USRE41580EExpiredUtilityPatentIndex 84
Lactone-containing compounds, polymers, resist compositions, and patterning method
Est. expirySep 25, 2018(expired)· nominal 20-yr term from priority
C07D 307/00G03F 7/0395G03F 7/0045G03F 7/0397C07D 313/04
84
PatentIndex Score
8
Cited by
16
References
48
Claims
Abstract
A novel lactone-containing compound is provided as well as a polymer comprising units of the compound. The polymer is used as a base resin to formulate a resist composition having a high sensitivity, resolution and etching resistance.
Claims
exact text as granted — not AI-modified1. A lactone-containing compound of the following formula (1):
wherein R 1 is hydrogen, methyl or CH 2 CO 2 R 5 , R 2 is hydrogen, methyl or CO 2 R 5 , R 3 is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R 4 is hydrogen or CO 2 R 5 , R 5 is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH 2 , CH 2 CH 2 , O or S.
2. A compound of claim 1 , wherein in formula (1), R 3 is hydrogen or a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl group, and each R 5 is independently a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl or butyladamantyl group.
3. A polymer comprising units of the following formula (1a) and having a weight average molecular weight of 1,000 to 500,000,
wherein R 1 is hydrogen, methyl or CH 2 CO 2 R 5 , R 2 is hydrogen, methyl or CO 2 R 5 , R 3 is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R 4 is hydrogen or CO 2 R 5 , R 5 is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH 2 , CH 2 CH 2 , O or S.
4. A polymer of claim 3 , wherein in formula (1a), R 3 is hydrogen or a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl group, and each R 5 is independently a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl or butyladamantyl group.
5. A polymer of claim 3 , which polymer has a weight average molecular weight of about 3,000 to 100,000.
6. The polymer of claim 3 further comprising units of at least one of the following formulae (2a) to (10a):
wherein R 1 and R 2 are as defined above,
R 6 is hydrogen or a carboxyl or hydroxyl-containing monovalent hydrocarbon group of 1 to 15 carbon atoms,
at least one of R 7 to R 10 is a carboxyl or hydroxylcontaining monovalent hydrocarbon group of 1 to 15 carbon atoms, and the remainder are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or R 7 to R 10 , taken together, may form a ring, and when they form a ring, at least one of R 7 to R 10 is a carboxyl or hydroxyl-containing divalent hydrocarbon group of 1 to 15 carbon atoms, and the remainder are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms,
R 11 is a monovalent hydrocarbon group of 3 to 15 carbon atoms containing a —CO 2 — partial structure,
at least one of R 12 to R 15 is a monovalent hydrocarbon group of 2 to 15 carbon atoms containing a —CO 2 — partial structure, and the remainder are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or R 12 to R 15 , taken together, may form a ring, and when they form a ring, at least one of R 12 to R 15 is a divalent hydrocarbon group of 1 to 15 carbon atoms containing a —CO 2 — partial structure, and the remainder are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms,
R 16 is a polycyclic hydrocarbon group of 7 to 15 carbon atoms or an alkyl group containing such a polycyclic hydrocarbon group,
R 17 is an acid labile group, and
k is equal to 0 or 1.
7. A resist composition, comprising the polymer of claim 3 .
8. A resist composition comprising the polymer of claim 3 , a photoacid generator capable of generating an acid upon exposure to high-energy radiation or electron beams, and an organic solvent.
9. A resist composition of claim 8 , wherein the photoacid generator is an onium salt, a diazomethane or glyoxime derivative or a combination thereof.
10. A resist composition of claim 8 , wherein the photoacid generator is provided in the composition in an amount of about 0.1 to 15 parts by weight per 100 parts by weight of the polymer.
11. A resist composition of claim 8 , wherein the organic solvent comprises diethylene glycol dimethyl ether, 1-ethoxy-2-propanol or propylene glycol monomethyl ether acetate.
12. A resist composition of claim 8 , wherein the solvent is provided in the composition in an amount of 200 to 1000 parts by weight per 100 parts by weight of the polymer.
13. A resist composition of claim 8 , which further comprises a dissolution inhibitor.
14. A resist composition of claim 8 , which further comprises a basic compound.
15. A resist composition comprising a polymer according to claim 6 .
16. A resist composition comprising a polymer according to claim 6 , a photoacid generator capable of generating an acid upon exposure to high-energy radiation or electron beams, and an organic solvent.
17. A method for preparing a polymer comprising effecting radical or anionic polymerization between a atom-containing compound of the general formula (1) and another compound having a carbon-to-carbon double bond
wherein R 1 is hydrogen, methyl or CH 2 CO 2 R 5 , R 2 is hydrogen, methyl or CO 2 R 5 , R 3 is H or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R 4 is hydrogen or CO 2 R 5 , R 5 is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH 2 , C 2 CH 2 , O or S.
18. A method for forming a resist pattern comprising the steps of:
(i) applying a resist composition according to claim 7 onto a substrate to form a film, (ii) heat treating the film and then exposing it to high-energy radiation or electron beams through a photo mask, and (iii) optionally heat treating the exposed film and developing it with a developer.
19. A method for forming a resist pattern comprising the steps of:
(i) applying a resist composition according to claim 8 onto a substrate to form a film, (ii) heat treating the film and then exposing it to high-energy radiation or electron beams through a photo mask, and (iii) optionally heat treating the exposed film and developing it with a developer.
20. A compound of claim 1 wherein R 3 is hydrogen.
21. A lactone- containing compound of claim 1 wherein the following formula ( 1 ):
wherein R 1 is hydrogen, methyl or CH 2 CO 2 R 5 , R 2 is hydrogen, methyl or CO 2 R 5 , R 3 is isopropyl, R 4 is hydrogen or CO 2 R 5 , R 5 is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH 2 , CH 2 CH 2 , O or S .
22. A lactone- containing compound of the following formula ( 1 ):
wherein R
1
is hydrogen, methyl or CH
2
CO
2
R
5
, R
2
is hydrogen, methyl or CO
2
R
5
, R
3
is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R
4
is hydrogen or CO
2
R
5
, R
5
is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is O or S.
23. The compound of claim 22 , wherein X is O.
24. A lactone containing compound of the following formula ( 1 ):
wherein R
1
is hydrogen, methyl or CH
2
CO
2
R
5
, R
2
is hydrogen, methyl or CO
2
R
5
, R
3
is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R
4
is CO
2
R
5
, R
5
is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH
2
, CH
2
CH
2
, O or S.
25. A polymer comprising units of the following formula ( 1 a ) and having a weight average molecular weight of 1 , 000 to 500 , 000 :
wherein R
1
is hydrogen, methyl or CH
2
CO
2
R
5
, R
2
is hydrogen, methyl or CO
2
R
5
, R
3
is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R
4
is hydrogen or CO
2
R
5
, R
5
is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is O or S.
26. The polymer of claim 24 , further comprising at least one unit of at least one of the following formulae ( 2 a ) to ( 10 a ):
wherein
R
1
and R
2
are as defined above,
R 6 is hydrogen or a carboxyl or hydroxyl - containing monovalent hydrocarbon group of 1 to 15 carbon atoms,
at least one of R 7 to R 10 is a carboxyl or hydroxyl - containing monovalent hydrocarbon group of 1 to 15 carbon atoms, and the remainder are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or two of R 7 to R 10 , taken together, may form a ring, and when they form a ring, they together are a carboxyl - or hydroxyl - containing divalent hydrocarbon group of 1 to 15 carbon atoms, and the remainder of R 7 to R 10 are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms,
R
11
is a monovalent hydrocarbon group of 3 to 15 carbon atoms containing a —CO
2
— partial structure,
at least one of R
12
to R
15
is a monovalent hydrocarbon group of 2 to 15 carbon atoms containing a —CO
2
— partial structure, and the remainder are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or two of R
12
to R
15
, taken together, may form a ring, and when they form a ring, they together are a divalent hydrocarbon group of 1 to 15 carbon atoms containing a —CO
2
— partial structure, and the remainder of R
12
to R
15
are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms,
R
16
is a polycyclic hydrocarbon group of 7 to 15 carbon atoms or an alkyl group containing such a polycyclic hydrocarbon group,
R
17
is an acid labile group, and
k is equal to 0 or 1 .
27. A resist composition, comprising the polymer of claim 26 and a photoacid generator.
28. A resist composition comprising the polymer of claim 26 , a photoacid generator capable of generating an acid upon exposure to high- energy radiation or electron beams, and an organic solvent.
29. A method for forming a resist pattern comprising the steps of:
( i ) applying a resist composition according to claim 28 onto a substrate to form a film, ( ii ) heat treating the film and then exposing it to high - energy radiation or electron beams through a photo mask, and ( iii ) optionally heat treating the exposed film and developing it with a developer.
30. The polymer of claim 26 , wherein X is O.
31. A resist composition, comprising the polymer of claim 25 and a photoacid generator.
32. A resist composition comprising the polymer of claim 25 , a photoacid generator capable of generating an acid upon exposure to high- energy radiation or electron beams, and an organic solvent.
33. A method for forming a resist pattern comprising the steps of:
( i ) applying a resist composition according to claim 32 onto a substrate to form a film, ( ii ) heat treating the film and then exposing it to high - energy radiation or electron beams through a photo mask, and ( iii ) optionally heat treating the exposed film and developing it with a developer.
34. The polymer of claim 25 , wherein X is O.
35. A resist composition, comprising the polymer of claim 34 and a photoacid generator.
36. A method for forming a resist pattern comprising the steps of:
( i ) applying a resist composition according to claim 35 onto a substrate to form a film, ( ii ) heat treating the film and then exposing it to high - energy radiation or electron beams through a photo mask, and ( iii ) optionally heat treating the exposed film and developing it with a developer.
37. A resist composition comprising the polymer of claim 34 , a photoacid generator capable of generating an acid upon exposure to high- energy radiation or electron beams, and an organic solvent.
38. A polymer comprising units of the following formula ( 1 a ) and having a weight average molecular weight of 1 , 000 to 500 , 000 :
wherein R
1
is hydrogen, methyl or CH
2
CO
2
R
5
, R
2
is hydrogen, methyl or CO
2
R
5
, R
3
is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R
4
is CO
2
R
5
, R
5
is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH
2
, CH
2
CH
2
, O or S.
39. The polymer of claim 38 , further comprising at least one unit of at least one of the following formulae ( 2 a ) to ( 10 a ):
wherein:
R
1
and R
2
are as defined above,
R 6 is hydrogen or a carboxyl or hydroxyl - containing monovalent hydrocarbon group of 1 to 15 carbon atoms,
at least one of R 7 to R 10 is a carboxyl or hydroxyl - containing monovalent hydrocarbon group of 1 to 15 carbon atoms, and the remainder are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or two of R 7 to R 10 , taken together, may form a ring, and when they form a ring, they together are a carboxyl - or hydroxyl - containing divalent hydrocarbon group to 1 to 15 carbon atoms, and the remainder of R 7 to R 10 are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms,
R
11
is a monovalent hydrocarbon group of 3 to 15 carbon atoms containing a —CO
2
— partial structure,
at least one of R
12
to R
15
is a monovalent hydrocarbon group of 2 to 15 carbon atoms containing a —CO
2
— partial structure, and the remainder are independently hydrogen or a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, or two of R
12
to R
15
, taken together, may form a ring, and when they form a ring, they together are a divalent hydrocarbon group of 1 to 15 carbon atoms containing a —CO
2
— partial structure, and the remainder of R
12
to R
15
are independently a single bond or a straight, branched or cyclic alkylene group of 1 to 15 carbon atoms,
R
16
is a polycyclic hydrocarbon group of 7 to 15 carbon atoms or an alkyl group containing such a polycyclic hydrocarbon group,
R
17
is an acid labile group, and
k is equal to 0 or 1 .
40. A resist composition, comprising the polymer of claim 39 and a photoacid generator.
41. A resist composition comprising the polymer of claim 39 , a photoacid generator capable of generating an acid upon exposure to high- energy radiation or electron beams, and an organic solvent.
42. A method for forming a resist pattern comprising the steps of:
( i ) applying a resist composition according to claim 41 onto a substrate to form a film, ( ii ) heat treating the film and then exposing it to high - energy radiation or electron beams through a photo mask, and ( iii ) optionally heat treating the exposed film and developing it with a developer.
43. A resist composition, comprising the polymer of claim 38 and a photoacid generator.
44. A resist composition comprising the polymer of claim 38 , a photoacid generator capable of generating an acid upon exposure to high- energy radiation or electron beams, and an organic solvent.
45. A method for forming a resist pattern comprising the steps of:
( i ) applying a resist composition according to claim 44 onto a substrate to form a film, ( ii ) heat treating the film and then exposing it to high - energy radiation or electron beams through a photo mask, and ( iii ) optionally heat treating the exposed film and developing it with a developer.
46. A method for preparing a polymer comprising effecting radical or anionic polymerization between a lactone- containing compound of the formula ( 1 ) and another compound having a carbon - to - carbon double bond
wherein R
1
is hydrogen, methyl or CH
2
CO
2
R
5
, R
2
is hydrogen, methyl or CO
2
R
5
, R
3
is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R
4
is hydrogen or CO
2
R
5
, R
5
is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is O or S.
47. The method of claim 46 , wherein X is O.
48. A method for preparing a polymer comprising effecting radical or anionic polymerization between a lactone- containing compound of the formula ( 1 ) and another compound having a carbon - to - carbon double bond
wherein R
1
is hydrogen, methyl or CH
2
CO
2
R
5
, R
2
is hydrogen, methyl or CO
2
R
5
, R
3
is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R
4
is CO
2
R
5
, R
5
is a straight, branched or cyclic alkyl group of 1 to 15 carbon atoms, and X is CH
2
, CH
2
CH
2
, O or S.Cited by (0)
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