WO1994018607A1 - Process for forming positive polyimide pattern - Google Patents
Process for forming positive polyimide pattern Download PDFInfo
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- WO1994018607A1 WO1994018607A1 PCT/JP1994/000104 JP9400104W WO9418607A1 WO 1994018607 A1 WO1994018607 A1 WO 1994018607A1 JP 9400104 W JP9400104 W JP 9400104W WO 9418607 A1 WO9418607 A1 WO 9418607A1
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- WIPO (PCT)
- Prior art keywords
- positive
- group
- forming
- film
- polyimide precursor
- Prior art date
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/107—Polyamide or polyurethane
Definitions
- the present invention relates to a method for forming a polyimide pattern using an actinic radiation-sensitive polyimide precursor composition, and more particularly, to a positive type polyimide using an actinic radiation-sensitive polyimide precursor composition.
- the present invention relates to a method for forming a mid pattern.
- the following method has been known as a method for forming a polyimide pattern using an actinic radiation-sensitive polyimide precursor composition.
- (C) A method for forming a polyimide pattern using an actinic radiation-sensitive polyimide precursor composition in which a photosensitive group is introduced into a polyamic acid by an ester group.
- the exposed portion was developed with a higher degree of curing than the unexposed portion, so that the exposed portion remained negative.
- a negative type if dust or the like adheres to a mask or the like used at the time of exposure, the portion becomes defective, and a pinhole is formed in the polyimide film. Therefore, when a polyimide film is used as a protective film for a semiconductor device or an interlayer insulating film of a multilayer wiring for high-density mounting, there is a problem that yield and reliability are reduced, and actinic radiation-sensitive polyimide is problematic.
- a method for forming a polyimide pattern using a polyimide precursor composition for example, JP-A-1-61747).
- a first object of the present invention is to provide a method for forming an excellent positive-type polyimide pattern using an actinic ray-sensitive polyimide precursor composition which is easy to produce.
- Another object of the present invention is to provide a method for forming a positive polyimide pattern having excellent photosensitivity (sensitivity, etc.).
- Another object of the present invention is to prevent a decrease in yield and a decrease in reliability when a polyimide film is used as a protective film of a semiconductor element or an interlayer insulating film of a multilayer wiring for a high-density mounting board. Disclosure of the invention
- an unexpected effect that a positive-type polyimide pattern can be formed using an actinic radiation-sensitive polyimide precursor composition originally used as a negative electrode can be obtained.
- actinic radiation-sensitive polyimide precursor composition originally used as the negative type is practical because it is easier to manufacture than the composition conventionally known as the posi type.o
- the photosensitive performance (sensitivity, etc.) becomes excellent.
- An object of the present invention is to form a film of an actinic ray-sensitive polyimide precursor composition on a substrate and selectively expose the film with actinic radiation, so that the unexposed film has a higher degree of curing than the exposed film.
- a method for forming a positive polyimide pattern which comprises a step of performing a process of increasing the thickness and subsequently removing a film on the exposed portion.
- the present inventors have conducted intensive studies in order to achieve the above object, and as a result, there has been a conventionally known technique of removing an exposed portion by utilizing a difference in the degree of cure between a film in an unexposed portion and a film in an exposed portion. It has been found that a positive type polyimide pattern can be formed by a mechanism that has not been achieved, and the present invention has been achieved.
- the actinic radiation-sensitive polyimide precursor composition in the present invention includes:
- a composition obtained by adding a compound having a photoreactive group and an amino group to a polyamic acid for example, US Pat. No. 4,243,743, US Pat. No. 4,451,551
- Polyamides having a compound having an amino group and an azido group and a composition obtained by adding a Z or bisazide compound eg, US Pat. No. 4,451,551, EP Publication No. 65352
- a Z or bisazide compound eg, US Pat. No. 4,451,551, EP Publication No. 65352
- Preferred actinic radiation-sensitive polyimide precursor compositions in the present invention include (a) a polymer (A) having a structural unit represented by the general formula (1) as a main component, and
- R 1 is a trivalent or tetravalent organic group having at least 2 carbon atoms
- R 2 is a divalent organic group having at least 2 carbon atoms
- is an alkali metal ion Represents an ammonium ion, hydrogen, or an organic group having 1 to 30 carbon atoms.
- n is 1 or 2.
- the polymer (A) having a structural unit represented by the general formula (1) as a main component in the present invention is a polymer having an imido ring or another cyclic structure by heating or an appropriate catalyst (hereinafter referred to as “polyimid”). Polymer).
- R 1 is a trivalent or tetravalent organic group having at least two carbon atoms. From the viewpoint of heat resistance, R 1 is preferably a trivalent or tetravalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Specifically, a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoro group Examples include, but are not limited to, propane groups.
- R 2 is a divalent organic group having at least two carbon atoms, but from the viewpoint of heat resistance, R 2 contains an aromatic ring or an aromatic heterocyclic ring, And a divalent group having 6 to 30 carbon atoms is preferable.
- an aliphatic group having a siloxane structure may be copolymerized as R 1 and R 2 as long as the heat resistance is not reduced.
- Specific examples include those obtained by copolymerizing bis (propyl) tetramethyldisiloxane groups with 1 to 10 mol%.
- R 3 represents an alkali metal ion, an ammonium ion, hydrogen, or an organic group having 1 to 30 carbon atoms.
- Preferred examples of R 3 include hydrogen, methyl group, ethyl group, isopropyl group, butyl group, ethyl methacrylate group, ethyl acrylate group, 0-; benzyl group and the like. Not limited. Particularly, hydrogen is preferable as R 3 .
- R 1 , R 2 , and R are each composed of one of these. Or a copolymer composed of two or more types.
- the polymer (A) may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. At that time, it is preferable that the content of the structural unit represented by the general formula (1) is 90 mol% or more.
- the type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.
- polymer (A) As a specific example of polymer (A),
- polyamide acids and their esters are synthesized by known methods. That is, in the case of polyamic acid, tetracarboxylic dianhydride and diamin are selected. Alternatively, they can be combined with a polar solvent containing N-methyl-12-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc. It is synthesized by reacting in The esterified product of the polyamic acid is synthesized, for example, by the method described in JP-A-61-72022, JP-B-55-30207.
- the compound (B) having an amino group or an amide group will be described.
- the amino group examples include a primary or quaternary amino group or a basic ring such as a pyridine ring.
- the amide group may include a urea group and a Z or urethane group. Those having an amino group or an amide group and having an organic group having a carbon atom are preferred. More preferably, it is a compound comprising an organic group having 2 to 30 carbon atoms, and more preferably a compound in which an amino group or an amide group is bonded to an aliphatic group.
- compounds having an amino group or an amide group compounds having a photoreactive group are preferred.
- the photoreactive group in the present invention refers to an ethylenically unsaturated double bond, an aromatic azide group, an aromatic sulfonyl azide group and the like.
- Preferred specific examples of the compound having a photoreactive group and an amino group or an amide group include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N —Dimethyl methacrylamide, N, N—Getyl acrylamide, N, N—Getyl methacrylamide, N—Methyl methacrylamide, N—Isopropyl methacrylamide, N—Isopropyl acrylamide, N—Butyl methacrylamide, N-butylacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-cyclohexylmethacrylamide, cyclohexylacrylamide, acryloyl morpholin, methacryloyl morpholin, acryloyl Peri-j
- a compound having an amino group or an amide group, and in which the photoreactive group is an ethylenically unsaturated double bond is particularly preferable. Further, a compound in which the ethylenically unsaturated double bond is an acryl group or a methacryl group is more preferable.
- Examples of the compound having an amino group or an amide group having no photoreactive group include triethylamine, propylamine, cyclohexylamine, dimethylaminoethyl acetate, getylaminoethyl ethyl sulphate, and dimethylamido.
- Noethanol, dimethylaminoethyl propionate, acetate, N-methylacetamide, N-ethylacetamide, N-methylformamide, N-ethylformamide, .N, N-dimethylacetamide, N Examples include, but are not limited to, N-dimethylformamide.
- Some compounds with amide groups dissolve polyimide precursors, such as N, N-dimethylacetamide and N, N-dimethylformamide. Some also act as solvents.
- a compound having an amino group or an amide group, which does not itself dissolve the polyimide precursor must have an equivalent of at least 5%, preferably 30%, of all the structural units of the polymer component, and It is desirable that the mixture be mixed at a ratio of 5 times or less the equivalent of all carboxyl groups in the polymer component. Outside of this range, the sensitivity will deteriorate and the image will be more restricted.
- the actinic radiation-sensitive polyimide precursor composition preferably contains a photoinitiator, a photosensitizer, and a photoreactive monomer.
- photoinitiators include aromatic amide compounds such as Michler's ketone, 4,4'-Jetylamino benzophenone, ⁇ -phenyl benzene, ⁇ -phenylglycine, and 1-phenylpropanedione.
- Acyclic oxime ester compounds such as 2-diphenyl-1-ethanedione-11- (0-benzyl) oxime and cyclic oxime ester compounds such as 3-phenyl-5-isoxazolone are effective. It is not limited to. Particularly, oxime ester compounds are desirable in terms of sensitivity. These photoinitiators are used alone or in combination of two or more.
- the amount of the photoinitiator is preferably 1 to 100% by weight, more preferably 1 to 50% by weight, based on the polymer component. If the ratio is out of this range, the sensitivity is lowered and the restriction on development is increased.
- Examples of sensitizers include Michler's Ketone, 4,4'-Jethylamino benzophenone, 3,3'-carbonylbis (Jetylamino coumarin), and "Kumarin” 339, "Kumarin” of Kodak Company, Ltd. 338, "coumarin” 314, “coumarin” 7, etc. are valid, but not limited to these. These sensitizers are used alone or as a mixture of two or more.
- the amount of the sensitizer is preferably from 0.1 to 20% by weight, more preferably from 0.2 to 10% by weight, based on the amount of the polymer component, from the viewpoint of sensitivity.
- a combination of an oxime ester compound as a photoinitiator and a coumarin compound as a photosensitizer is particularly effective.
- Photoreactive monomers include 2-hydroxylethyl methacrylate, methacrylic acid, and trimethyl methacrylate. Recreatorate, trimethylolproha. Methacrylate and ethylene glycol dimethacrylate. These photoreactive monomers are used alone or in combination of two or more. If these photoreactive monomers are added in an amount of 1 to 20% by weight based on the amount of the polymer component, further improvement in sensitivity can be expected.
- the solvents used at this time include N-methyl-12-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide, Non-protonic polar solvents such as 7-butyrolactone and N, N-dimethylacrylamide are preferably used alone or as a mixture of two or more, but are not limited thereto.
- a surfactant for improving the wettability of the polyimide precursor composition with a substrate, or Si0 a surfactant for improving the wettability of the polyimide precursor composition with a substrate, or Si0.
- Inorganic particles such as TiO 2 and Tio 2 or particles of polyimide may be added.
- the actinic radiation-sensitive polyimide precursor composition is applied on a substrate.
- a substrate Recon aluminum, aluminum nitride, alumina ceramic, glass ceramic, sapphire, a substrate on which a semiconductor is formed, and the like are used, but are not limited thereto.
- the coating method include, but are not limited to, spin coating using a spinner, spray coating, dipping, and mouth coating.
- the thickness of the applied film varies depending on the application means, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 m.
- the substrate coated with the polyimide precursor composition is dried to obtain a polyimide precursor composition coating film. Drying is preferably performed at a temperature in the range of 50 to 100 ° C. for 1 minute to several hours.
- Actinic radiation used for exposure includes ultraviolet light, visible light, electron beam, X-ray and the like. Particularly, ultraviolet rays and visible rays are preferable.
- heat treatment infrared irradiation treatment, microwave irradiation treatment, etc. are effective as treatments in which the film in the unexposed portion has a higher degree of curing than the film in the exposed portion, and is particularly preferable in that heat treatment is simple.
- the heat treatment is preferably carried out at the same or higher temperature as the drying step for 1 minute to several hours. Specifically, the temperature is 60 to 180 ° C, more preferably 90 to 170 ° C.
- the curing degree ratio varies depending on the exposure dose and the processing conditions for promoting curing, but is preferably 0.98 or less. Even more preferred Or 0.97 or less.
- the treatment for promoting curing is not performed (curing ratio 1, GOO)
- a negative image is formed for a moment in the early stage of development, but disappears soon.
- Removal is performed by peeling, dissolving, etching or the like. Specific examples include mechanical peeling, plasma etching, and a method using a developing solution, and a method using a developing solution is particularly preferable because it is simple.
- an aqueous solution containing 0.5 to 30% by weight of an amino alcohol and an alcohol other than amino alcohols, or an aqueous solution of organic ammonium hydroxide is preferable.
- Amino alcohols include monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, dimethylaminoamine, triisopropanolamine, and 2-hydroxyamine.
- Examples include, but are not limited to, droxymethylaminoethanol, N-isobutylgenolamine, 2-aminocyclohexanol, 2-aminomethylcyclohexanol, and the like. Preference is given to monoethanolamine, jetanolamine and isopropanolamine.
- the content of the amino alcohol is preferably 0.5 to 30% by weight in the developer. More preferably, it is 1.5 to 20% by weight. If the content is less than 0.5% by weight, the development time greatly varies depending on the type of the positive photosensitive polyimide precursor, drying conditions and exposure conditions, and the process becomes unstable. . In particular, when the thickness of the photosensitive polyimide precursor film is large, the development is difficult to proceed, and the development time is significantly increased. On the other hand, if it exceeds 30% by weight, there is a disadvantage that the developing time is too fast, and there is a problem that it is difficult to control the developing time.
- Alcohols other than amino alcohols include organic ammonium hydroxide aqueous solution such as tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, and colline aqueous solution, sodium hydroxide aqueous solution, water
- organic ammonium hydroxide aqueous solution such as tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, and colline aqueous solution, sodium hydroxide aqueous solution, water
- examples include an aqueous solution of potassium oxide, an aqueous solution of barium hydroxide, an aqueous solution of lithium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of barium carbonate, an aqueous solution of lithium carbonate, and the like.
- an aqueous tetramethylammonium hydroxide solution is an aqueous solution of organic ammonium hydroxide such as an aqueous solution of tetraethylammonium hydroxide and an aqueous solution of choline.
- organic ammonium hydroxide such as an aqueous solution of tetraethylammonium hydroxide and an aqueous solution of choline.
- the concentration of the alkali other than the amino alcohols in the developer is preferably 0.5 to 15% by weight. More preferably, it is 1.5 to 10% by weight.
- concentration is less than 0.5% by weight, the development of the photosensitive polyimide precursor hardly progresses.
- concentration exceeds 15% by weight, the development is accelerated, and it becomes difficult to control the development time. . In addition, it also dissolves the unexposed portions that should remain, making it difficult to form a good positive pattern.
- the aqueous solution of organic ammonium hydroxide can be used as a developer even when it is not mixed with amino alcohols.
- the aqueous solution of organic ammonium hydroxide is generally used in the field of positive photoresist, for example, an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of tetraethylammonium hydroxide, and an aqueous solution of choline.
- the concentration of the aqueous solution is preferably 0.05 to 15% by weight.
- NMD-3 (a 2.38% aqueous solution of tetramethylammonium hydroxide) manufactured by Tokyo Ohka Kogyo Co., Ltd. can be used.
- the developer according to the present invention may contain additional components as long as the effects of the present invention are not impaired.
- the water is preferably washed with an alcohol such as methanol, ethanol or isopropyl alcohol.
- an alcohol such as methanol, ethanol or isopropyl alcohol.
- the polyimide precursor is imidized by pressing to obtain a polyimide insulating film: After development, the temperature is selected and the temperature is increased stepwise or a certain temperature range is continuously selected. Do not raise temperature: Perform for 5 minutes to 5 hours.
- the maximum temperature of the curing is preferably 250 to 500 ° C, and more preferably, 300 to 450 ° C.
- heat treatment is performed at 130 ° C., 200 ° C., and 400 ° C., respectively, for 30 minutes.
- the temperature may be raised linearly from room temperature to 400 ° C. over 2 hours.
- Example 1 the present invention will be specifically described based on examples, but the present invention is not limited thereto.
- Example 1 the present invention will be specifically described based on examples, but the present invention is not limited thereto.
- the polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 60 at 30 minutes in a nitrogen atmosphere to form a film having a thickness of 5.28 m.
- a UV exposure machine PLA-501F manufactured by Canon Inc. exposure was performed at 100 OmJ / cm 2 (ultraviolet intensity of 365 nm) through a chrome photomask.
- a heat treatment was performed for 3 minutes at 140 ° C. on a hot plate to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a thickness of 13 jum
- the exposed film had a thickness of 4.42 jt / m
- the degree of cure was 0.934.
- Example 1 without heat treatment after exposure (curing degree ratio: 1.000), when immersed in a developing solution consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, the unexposed portion was dissolved. However, a negative image with the exposed portion remaining was temporarily formed, but as the development proceeded, the unexposed portion and the exposed portion were dissolved, and a force that could not form a positive pattern was applied.
- Example 2 To the polymer solution obtained in Example 1 was added 23.6 g of 1-phenylpropanedione-2- (0-ethoxycarbonyl) oxime, 339.23.36 g of "coumarin” of Kodak Co., Ltd. An actinic radiation-sensitive polyimide precursor composition was prepared by adding 315 g of tonnes and an equivalent (71.08 g) to all carboxyl groups in the polymer.
- This polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 80 ° C. for 3 minutes using a hot plate to form a 5. jt / m-thick polyimide precursor coating.
- Kyano emissions Ltd. UV exposure machine PLA-5 with 0 1 F, l OOO m J Zc m 2 (365 nm intensity of ultraviolet light) through a chrome follower Thomas click exposed.
- a heat treatment was performed for 3 minutes at 140 ° C. using a hot plate to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a thickness of 4.30 m
- the exposed film had a film thickness of 4.64 // m, and the degree of cure was 0.927.
- Example 2 To the polymer solution obtained in Example 1 were added 23.6 g of 3-phenyl-5-isoxazolone, 2.36 g of 3,3′-carbonylbis (decylaminocoumarin), 315 g of 7-butyrolactone and 315 g of diacetone acrylic.
- An actinic radiation-sensitive polyimide precursor composition was prepared by adding an amide in an equivalent amount (169.22 g) to all carboxyl groups in the polymer.
- the polyimide precursor composition was applied on a 4-inch silicon wafer and dried at 80 ° C. for 3 minutes by a hot plate to form a 6.83 m-thick polyimide precursor coating.
- Kyano emissions Ltd. UV exposure machine PLA-5 with 0 1 F, l OO Om J Zc m 2 (365 nm intensity of ultraviolet light) through a chrome follower Thomas click exposed.
- a heat treatment was performed for 3 minutes at 140 ° C. using a hot plate to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a film thickness of 4.54 // m
- the exposed film had a film thickness of 5.51 m
- the degree of cure was 0.823.
- it was immersed in a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide and rinsed with water, and then nitrogen-blown to form a positive polyimide pattern.
- the polyimide precursor composition was applied on a 4-inch silicon wafer and dried at 80 ° C. for 3 minutes by a hot plate to form a 4.55 m-thick polyimide precursor coating.
- a UV exposure machine PLA-501F manufactured by Canon Inc. exposure was performed through a chrome photomask at 1,000 mJZcm 2 (ultraviolet intensity of 365 nm).
- a heat treatment was performed on a hot plate at 140 ° C. for 3 minutes to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a thickness of 3.61 ⁇ m
- the exposed film had a thickness of 4.44 m
- the degree of cure was 0.813.
- Example 1 In Example 1, 141. ⁇ g of acryloylmorpholine was added instead of methylacrylamide to prepare an actinic ray-sensitive polyimide precursor composition.
- the polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 80 ° C. for 3 minutes using a hot plate to form a polyimide precursor coating film having a thickness of 4.54 // m.
- a hot plate Using Kyano emissions Co. ultraviolet exposure machine Yu LA- 50 1 F, (UV intensity of 365 nm) l OO Om J Zcm 2 via the chrome follower Thomas click exposed.
- a heat treatment was performed for 3 minutes at 140 ° C. on a hot plate to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a thickness of 3.55 m and the exposed film had a thickness of 4.02 m, and the degree of cure was 0.883.
- it was immersed and developed in a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsed with water, and then blown with nitrogen to form a positive-type image polyimide pattern.
- Example 1 N-isopropylacrylamide was used instead of methacrylamide. was added to prepare an actinic radiation-sensitive polyimide precursor composition.
- This polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 80 ° C. for 3 minutes using a hot plate to form a polyimide precursor film having a thickness of 5.18 // m.
- a UV exposure machine PLA-501F manufactured by Canon Inc. exposure was carried out through a chrome photomask using lOO Om JZcm 2 (ultraviolet intensity of 365 nm).
- a heat treatment was performed for 3 minutes at 140 ° C. on a hot plate to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a thickness of 4.12 zm
- the exposed film had a thickness of 4.44 m
- the degree of cure was 0.928.
- Example 1 59.07 g of acetamide and 260.0 g of 2-hydroxyshethyl methacrylate were added in place of methamide and amide to prepare an actinic ray-sensitive polyimide precursor composition.
- the polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 80 at a hot plate for 3 minutes to form a polyimide precursor film having a thickness of 5.44 m.
- a UV exposure machine PLA-501F manufactured by Canon Inc. exposure was carried out through a chrome photomask using a lOO Om JZcm 2 (ultraviolet intensity of 365 nm).
- a heat treatment was performed on a hot plate at 140 ° C. for 3 minutes to obtain a positive photosensitive polyimide precursor coating.
- the unexposed film had a thickness of 3.96 m
- the exposed film had a thickness of 4.38 / zm
- the degree of cure was 0 905.
- it was immersed and developed in a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide and rinsed with water, followed by nitrogen blow to form a positive polyimide pattern.
- This photosensitive polyimide precursor composition is applied on a 4-inch silicon wafer and dried at 60 ° C for 30 minutes in a nitrogen atmosphere to form a 4.72 m-thick photosensitive polyimide precursor coating.
- Example 8 without heat treatment after exposure, when immersed in a developing solution composed of a 2.38% aqueous solution of tetramethylammonium hydroxide, the unexposed portion was dissolved and the exposed portion remained ( (Negative type) was formed at the time, but as the development proceeded, both the unexposed and exposed portions dissolved, and a pattern could not be formed.
- Example 8 To the polymer (A) solution obtained in Example 8 was added 47.27 g of 3-phenyl-5-isoxazolone, 2.36 g of 3,3′-carbonylbis (decylaminocoumarin), 190 g of N-methyl-1-pyrrolidone and Dimethylaminoethyl acetate in polymer An actinic radiation-sensitive polyimide precursor composition was prepared in which trimethylolpropane trimethacrylate was added in an amount equivalent to the ropoxyl group at 15% relative to the polymer.
- This photosensitive polyimide precursor composition was applied to a 4-inch silicon wafer, and dried at 80 ° C for 3 minutes on a hot plate to form a 5.000 m thick polyimide precursor coating.
- a UV exposure machine PLA-501F manufactured by Canon Inc. the film was exposed through a chrome photomask to 2000 mJZcm 2 (ultraviolet intensity of 365 nm). After exposure, heat treatment was performed at 140 ° C for 3 minutes using a hot plate. By this treatment, the unexposed film had a thickness of 3.90 m, the exposed film had a thickness of 4.02 jt / m, and the degree of cure was 0.970.
- a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsed with water, and blown with nitrogen to obtain a positive image.
- This polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 80 ° C. for 3 minutes by a hot plate to form a polyimide precursor film having a thickness of 5.0000 / m.
- SOO Om JZcm 2 (ultraviolet light intensity of 365 nm) was exposed through a chromium photomask using an ultraviolet exposure apparatus PLA-501F manufactured by Canon Inc. After exposure, heat treatment was performed for 3 minutes at 140 ° C using a hot plate. As a result of this treatment, the unexposed film had a thickness of 3.88 m, the exposed film had a thickness of 4.03 m, and the degree of cure was 0.963. Next, it was immersed and developed in a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsed with water, and blown with nitrogen to obtain a positive image.
- Example 13 instead of N-phenylglycine and 3,3'-carbonylbis (getylaminocoumarin), 5.25 g of Michler's ketone was added to prepare an actinic radiation-sensitive polyimide precursor composition. did.
- This polyimide precursor composition was applied on a 4-inch silicon wafer and dried at 80 ° C for 3 minutes by a hot plate to form a polyimide precursor film having a thickness of 5.00 m.
- a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsed with water, and blown with nitrogen to obtain a positive image.
- an actinic ray-sensitive polyimide precursor composition was prepared in which dimethylaminopropylmethacrylamide was added in an equivalent amount to all carboxyl groups and 2-hydroxylethyl methacrylate was added in an amount of 10% to the polymer.
- This polyimide precursor composition was applied on a 4-inch silicon wafer, and dried at 80 ° C for 3 minutes by a hot plate to form a 5.00 m-thick polyimide precursor coating.
- a UV exposure machine PLA-501F manufactured by Canon Inc. exposure was performed through a chrome photomask at 60 Om J / cm 2 (ultraviolet intensity of 365 nm). After exposure, heat treatment was performed on a hot plate at 130 ° C for 7 minutes. As a result of this treatment, the unexposed film had a film thickness of 3.64) ⁇ m, and the exposed film had a film thickness of 4.
- the curing degree ratio was 0.888.
- it was immersed and developed in a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsed with water, and blown with nitrogen to obtain a positive image.
- a developer consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide
- This polyimide precursor composition was applied to a 4-inch silicon wafer treated with Toray Co., Ltd.'s adhesion modifier AP-400, and dried in a dryer at 60 ° C for 30 minutes to obtain a 5.00 m film thickness polyimide.
- a precursor coating was formed.
- the film was exposed to 100 Om JZcm 2 (ultraviolet light intensity of 365 nm) through a chrome photomask using an ultraviolet exposure apparatus PLA-501F manufactured by Canon Inc. After the exposure, heat treatment was performed on a hot plate at 120 ° C for 15 minutes. As a result of this treatment, the unexposed film had a thickness of 3.74 jum, the exposed film had a film thickness of 4.19 jum, and the degree of cure was 0.893. Next, it was immersed and developed in a developer consisting of a 5% aqueous solution of choline, rinsed with water, and blown with nitrogen to obtain a positive image.
- Reference example 1
- a developer for actinic radiation-sensitive polyimide precursor containing 15% by weight of monoethanolamine in the aqueous solution having a concentration of tetramethylammonium hydroxide of 2.5% by weight was prepared.
- the actinic radiation-sensitive polyimide precursor composition (A) obtained in Reference Example 1 was spin-coated on a 4-inch silicon wafer, and dried in an oven at 60 ° C for 30 minutes. went. At this time, the film thickness was 6.4 ⁇ m. Thereafter, exposure was performed at 200 mJZcm 2 at a wavelength of 365 nm using a contact mask liner PLA-501F manufactured by Canon Inc. through a chrome photomask. After the exposure, a heat treatment was performed on a hot plate at 140 ° C. for 3 minutes. The sample was immersed in the developing solution, rinsed with water, and dried by blowing with nitrogen.
- Example 17 was repeated except that a developer for actinic ray-sensitive polyimide precursor containing 15% by weight of monoethanolamine was used in the aqueous solution having a choline concentration of 5% by weight.
- the pattern processing was performed under exactly the same conditions as described above.
- the pattern processing was performed under exactly the same conditions as in Example 17 except that the film thickness after application and drying of the actinic ray-sensitive polyimide precursor composition (A) obtained in Reference Example 1 was changed to 12.3 m. I got it.
- the through hole of 20 / m was completely resolved, and uniform resolution was obtained from the center to the periphery of the wafer.
- the film thickness after development was 11.5 / zm, and the film thickness retention ratio was 94% better than the film thickness before development.
- a pattern was processed under the same conditions as in Example 17 except that the actinic ray-sensitive polyimide precursor composition (B) obtained in Reference Example 2 was used.
- a pattern was processed under the same conditions as in Example 17 except that the actinic ray-sensitive polyimide precursor composition (C) obtained in Reference Example 3 was used.
- the positive type polyimide insulating film obtained by the method of the present invention is used as a passivation film of a semiconductor, a protective film of a semiconductor element, and an interlayer insulating film of a multilayer wiring for high-density mounting.
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94905210A EP0634698A4 (en) | 1993-02-03 | 1994-01-26 | PROCESS FOR FORMING A POSITIVE POLYIMIDE PATTERN. |
US08/692,337 US5614354A (en) | 1993-02-03 | 1994-01-26 | Method of forming positive polyimide patterns |
KR1019940703469A KR950701093A (ko) | 1993-02-03 | 1994-10-01 | 포지형 폴리이미드패턴의 형성방법(a method of forming positive polyimide patterns) |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1630293 | 1993-02-03 | ||
JP5/16302 | 1993-02-03 | ||
JP5/63894 | 1993-03-23 | ||
JP06389493A JP3319004B2 (ja) | 1993-02-03 | 1993-03-23 | ポジ型ポリイミドパターンの形成方法 |
JP5/90130 | 1993-04-16 | ||
JP9013093A JP3303416B2 (ja) | 1993-04-16 | 1993-04-16 | 感光性ポリイミド前駆体用現像液 |
Publications (1)
Publication Number | Publication Date |
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WO1994018607A1 true WO1994018607A1 (en) | 1994-08-18 |
Family
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1994/000104 WO1994018607A1 (en) | 1993-02-03 | 1994-01-26 | Process for forming positive polyimide pattern |
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US (1) | US5614354A (ja) |
KR (1) | KR950701093A (ja) |
WO (1) | WO1994018607A1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US6403289B1 (en) | 1997-10-31 | 2002-06-11 | Nippon Zeon Co., Ltd. | Developer for photosensitive polyimide resin composition |
US6887916B2 (en) | 2000-12-28 | 2005-05-03 | Kimberly-Clark Worldwide, Inc. | Materials having controlled shrinkage and patterns and methods of making same |
US7499125B2 (en) * | 2004-01-28 | 2009-03-03 | Kent State University | Method of fabricating electro-optical devices with polymer-stabilized liquid crystal molecules |
KR100764375B1 (ko) * | 2005-12-15 | 2007-10-08 | 주식회사 하이닉스반도체 | 반도체 소자의 하드마스크용 고분자 및 이를 함유하는조성물 |
CN110462514B (zh) * | 2017-03-29 | 2023-12-15 | 富士胶片株式会社 | 感光性树脂组合物、固化膜、层叠体、固化膜的制造方法及半导体器件 |
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JPS6461747A (en) * | 1987-09-01 | 1989-03-08 | Mitsubishi Electric Corp | Positive type photosensitive heat-resisting material |
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JPS59160139A (ja) * | 1983-03-04 | 1984-09-10 | Hitachi Ltd | 感光性重合体組成物 |
DE3660339D1 (en) * | 1985-01-15 | 1988-07-28 | Merck Patent Gmbh | Photoresist compositions with enhanced sensitivity using polyamide esters |
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DE69030484T2 (de) * | 1989-11-30 | 1997-08-28 | Sumitomo Bakelite Co | Fotoempfindliche Harzzusammensetzung |
US5114826A (en) * | 1989-12-28 | 1992-05-19 | Ibm Corporation | Photosensitive polyimide compositions |
JPH0415226A (ja) * | 1990-05-10 | 1992-01-20 | Chisso Corp | ヒドロキシフェニル基を有する感光性耐熱重合体 |
DE69128187T2 (de) * | 1990-09-28 | 1998-03-26 | Toshiba Kawasaki Kk | Fotoempfindliche Harzzusammensetzung zum Herstellen eines Polyimidfilmmusters und Verfahren zum Herstellen eines Polyimidfilmmusters |
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- 1994-01-26 WO PCT/JP1994/000104 patent/WO1994018607A1/ja not_active Application Discontinuation
- 1994-01-26 US US08/692,337 patent/US5614354A/en not_active Expired - Fee Related
- 1994-10-01 KR KR1019940703469A patent/KR950701093A/ko not_active Application Discontinuation
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JPS62135824A (ja) * | 1985-12-05 | 1987-06-18 | インタ−ナショナル ビジネス マシ−ンズ コ−ポレ−ション | フオトレジスト組成物 |
JPS62145239A (ja) * | 1985-12-19 | 1987-06-29 | Mitsubishi Electric Corp | ポジ型感光性耐熱材料 |
JPS6461747A (en) * | 1987-09-01 | 1989-03-08 | Mitsubishi Electric Corp | Positive type photosensitive heat-resisting material |
JPH02126974A (ja) * | 1988-06-23 | 1990-05-15 | Toray Ind Inc | ポリイミド積層膜の製造方法 |
JPH02135449A (ja) * | 1988-09-26 | 1990-05-24 | Internatl Business Mach Corp <Ibm> | パターンを形成する方法及びポジテイブ型ポリイミドを生成する方法 |
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US5614354A (en) | 1997-03-25 |
KR950701093A (ko) | 1995-02-20 |
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