US4699870A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Patterning method
Assignee: NTT Inc
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Filing: 1985-07-22
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Granted: 1987-10-13
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Expires: 2005-07-22
Abstract
Abstract PCT No. PCT/JP85/00411 Sec. 371 Date Mar. 19, 1986 Sec. 102(e) Date Mar. 19, 1986 PCT Filed Jul. 22, 1985 PCT Pub. No. WO86/01009 PCT Pub. Date Feb. 13, 1986.In a fine pattern forming method for use in the manufacture of semiconductor integrated circuits, optical integrated circuits, Josephson elements, and so forth, a positive resist mixture is used which is composed of a resist having a carboxyl group in the side chain and an additive which is an oxide, halide, or organic acid salt of a bivalent metal and which, when heated, forms Ionomer to produce thermal crosslinks. The positive resist mixture is developed using a developer having carboxylic acid mixed in an organic solvent, thereby permitting the formation of an ultra-fine and high precision pattern.
Inventors
- 👤 Kazumi Iwadate
- 👤 Katsuhiro Harada
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 18:35
CPC Classifications
G; G03; G03F; G03F7/00; G03F7/004; G03F7/039; G03F7/20; G03F7/2002; G03F7/2004; G03F7/26; Y; Y10; Y10S; Y10S430/00; Y10S430/143; Y10S430/167; Y10S430/168
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
116 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer thereby forming a desired pattern.
Claim 2
Dependent Claim
116 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer thereby forming a desired pattern.
Claim 3
Dependent Claim
67 words
A patterning method according to claim 1 wherein said oxide of a bivalent metal is BaO, said halide of a bivalent metal is selected from the group consisting of the chlorides, bromides and iodides of Cu, Ca, Ba, Zn and Fe and said organic acid salt of a bivalent metal is selected from the group consisting of formates, acetates and propionates of Cu, Ca, Ba and Zn.
Claim 4
Dependent Claim
19 words
A patterning method according to claim 1 wherein the amount of said additives is from 0.1 to 5 wt.%.
Claim 5
Dependent Claim
27 words
A patterning method according to claim 1 wherein said developer is a mixture of 1,4-dioxane with a member of the group consisting of diisobutylketone, hexane and cyclohexane.
Claim 6
Dependent Claim
20 words
A patterning method according to claim 1 wherein said irradiation is carried out using ultraviolet rays, electron beam or X-rays.
Claim 7
Dependent Claim
36 words
A patterning method according to claim 1 wherein said additive is a member selected from the group consisting of ZnBr 2 , BaO, CuCl 2 , ZnI 2 , calcium formate, barium acetate and zinc propionate.
Claim 8
Dependent Claim
20 words
A patterning method according to claim 1 wherein said additive is ZnBr 2 and said polymer is poly(methyl methacrylate-co-methacrylic acid)copolymer.
Claim 9
Dependent Claim
119 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer containing a carboxylic acid in an organic solvent.
Claim 10
Dependent Claim
119 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer containing a carboxylic acid in an organic solvent.
Claim 11
Dependent Claim
144 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer thereby forming a desired pattern, wherein said film formed by said coating and baking is made up of at least two layers of resist mixtures having different compositions and/or concentrations of said additive.
Claim 12
Dependent Claim
144 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer thereby forming a desired pattern, wherein said film formed by said coating and baking is made up of at least two layers of resist mixtures having different compositions and/or concentrations of said additive.
Claim 13
Dependent Claim
23 words
A patterning method according to claim 9 wherein each of said at least two layers of resist mixtures are baked at different temperatures.
Claim 14
Dependent Claim
39 words
A patterning method according to claim 9 wherein said at least two layers of resist mixtures are formed so that the lowermost of said layers is soluble in the developer at a greater rate than is an upper layer.
Claim 15
Dependent Claim
176 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer thereby forming a desired pattern, wherein said film formed by said coating and baking is made up of at least two layers of resist mixtures having different compositions and/or concentrations of said additive and wherein a developer containing a carboxylic acid in an organic solvent and a developer free of carboxylic acid in the organic solvent are each used at least once as the developer.
Claim 16
Dependent Claim
176 words
A patterning method which comprises applying a coating of a positive resist mixture composed of a homogeneous mixture of a resist having a carboxyl group in the side chain and decomposable by irradiation with high-energy rays and at least one additive selected from the group consisting of oxides, halides and organic acid salts of bivalent metals to form a film of said coating on the surface of a substrate, baking said coated substrate whereby intermolecular crosslinking results from the formation of ionomer by said carboxyl group and bivalent metals, thereafter irradiating a portion of said film with high energy rays and dissolving the irradiated portion of said film with a developer thereby forming a desired pattern, wherein said film formed by said coating and baking is made up of at least two layers of resist mixtures having different compositions and/or concentrations of said additive and wherein a developer containing a carboxylic acid in an organic solvent and a developer free of carboxylic acid in the organic solvent are each used at least once as the developer.
Claim 17
Dependent Claim
120 words
A patterning method according to claim 12, wherein the resist having the carboxyl group in the side chain and decomposable by irradiation with high-energy rays is a polymer having the following formula (I): ##STR2## where R 1 , R 2 , . . . R n represent alkyl groups, halogenated alkyl groups, or aryl groups having five or fewer carbon atoms, or --COORa or --CORb (where Ra and Rb are alkyl groups or halogenated alkyl or aryl groups having five or fewer carbon atoms), and when ##EQU2## m c /M is in the range of 0.01 to 1.0 and m 1 /M, m 2 /M, . . . m n /M are respectively in the range of 0.99 to 0.
Claim 18
Dependent Claim
36 words
A patterning method according to claim 13 wherein said polymer is selected from the group consisting of poly(methylmethacrylate-co-methacrylic acid), poly(butyl methacrylate-co-methacrylic acid), poly(hexafluorobutyl methacrylate-co-methacrylic acid), poly(isobutylene-co-methacrylic acid), poly(methacrylonitrile-co-methacrylic acid), poly(phenyl methacrylate-co-methacrylic acid), and poly(β-naphthyl methacrylate-co-methacrylic acid).
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