet and toluene
(amount=100 milliliters) was added. The solution was then
neutralized with 6N HCl. The resulting water was removed. The
toluene solution was then stirred with 100 mL of 6N HCl at
60.degree. C. for 30 min. The mixture was filtered through
celite.RTM.. The aqueous solution was then removed. The HCl
extraction was repeated for two more times. The toluene solution
was then washed with 100 mL of deionized water twice. The solution
was stirred with 100 mL of 0.1M of N-acetyl-cysteine in ammonia
solution at 60.degree. C. for 30 min. The aqueous solution was then
removed. The ammonia extraction was repeated for five more times.
The toluene was then removed by rotary evaporator and the resulting
solid was dried under vacuum overnight. The preceding reaction
scheme is shown in FIG. 16 where although only
1,3/4-bis[1',3',5'-tris(3"/4"-bromophenyl)adamant-7'-yl]benzene is
shown, it is understood that similar reactions occur for
1,3,5,7-tetrakis(3'/4'-- bromophenyl)adamantane and
1,3-bis{3'/14'-[1",3",5"-tris(3'"/4'"-bromophen-
yl)adamant-7"-yl]phenyl}-5,7-bis{3""/4""-bromophenyl)adamantane.
[0258] To a 125-milliliter plastic bottle were added 2 grams of the
above solid, polycarbosilane (CH.sub.2SiH.sub.2).sub.q where q is
20-30 (amount=0.1334 gram; supplied by Starfire Systems, Inc.) and
20 g of xylenes (amount=20 grams). The solution was heated at
145.degree. C. for 15.5 hours. The solution was then filtered
through a 0.1 .mu.m teflon filter.
[0259] The composition was applied to a substrate using typical
coating conditions known to those skilled in the art. The resulting
spun-on composition was baked for one minute under N.sub.2 (<50
ppm O.sub.2) at each of the following temperatures: 125.degree. C.,
250.degree. C., and 300.degree. C. The furnace cure condition was
400.degree. C. for 60 minutes in N.sub.2 (26 liters/minute) with
ramping up from 250.degree. C. at 5.degree. K per minute. The cure
temperature range was from 350.degree. C. to 450.degree. C. In each
composition, the porogen decomposed and the decomposed porogen
volatilized whereby pores formed in the composition. After bake,
the layer had a refractive index of 1.617 and a thickness of 5640
Angstroms. After cure, the layer had a refractive index of 1.593
and a thickness of 3784 Angstroms. The above formulation without
the adhesion promoter had an after base refractive index of 1.639,
an after bake thickness of 1369 Angstroms, an after cure refractive
index of 1.584, an after cure thickness of 993 Angstroms, a
degassed dielectric constant of 2.66, and an additional cure
refractive index of 1.562.
* * * * *