US2005020702A1PendingUtilityA1

Organic compositions

Priority: May 30, 2001Filed: Dec 12, 2003Published: Jan 27, 2005

Est. expiryMay 30, 2021(expired)· nominal 20-yr term from priority

Inventors:Bo Li Paul Apen Kreisler Lau Edward J. Sullivan

H10P 14/6922H10P 14/6342H10P 14/683H10P 14/665H10W 70/695H05K 1/024C07C 25/22H05K 1/0313H05K 3/4676C07C 17/10C08G 61/02C07C 25/24C08L 65/00C07C 17/266C08J 9/26H10K 10/00

PatentIndex Score

Cited by

References

Claims

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.

Claims

exact text as granted — not AI-modified

1 . A composition comprising:
(a) thermosetting component comprising: (1) optionally monomer of Formula I and (2) at least one oligomer or polymer of Formula II where 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

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

where 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 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 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

or said (2) diamantane oligomer or polymer is dimer of Formula X

15 . The composition of claim 13 wherein said (2) adamantane oligomer or polymer is trimer of Formula XI

or said (2) diamantane oligomer or polymer is trimer of Formula XII

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

and adamantane trimer of Formula XI

or diamantane dimer of Formula X

and diamantane trimer of Formula XII

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 1 C≡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 2 ) k (R 3 ) l Si(R 4 ) m (R 5 ) n wherein R 2 , R 3 , R 4 , and R 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 2 , R 3 , R 4 , and R 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: in which R 8 , R 14 , and R 17 each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R 9 , R 10 , R 11 , R 12 , R 15 , and R 16 each independently represents hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be linear or branched, R 13 represents organosilicon, silanyl, siloxyl, or organo group, and p, q, r, and s satisfy the conditions of [4≦p+q+r+s≦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 18 C 6 H 2 (OH)(R 19 )] t — where R 18 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl, R 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

and (2) at least one oligomer or polymer of Formula II

where 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

and (2) adamantane oligomer or polymer of Formula IV

or (1) diamantane monomer of Formula V

and (2) diamantane oligomer or polymer of Formula VI

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 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

or said (2) diamantane oligomer or polymer is dimer of Formula X

47 . The method of claim 45 wherein said (2) adamantane oligomer or polymer is trimer of Formula XI

or said (2) diamantane oligomer or polymer is trimer of Formula XII

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

and adamantane trimer of Formula XI

or diamantane dimer of Formula X

and diamantane trimer of Formula XII

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 1 C≡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 2 ) k (R 3 ) l Si(R 4 ) m (R 5 ) n wherein R 2 , R 3 , R 4 , and R 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 2 , R 3 , R 4 , and R 5 represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical, and k+l+m+n≦4; or polycarbosilane of the Formula XXV: in which R 8 , R 14 , and R 17 each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R 9 , R 10 , R 11 , R 12 , R 15 , and R 16 each independently represents hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be linear or branched, R 13 represents organosilicon, silanyl, siloxyl, or organo group, and p, q, r, and s satisfy the conditions of [4≦p+q+r+s≦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 18 C 6 H 2 (OH)(R 19 )] t — where R 18 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl, R 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:

where 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:

or polymer of Formula IV:

the diamantane monomer of Formula V:

or the diamantane oligomer or polymer of Formula VI

where h is from 0 to 10; i is from 0 to 10; j is from 0 to 10; each of R 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 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

or the structure of Formula X:

74 . The composition of claim 55 , wherein the at least one oligomer or polymer comprises the structure of Formula XI:

or the structure of Formula XII:

75 . The composition of claim 55 , wherein the thermosetting component comprises a mixture of the compound of Formula IX

and Formula XI

or Formula X

and Formula XII

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 1 C≡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 2 ) k (R 3 ) l Si(R 4 ) m (R 5 ) n wherein R 2 , R 3 , R 4 , and R 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 2 , R 3 , R 4 , and R 5 represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical, and k+l+m+n&lt;4; polycarbosilane of the Formula XXV: in which R 8 , R 14 , and R 17 each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R 9 , R 10 , R 11 , R 12 , R 15 , and R 16 each independently represents hydrogen atom, alkyl, alkylene, vinyl, cycloalkyl, allyl, aryl, or arylene and may be linear or branched, R 13 represents organosilicon, silanyl, siloxyl, or organo group, and p, q, r, and s satisfy the conditions of [4&lt;p+q+r+s≦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 18 C 6 H 2 (OH)(R 19 )] t — where R 18 is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl, R 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.

Join the waitlist — get patent alerts

Track US2005020702A1 — get alerts on status changes and closely related new filings.

We store only your email — no account needed. See our privacy policy.