US4927736A
Expired / Lapsed
US
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Hydroxy polyimides and high temperature positive photoresists therefrom
Assignee: EMD Performance Materials Corp
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Filing: 1987-07-21
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Granted: 1990-05-22
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Expires: 2007-07-21
Abstract
Abstract This invention relates to novel hydroxy polyimides and radiation sensitive compositions prepared therefrom. More particularly the invention relates to positive photoresists useful in the preparation of a thermally stable relief pattern on a substrate e.g. a silicon wafer or aluminum plate. The novel hydroxy polyimides of the invention may also be used to provide thermally stable organic protective films and layers e.g. an insulating and/or a passivating layer in a semi-conductor component. The novel hydroxy polyimides of in this invention can be synthesized by the condensation of a hydroxy-substituted aminophenol and a dianhydride. Radiation sensitive compositions prepared from the novel hydroxy polyimides of the invention can be developed in aqueous base developer or organic solvent developer; preferably aqueous base developer. Also, the base developer dissolution properties of the polyimides can be controlled by incorporating a non-hydroxyl diamine into the polyimide. The polyimides utilized in this invention have good solubility properties in various organic solvents and also have good mechanical, electrical, adhesion and thermal properties. Radiation sensitive compositions made from hydroxy polyimides of this invention provide high-resolution relief images which are thermally stable up to a temperature of approximately 300° C.
Inventors
- 👤 Werner H. Mueller
- 👤 Dinesh N. Khanna
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 22:16
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1057; C08G73/1064; C08G73/1039; C08G73/1067; C08G73/1071; C08G73/1075; C08G73/1078; G; G03; G03F; G03F7/00; G03F7/004; G03F7/016; G03F7/022; G03F7/023; G03F7/0233; G03F7/038; G03F7/0387
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
130 words
A hydroxy-substituted polyimide having the recurring unit: ##STR12## wherein A is a tetravalent moiety containing at least one aromatic ring of six carbon atoms, wherein each of the four carbonyl groups are directly attached to separate carbons in the ring of the moiety A; wherein each pair of carbonyl groups are attached to adjacent carbon atoms in a ring of the moiety A; wherein the moiety B is a divalent radical containing at least one aromatic ring of six carbon atoms and wherein the moiety B contains at least one hydroxy-substituent said polyimide further characterized in that there is present at least one of moiety A comprised of the radical: ##STR13## or a moiety B comprised of the radical: ##STR14## wherein N is an integer independently selected from 0 to
Claim 2
Dependent Claim
130 words
A hydroxy-substituted polyimide having the recurring unit: ##STR12## wherein A is a tetravalent moiety containing at least one aromatic ring of six carbon atoms, wherein each of the four carbonyl groups are directly attached to separate carbons in the ring of the moiety A; wherein each pair of carbonyl groups are attached to adjacent carbon atoms in a ring of the moiety A; wherein the moiety B is a divalent radical containing at least one aromatic ring of six carbon atoms and wherein the moiety B contains at least one hydroxy-substituent said polyimide further characterized in that there is present at least one of moiety A comprised of the radical: ##STR13## or a moiety B comprised of the radical: ##STR14## wherein N is an integer independently selected from 0 to
Claim 3
Dependent Claim
25 words
A hydroxy-substituted polyimide according to claim 1 wherein the moiety A is a tetravalent radical containing at least two aromatic rings of six carbon atoms.
Claim 4
Dependent Claim
25 words
A hydroxy-substituted polyimide according to claim 1 wherein the moiety B is a divalent radical containing at least two aromatic rings of six carbon atoms.
Claim 5
Dependent Claim
134 words
A polyimide according to claim 1 wherein the tetravalent aromatic moiety A is selected from the group consisting of substituted and unsubstituted benzene nuceli, naphthalene nuceli, polyphenyl nuceli and mixtures thereof wherein said nuceli are selected from the group consisting of ##STR15## or wherein the moiety B is a hydroxy-substituted divalent radical selected from the group consisting of ##STR16## wherein X is a divalent linking group independently selected from the group consisting of a covalent carbon to carbon bond; oxy; carbonyl; sulfonyl; methylene; polymethylene from 2 to 6 carbons; perfluoromethylene; polyperfluoromethylene having 2-6 carbons ; isopropylidene; hexafluoroisopropylidene; and trifluoroisopropylidene; wherein m is an integer from 0 to 4 and wherein n is an integer independently selected from 0 to 3 with the proviso that the divalent moiety B contains at least one hydroxy substituent.
Claim 6
Dependent Claim
18 words
A polyimide according to claim 4 wherein the moiety A is selected from the group consisting of ##STR17##
Claim 7
Dependent Claim
12 words
A polyimide according to claim 5 where the moiety B comprises ##STR18##
Claim 8
Dependent Claim
70 words
The polyimide of claim 1 which is a copolyimide comprising at least about 20 mole percent of recurring units of the formula ##STR19## and up to about 80 mole percent of recurring units of the formula: ##STR20## wherein the moiety D is an aromatic divalent radical having at least one six carbon ring having benzenoid unsaturation and further characterized by the absence of hydroxy substituents on said six carbon ring.
Claim 9
Dependent Claim
33 words
A copolyimide according to claim 7 wherein the moiety D is present in an amount up to about 50 mole percent of the total number of moles of the moieties B and D.
Claim 10
Dependent Claim
29 words
A copolyimide according to claim 7 wherein the moiety D is present in an amount up to about 30 mole percent of the total moles of B and D.
Claim 11
Dependent Claim
208 words
A copolyimide according to claim 7 wherein the tetravalent moiety A is selected from the group consisting of substituted and unsubstituted benzene nuceli, naphthalene, nuceli, polyphenyl nuceli and mixture thereof wherein said nuceli are selected from the group consisting of ##STR21## m' is an integer from the group consisting of 0 to 2; wherein the moiety B is a hydroxy substituted divalent radical selected from the group consisting of ##STR22## and mixtures thereof; wherein X is a divalent linking group independently selected from a covalent carbon to carbon bond; oxy; carbonyl; sulfonyl; methylene; polymethylene from 2 to 6 carbons; perfluoromethylene; polyperfluoromethylene having 2-6 carbons ; isopropylidene; hexafluoroisopropylidene; and trifluoroisopropylidene; wherein m is an integer from the group consisting of 0 to 4 and wherein n is an integer independently selected from 0 to 3 with the proviso that the divalent moiety B contains at least one hydroxy substituent; wherein D is a divalent radical selected from the group consisting of ##STR23## and mixtures thereof; wherein m is an integer from 0 to 4; and R is independently selected from lower alkyl of 1 to 6 carbons, lower alkoxy of 1 to 6 carbons, carboxylic acyl having up to 10 carbons, halogen, hydrogen and wherein X is defined above.
Claim 12
Dependent Claim
32 words
A copolyimide according to claim 10 wherein the moiety D is present in amount up to about 50 mole percent based upon the number of moles of the moieties B and D.
Claim 13
Dependent Claim
31 words
A copolyimide according to claim 10 wherein the moiety D is present in an amount up to about 30 mole percent based upon the number of moles of B and D.
Claim 14
Dependent Claim
50 words
A copolyimide according to claim 11 wherein the moiety A comprises: the group consisting of ##STR24## wherein X is selected from a covalent carbon to carbon bond, oxy, carbonyl, sulfonyl, methylene, polymethylene containing 2 to 6 carbons, perfluoromethylene, polyperfluoromethylene containing 2 to 6 carbon atoms, hexafluoroisopropylidene, trifluoroisopropylidene and mixtures thereof.
Claim 15
Dependent Claim
50 words
A copolyimide according to claim 12 wherein the moiety A comprises: ##STR25## wherein X is selected from the group consisting of a covalent carbon to carbon bond, oxy, carbonyl, sulfonyl, methylene, polymethylene containing 2 to 6 carbons, perfluoromethylene, polyperfluoromethylene containing 2 to 6 carbon atoms, hexafluoroisopropylidene, trifluoroisoropylidene and mixture thereof.
Claim 16
Dependent Claim
57 words
A copolyimide according to claim 12 wherein the moiety B is selected from the group consisting of ##STR26## wherein X is independently selected from the group consisting of a covalent carbon to carbon bond, oxy, carbonyl, sulfonyl, methylene, polymethylene containing 2 to 6 carbons, perfluoromethylene, polyperfluoromethylene containing 2 to 6 carbon atoms, hexafluoroisopropylidene, trifluoroisopropylidene and mixtures thereof.
Claim 17
Dependent Claim
103 words
A copolyimide according to claim 12 wherein the moiety D is selected from the group consisting of ##STR27## and mixtures thereof; wherein X is a divalent linking group independently selected from the group consisting of a covalent carbon to carbon bond; oxy; carbonyl; sulfonyl; methylene; polymethylene from 2 to 6 carbons; perfluoromethylene; polyperfluoromethylene having 2-6 carbons; isopropylidene; hexafluoroisopropylidene; and trifluoroisopropylidene; wherein m is an integer from 0 to 4; and R is independently selected from the group consisting of lower alkyl of 1 to 6 carbons, lower alkoxy of 1 to 6 carbons, carboxylic acyl having up to 10 carbons, halogen, and hydrogen.
Claim 18
Dependent Claim
12 words
A copolyimide according to claim 15 wherein the moiety A comprises: ##STR28##
Claim 19
Dependent Claim
12 words
A copolyimide according to claim 15 wherein the moiety B comprises: ##STR29##
Claim 20
Dependent Claim
12 words
A copolyimide according to claim 15 wherein the moiety D comprises: ##STR30##
Claim 21
Dependent Claim
28 words
A positive working photoresist composition comprising a radiation sensitizer and a polyimide condensation product of at least one aromatic dianhydride and at least one hydroxy substituted aromatic diamine.
Claim 22
Dependent Claim
28 words
A positive working photoresist composition comprising a radiation sensitizer and a polyimide condensation product of at least one aromatic dianhydride and at least one hydroxy substituted aromatic diamine.
Claim 23
Dependent Claim
33 words
A positive working photoresist composition according to claim 20 wherein said aromatic dianhydride is selected from the group consisting of hexafluoro-2,2-bis-(dicarboxyphenyl)propane dianhydride; 5,5'-oxy-bis-1,3-isobenzofurandione; 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 3,3',4,4'-diphenyl tetracarboxylic dianhydride and mixtures thereof.
Claim 24
Dependent Claim
41 words
A positive working photoresist composition according to claim 21 wherein said hydroxy substituted aromatic diamine is selected from the group consisting of 3,3'-dihydroxy benzidine; 3,4'-diamino-3'4-dihydroxybiphenyl; 3,3'-dihydroxy-4,4'-diamino diphenyloxide; 3,3'-dihydroxy-4,4'-diamino diphenylsulphone; 2,2-bis-(3-amino-4-hydroxyphenyl)propane; bis-(3-hydroxy-4-aminophenyl)methane; 2,4-diaminophenol; 3,3'-dihydroxy-4,4'-diamino benzophenone; 1,1-bis-(3-hydroxy-4-aminophenyl)ethane; 1,3-bis-(3-hydroxy-4-aminophenyl)propane; 2,2-bis-(3-hydroxy-4-aminophenyl)propane; hexafluoro-2,2-bis-(3-amino-4-hydroxyphenyl)propane and mixtures thereof.
Claim 25
Dependent Claim
19 words
A positive working photoresist composition according to claim 22 wherein said hydroxy substituted aromatic diaxine is a hexafluoro 2,2-bis-(hydroxyaminophenyl)propane.
Claim 26
Dependent Claim
19 words
A photosensitive article comprising a support substrate having coated thereon a positive working photoresist composition according to claim 20.
Claim 27
Dependent Claim
19 words
A photosensitive article comprising a support substrate having coated thereon a positive working photoresist composition according to claim 21.
Claim 28
Dependent Claim
19 words
A photosensitive article comprising a support substrate having coated thereon a positive working photoresist composition according to claim 22.
Claim 29
Dependent Claim
19 words
A photosensitive article comprising a support substrate having coated thereon a positive working photoresist composition according to claim 23.
Claim 30
Dependent Claim
13 words
An article according to claim 24 wherein said substrate is a metallic substrate.
Claim 31
Dependent Claim
12 words
An article according to claim 24 wherein substrate is a semiconductor wafer.
Claim 32
Dependent Claim
12 words
A protective coating comprising a film of the polyimide of claim 1.
Claim 33
Dependent Claim
17 words
The positive working photoresist composition of claim 20 dissolved in a solvent comprising propylene glycol methyl ether.
Claim 34
Dependent Claim
14 words
The positive working photoresist composition of claim 20 dissolved in a solvent comprising N-methylpyrrolidone.
Claim 35
Dependent Claim
49 words
A method for forming a thermally stable positive photoresist relief pattern which comprises forming a coating of the photosensitive composition of claim 20 on a substrate, imagewise exposing said coating to actinic radiation, and developing the exposed photosensitive composition in an alkaline aqueous developer to remove the exposed area.
Claim 36
Dependent Claim
12 words
The polyimide of claim 1 having recurring groups of the structure: ##STR31##
Claim 37
Dependent Claim
12 words
The polyimide of claim 1 having recurring groups of the structure: ##STR32##
Claim 38
Dependent Claim
12 words
The polyimide of claim 1 having recurring groups of the structure: ##STR33##
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1993-05-21 | 1993-11-20 | 1994-05-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-05-21 | 1997-11-20 | 1998-05-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-05-21 | 2001-11-20 | 2002-05-22 | $7700.00 | Window Closed / Lapsed |