WO2017038828A1 - Composition de résine photosensible de type positif, motif de résine non durci formé avec ladite composition de résine, motif de résine durci, dispositif semi-conducteur l'utilisant, et son procédé de fabrication - Google Patents

Composition de résine photosensible de type positif, motif de résine non durci formé avec ladite composition de résine, motif de résine durci, dispositif semi-conducteur l'utilisant, et son procédé de fabrication Download PDF

Info

Publication number
WO2017038828A1
WO2017038828A1 PCT/JP2016/075352 JP2016075352W WO2017038828A1 WO 2017038828 A1 WO2017038828 A1 WO 2017038828A1 JP 2016075352 W JP2016075352 W JP 2016075352W WO 2017038828 A1 WO2017038828 A1 WO 2017038828A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
semiconductor device
resin
resin composition
general formula
Prior art date
Application number
PCT/JP2016/075352
Other languages
English (en)
Japanese (ja)
Inventor
馬場修
亀本聡
奥田良治
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN201680049884.7A priority Critical patent/CN107924125B/zh
Priority to JP2016555372A priority patent/JP6760073B2/ja
Priority to KR1020187006706A priority patent/KR102542820B1/ko
Publication of WO2017038828A1 publication Critical patent/WO2017038828A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond

Definitions

  • the present invention relates to a positive photosensitive resin composition, an uncured resin pattern formed from the resin composition, a cured resin pattern, a semiconductor device using the same, and a method for manufacturing the same.
  • the present invention relates to a positive photosensitive resin composition that is suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.
  • organic electroluminescence device insulation layer and TFT substrate flattening film For semiconductor device surface protection film and interlayer insulation film, organic electroluminescence device insulation layer and TFT substrate flattening film, polyimide resin, polybenzoxazole resin, polyamideimide resin with excellent heat resistance and mechanical properties, etc. Resins are widely used. Conventionally, a coating film is first formed in the state of a heat-resistant resin precursor having high solubility in an organic solvent, and then a desired pattern is formed using a photoresist based on a novolak resin or the like. A method has been adopted in which the body is heat-cured to obtain an insoluble and infusible heat-resistant resin.
  • the photoresist process has been simplified by using a negative-type or positive-type photosensitive resin composition that itself can be processed to form a desired pattern.
  • a positive photosensitive resin composition (see Patent Document 1) containing an alkali-soluble resin, a photosensitive agent, and a thermal base generator, a hydroxystyrene resin, a specific phenol resin, and a photoacid generator, A positive photosensitive resin composition containing a solvent (see Patent Document 2), an alkali-soluble resin, a photoacid generator, and a solvent, having a glass transition temperature after curing of 200 ° C. or higher and an internal stress of 40 MPa or less.
  • Type photosensitive resin compositions (see Patent Document 3) have been proposed.
  • JP 2013-152381 A (page 1-2) JP 2014-211151 A (page 1-3) Japanese Patent Laying-Open No. 2015-7675 (page 1-3)
  • the O 2 ashing process is performed before the electroless plating process, and the residue in the pad opening is removed.
  • the present invention has been made in view of the above problems, and is highly sensitive to i-line of a mercury lamp, excellent in chemical resistance to strong acidic aqueous solution and strong alkaline aqueous solution, and particularly in an electroless plating process that has undergone O 2 ashing. It is an object to provide a positive photosensitive resin composition capable of obtaining a cured resin pattern having excellent adhesion reliability with a pad, a resin pattern using the resin composition, and a method for producing a semiconductor using the same. .
  • the positive photosensitive resin composition of the present invention has the following constitution. [1] containing (a) an alkali-soluble resin, and (b) a quinonediazide compound, wherein (a) the alkali-soluble resin is (A1)
  • the content of the tetracarboxylic acid represented by the general formula (1) is 5 to 50 mol% in the total tetracarboxylic acid residues, and the diamine residue represented by the general formula (2) is all diamines.
  • a positive photosensitive resin composition comprising:
  • A represents a tetravalent monocyclic or bicyclic aromatic hydrocarbon group containing no hetero atom, and two or more types may be used.
  • B represents a group selected from O, S, SO 2 , CH 2 , CH (CH 3 ), C (CH 3 ) 2 , and C (CF 3 ) 2 , Two or more types may be used.
  • the solution is an electrolytic plating solution or an electroless plating solution
  • the method for manufacturing a semiconductor device according to [13] further including a step of plating growth of a first type of metal or alloy and a step of plating growth of a second type of metal or alloy different from the first type.
  • the positive photosensitive resin composition of the present invention is highly sensitive to i-line and excellent in chemical resistance against strong acidic aqueous solution and strong alkaline aqueous solution. In particular, it is in close contact with an aluminum pad even in an electroless plating process after O 2 ashing. A resin pattern having excellent reliability and a semiconductor using the resin pattern can be obtained.
  • the positive photosensitive resin composition of the present invention contains (a) an alkali-soluble resin and (b) a quinonediazide compound, and the (a) alkali-soluble resin is represented by (a1) the general formula (1). Having 5-50 mol% of tetracarboxylic acid residues in all tetracarboxylic acid residues, and 10-80 mol% of diamine residues represented by the general formula (2) in all diamine residues, Further, it contains a polyimide precursor having 10 to 90 mol% of the diamine residues represented by the general formula (3) and / or (a2) a polyimide corresponding to the above (a1).
  • the polyimide corresponding to (a1) represents one in which (a1) is closed to become a polyimide.
  • a polyimide precursor having a structure of (a1) and / or a polyimide having a structure of (a2) will be referred to as “a polyimide of (a1,2) (precursor)”, and “polyimide precursor and / or Or “polyimide” is expressed as “polyimide (precursor)”, and the residues of tetracarboxylic acid and diamine constituting “polyimide (precursor) of (a1,2)” are represented by “(a1,2)”. This is expressed as “monomer residue of polyimide (precursor)”.
  • the residue of tetracarboxylic acid represented by polyimide Formula contained in the (precursor) (1) of the (a1,2) does not include the rigid and the other functional groups, the resin film during O 2 ashing It is thought that surface oxidation is suppressed, and this suppresses deterioration of chemical resistance after O 2 ashing.
  • the tetracarboxylic acid residue represented by the general formula (1) is contained in an amount of 5 mol% or more in all tetracarboxylic acid residues from the viewpoint of expressing the effect of suppressing the surface oxidation of the resin film during O 2 ashing. Preferably, it is contained in an amount of 7 mol% or more, more preferably 9 mol% or more. On the other hand, from the viewpoint of maintaining high sensitivity, it is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less in the total tetracarboxylic acid residues. Any tetracarboxylic acid residue other than that represented by the general formula (1) may be used.
  • a diamine having a higher molecular weight was used because the residue of the diamine represented by the general formula (2) contained in the polyimide (precursor) of (a1, 2) was a dinuclear body and a relatively low molecular weight.
  • the ratio of the imide (precursor) unit of the entire polyimide (precursor) resin (a1,2) compared to the case is kept high, which is the same as the residue of the general formula (1) during O 2 ashing. It is thought to suppress the surface oxidation of the film, thereby suppressing the deterioration of chemical resistance after O 2 ashing.
  • the residue of the diamine represented by the general formula (2) also has the effect of suppressing light absorption by breaking the ⁇ -conjugated system of two benzene rings in the molecule, and the sensitivity during exposure is reduced. Suppressed, these contribute to both chemical resistance and high sensitivity after O 2 ashing.
  • Residues of diamine represented by the general formula (2) from the viewpoint of expressing surface oxidation inhibiting effect of the resin film during O 2 ashing, it is preferable to contain 10 mol% or more on the total diamine residues, More preferably, it is contained in an amount of 12 mol% or more, more preferably 15 mol% or more. On the other hand, from the viewpoint of maintaining high sensitivity, it is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, and particularly preferably 50 mol% or less in all diamine residues.
  • Residue of diamine represented by the general formula (3) contained in the polyimide (precursor) of (a1,2) is moderately alkaline developable and organic solvent for the polyimide (precursor) of resin (a1,2) Adding the solubility increases the sensitivity of the positive photosensitive resin composition and improves the storage stability.
  • the diamine residue represented by the general formula (3) is preferably contained in an amount of 10 mol% or more in the total diamine residues from the viewpoint of expressing the effects of increasing sensitivity and improving storage stability, It is more preferably contained, more preferably 20 mol% or more, and particularly preferably 25 mol% or more.
  • it is preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, in all diamine residues, 75 A mol% or less is particularly preferred.
  • the total amount of the diamine residue represented by the general formula (2) and the diamine residue represented by the formula (3) is based on the total diamine residue. 20 to 100 mol%. By being 20 mol% or more, it becomes possible to suppress high sensitivity and deterioration of chemical resistance after O 2 ashing. From this viewpoint, it is preferably 30 mol% or more, more preferably 35 mol% or more, Preferably it is 40 mol% or more.
  • A represents a tetravalent monocyclic or bicyclic aromatic hydrocarbon group not containing a hetero atom.
  • aromatic hydrocarbon groups include, but are not limited to, groups derived from a benzene ring, a cyclotetradecaheptaene ring, a cyclooctadecanaene ring, a naphthalene ring, and an azulene ring.
  • groups derived from a benzene ring, a naphthalene ring, and an azulene ring are preferably used from the viewpoint of chemical stability.
  • Preferred examples of the general formula (1) include, but are not limited to, the following (A-1) group structure, and two or more of these may be used.
  • particularly preferable structures include the structures of the following group (A-2), and two or more of these may be used.
  • B is O, S, SO 2 , CH 2 , CH (CH 3 ), C (CH 3 ) 2 , C A group selected from (CF 3 ) 2 is represented, and two or more of these may be used.
  • Preferred examples of B include O, S, SO 2 , CH 2 and C (CF 3 ) 2 , and particularly preferred examples include O, S, SO 2 and CH 2 .
  • examples include, but are not limited to, phenolic resins such as polyhydroxystyrene and resole. These include (a1,2) polyimide (precursor).
  • the polyimide (precursor) of (a1, 2) may be a copolymer of these resins. Two or more of these resins may be contained.
  • the content thereof is 60% of the total amount of (a) alkali-soluble resin in order to maintain chemical resistance after O 2 ashing. It is preferably at most mass%, more preferably at most 50 mass%, further preferably at most 45 mass%.
  • a phenol group resin such as carboxyl group-containing resin, novolak, polyhydroxystyrene, and resol has low chemical resistance after O 2 ashing, and therefore the preferred amount used is (a) 45% by mass of the entire alkali-soluble resin.
  • it is more preferably 40% by mass or less, and further preferably 35% by mass or less.
  • polyimide precursor preferably used as the (a) alkali-soluble resin of the present invention examples include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide and the like.
  • the polyamic acid can be obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride and the like with a diamine, a corresponding diisocyanate compound, and a trimethylsilylated diamine.
  • a part of the diamine may be replaced with a monoamine which is an end-capping agent, and similarly, a part of tetracarboxylic dianhydride is an acid anhydride or a mono-acid chloride which is an end-capping agent.
  • a compound or a monoactive ester compound may be substituted.
  • the polyamic acid ester is prepared by a method using tetracarboxylic acid diester dichloride instead of tetracarboxylic acid in the above method, or N, N-dimethylformamide dimethyl acetal, N, N for the polyamic acid obtained by the above method.
  • the polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment such as acid or base.
  • Examples of tetracarboxylic acids corresponding to preferred tetracarboxylic acid residues contained in the polyimide (precursor) of the alkali-soluble resin include, in addition to the structure of the group (A-1), 3, 3 ′, 4, 4'-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetra Carboxylic acid, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) Hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-bis
  • diamines corresponding to preferred diamine residues contained in the polyimide (precursor) of the alkali-soluble resin include, in addition to diamines having the structures of the general formulas (2) and (3), 2,2- Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino -4-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) ether, 3,3'-diamino-4,4'-biphenol, 9,9-bis (3-amino-4-hydroxyphenyl) Hydroxyl group-containing diamines such as fluorene and sulfonic acid groups such as 3-sulfonic acid-4,4′-diaminodiphenyl ether Thiol group-containing diamines such as diamine and dimercaptophenylenedi
  • diamines can be used as they are or as the corresponding diisocyanate compounds and trimethylsilylated diamines. These two or more diamines may be used in combination.
  • an aromatic diamine in an amount of 50 mol% or more of the total diamine.
  • the polyimide (precursor) resin of the alkali-soluble resin has a main chain terminal at the monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound. It is preferable to seal with a terminal blocking agent such as a monoactive ester compound.
  • the introduction ratio of the monoamine used as the end-capping agent is preferably at least 0.1 mol%, particularly preferably at least 5 mol%, based on the total amine component.
  • the molecular weight of the polyimide (precursor) is preferably 60 mol% or less, particularly preferably 50 mol% or less, in terms of maintaining a high molecular weight.
  • the introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, more preferably 5 mol%, relative to the diamine component. Further, it is preferably 100 mol% or less, more preferably 90 mol% or less.
  • a plurality of different end groups may be introduced by reacting a plurality of end-capping agents.
  • monoamines having at least one alkenyl group or alkynyl group acid anhydrides, monocarboxylic acids, monoacid chloride compounds, Mono-active ester compounds can also be used.
  • the end-capping agent introduced into the resin can be easily detected by the following method.
  • a resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid component, which are constituent units of the resin, and this is decomposed into gas chromatography (GC) or nuclear magnetic resonance (NMR).
  • GC gas chromatography
  • NMR nuclear magnetic resonance
  • the terminal blocking agent is introduced resin directly, it is possible to detect by pyrolysis gas chromatography (PGC) or infrared spectrum and 13 C-NMR spectrum measurement.
  • RIM an imide ring cyclization rate molar ratio of units imide ring closure to all the imide (precursor) unit (R IM (%)) and by defining, R IM Can be preferably used in the whole range of 0% to 100%.
  • RIM is preferably 3% or more, more preferably 5% or more from the viewpoint of increasing storage stability, and preferably 70% or less, more preferably 50%, from the viewpoint of increasing sensitivity. Hereinafter, it is more preferably 25% or less.
  • carboxyl groups As for the polyamic acid ester used as alkali-soluble resin, all of the carboxyl groups may be esterified, or only some of the carboxyl groups may be esterified.
  • carboxyl group refers to a carboxyl group other than the carboxyl residue that constitutes the amide of the main chain of the polyamic acid corresponding to the polyamic acid ester that is neither esterified nor imide-cyclized.
  • R E is preferably It is 20% or more, more preferably 25% or more, preferably 100% or less, more preferably 95% or less.
  • the ester group of the polyamic acid ester used as the alkali-soluble resin can be expressed as COO-R 1 .
  • R 1 represents a monovalent organic group having 1 to 10 carbon atoms.
  • R 1 include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group, trimethylsilyl group. , Triethylsilyl group and the like, but not limited thereto, and two or more of them may be used.
  • the positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound.
  • a quinonediazide compound By containing the quinonediazide compound, an acid is generated in the ultraviolet-exposed area, and the solubility of the exposed area in an alkaline aqueous solution is increased. Therefore, a positive pattern can be obtained by alkali development after the ultraviolet exposure.
  • the (b) quinonediazide compound used in the present invention may contain two or more quinonediazide compounds. Thereby, the ratio of the dissolution rate of the exposed part and the unexposed part can be increased, and a highly sensitive positive photosensitive resin composition can be obtained.
  • Examples of the (b) quinonediazide compound used in the present invention include those in which a sulfonic acid of quinonediazide is ester-bonded to a polyhydroxy compound, a sulfonic acid of quinonediazide to a sulfonamide bond to a polyamino compound, and a quinonediazide to a polyhydroxypolyamino compound.
  • Examples of the sulfonic acid include ester bonds and / or sulfonamide bonds.
  • the quinonediazide compound is preferably either a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group.
  • a compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.
  • the (b) quinonediazide compound used in the present invention can be synthesized by a known method. For example, there is a method in which 5-naphthoquinonediazide sulfonyl chloride and a polyhydroxy compound are reacted in the presence of triethylamine.
  • the content of the (b) quinonediazide compound used in the present invention is preferably 1 to 60 parts by mass with respect to (a) 100 parts by mass of the alkali-soluble resin.
  • content of a quinonediazide compound is preferably 3 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less in order not to impair the mechanical properties of the cured resin pattern.
  • the positive photosensitive resin composition of the present invention preferably further contains (c) a thermal crosslinking agent.
  • a thermal crosslinking agent a compound having at least two alkoxymethyl groups and / or methylol groups and a compound having at least two epoxy groups and / or oxetanyl groups are preferably used, but are not limited thereto.
  • a condensation reaction is caused with (a) the alkali-soluble resin to form a crosslinked structure, and mechanical properties such as elongation of the cured resin pattern are improved.
  • two or more kinds of thermal cross-linking agents may be used, which enables a wider range of designs.
  • Preferred examples of the compound having at least two alkoxymethyl groups and / or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, T OM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP
  • Preferred examples of the compound having at least two epoxy groups and / or oxetanyl groups include, for example, bisphenol A type epoxy resins, bisphenol A type oxetanyl resins, bisphenol F type epoxy resins, bisphenol F type oxetanyl resins, propylene glycol diesters.
  • examples thereof include, but are not limited to, epoxy group-containing silicones such as glycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl (glycidyloxypropyl) siloxane.
  • EPICLON registered trademark
  • EPICLON HP-4032 EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA-859CRP, EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (above trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin ( Registered trademark) BEO-60E (trade name, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, A Co., Ltd.) EKA, Ltd.) and the like, are available from each company. Two or more of these may be contained.
  • the content of the (c) thermal crosslinking agent used in the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 10 parts per 100 parts by mass of the (a) alkali-soluble resin. From the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less.
  • the positive photosensitive resin composition of the present invention may contain a solvent as necessary.
  • the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol Ethers such as monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl Esters such as acetate, ethyl lactate and methyl lactate, alcohols such as diacetone alcohol and 3-methyl-3-methoxybutanol, aroma
  • the content of the solvent is preferably 70 parts by mass or more, more preferably 100 parts by mass or more with respect to (a) 100 parts by mass of the alkali-soluble resin, from the viewpoint of obtaining an appropriate film thickness.
  • the amount is preferably 1800 parts by mass or less, more preferably 1500 parts by mass or less.
  • the positive photosensitive resin composition of the present invention may contain a thermal acid generator as necessary.
  • a thermal acid generator By containing the thermal acid generator, a cured resin pattern having a high crosslinking rate, benzoxazole ring closure rate, and imide ring closure rate can be obtained even when firing at 150 to 300 ° C., which is lower than usual.
  • the content of the thermal acid generator preferable for the purpose of manifesting the effect is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the (a) alkali-soluble resin. From the viewpoint of maintaining mechanical properties such as elongation, it is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.
  • the positive photosensitive resin composition of the present invention may contain a low-molecular compound having a phenolic hydroxyl group as long as it does not reduce the shrinkage residual film ratio after curing.
  • a low-molecular compound having a phenolic hydroxyl group By containing the low molecular weight compound having a phenolic hydroxyl group, it is easy to adjust the alkali solubility during pattern processing.
  • the content of the low molecular weight compound having a phenolic hydroxyl group that is preferable for the purpose of manifesting the effect is preferably 0.1 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the (a) alkali-soluble resin. From the viewpoint of maintaining mechanical properties such as elongation, it is preferably 30 parts by mass or less, more preferably 15 parts by mass or less.
  • the positive photosensitive resin composition of the present invention is a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone for the purpose of improving the wettability with the substrate as necessary. , Ketones such as methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.
  • the preferable content of the compound used for the purpose of improving the wettability with these substrates is 0.001 part by mass or more with respect to 100 parts by mass of (a) the alkali-soluble resin, and from the viewpoint of obtaining an appropriate film thickness, Preferably it is 1800 mass parts or less, More preferably, it is 1500 mass parts or less.
  • the positive photosensitive resin composition of the present invention may contain inorganic particles.
  • Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like.
  • the primary particle size of these inorganic particles is preferably 100 nm or less, particularly preferably 60 nm or less.
  • Specific surface area is defined as the sum of the surface areas contained in a unit mass of powder.
  • a specific method for measuring the specific surface area is the BET method, which can be measured using a specific surface area measuring device (such as HM model 1201 manufactured by Mounttech).
  • silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane as long as storage stability is not impaired in order to enhance adhesion to the silicon substrate. May be.
  • the preferred content of the silane coupling agent used for enhancing the adhesion to these silicon substrates is (a) 0.01 parts by mass or more with respect to 100 parts by mass of the alkali-soluble resin, maintaining mechanical properties such as elongation. In view of the above, it is preferably 5 parts by mass or less.
  • the viscosity of the positive photosensitive resin composition of the present invention is preferably 2 to 5000 mPa ⁇ s.
  • the solid content concentration so that the viscosity is 2 mPa ⁇ s or more, it becomes easy to obtain a desired film thickness.
  • the viscosity is 5000 mPa ⁇ s or less, it becomes easy to obtain a highly uniform coating film.
  • a resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.
  • an uncured pattern formed from the positive photosensitive resin composition of the present invention is referred to as an uncured resin pattern, and a pattern obtained by curing this is referred to as a cured resin pattern.
  • a resin pattern the uncured resin pattern and the cured resin pattern are collectively referred to.
  • the substrate on which the resin pattern is formed is not particularly limited, but the positive photosensitive resin composition of the present invention is preferably used in a semiconductor device, and when used in such applications, a circuit is formed as the substrate. It is preferable to form a resin pattern on a semiconductor element such as a silicon wafer.
  • the positive photosensitive resin composition of the present invention is applied to a substrate.
  • a wafer made of silicon, ceramics, gallium arsenide, or the like on which a metal is formed as an electrode or wiring is used, but is not limited thereto.
  • the metal used as the electrode and wiring include, but are not limited to, aluminum (Al), Al—Si, Al—Si—Cu, and Cu.
  • the present invention provides a cured resin pattern having excellent adhesion reliability with an aluminum pad and a semiconductor using the same even in an electroless plating process after O 2 ashing, and thus a substrate on which an aluminum pad is formed.
  • a coating method for coating the positive photosensitive resin composition of the present invention on a substrate methods such as spin coating using a spinner, spray coating, and roll coating can be applied.
  • the film thickness at the time of application varies depending on the application method, the solid content concentration of the positive photosensitive resin composition, the viscosity, etc., but is usually applied so that the film thickness after drying is 0.1 to 150 ⁇ m. It is preferable.
  • the substrate can be pretreated with the above-mentioned silane coupling agent.
  • a silane coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate at a concentration of 0.5 to 20% by mass.
  • the solution is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like.
  • the substrate coated with the positive photosensitive resin composition is dried to obtain an uncured film (hereinafter also referred to as a pre-baked film) of the positive photosensitive resin composition. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at 50 to 150 ° C. for 1 minute to several hours.
  • exposure is performed by irradiating actinic radiation on the uncured film of the positive photosensitive resin composition through a mask having a desired pattern.
  • actinic radiation used for exposure there are ultraviolet rays, visible rays, electron beams, X-rays and the like.
  • i rays (365 nm), h rays (405 nm) and g rays (436 nm) of a mercury lamp are preferably used.
  • the exposed portion is removed using a developer to form an uncured resin pattern.
  • Developers include tetramethylammonium hydroxide, choline hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethyl
  • An aqueous solution of a compound exhibiting alkalinity such as aminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred.
  • these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-d
  • a predetermined temperature is applied and heat treatment is performed, and a thermal crosslinking reaction, an imide ring-closing reaction, and an oxazole ring-closing reaction are advanced to form a cured resin pattern.
  • This heat treatment is preferably carried out for 5 minutes to 5 hours while selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature.
  • heat treatment is performed at 150 ° C., 220 ° C., and 320 ° C. for 30 minutes each.
  • a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.
  • the preferred thickness of the cured resin pattern formed using the positive photosensitive resin composition of the present invention is 0.1 ⁇ m or more and 150 ⁇ m or less, but in order to obtain sufficient chemical resistance, more preferably 3.0 ⁇ m or more, More preferably, it is 4.0 ⁇ m or more, and particularly preferably 4.5 ⁇ m or more. In order to increase sensitivity and resolution, it is more preferably 15.0 ⁇ m or less, further preferably 8.0 ⁇ m or less, particularly preferably 7.0 ⁇ m or less. is there.
  • the cured resin pattern formed by the positive photosensitive resin composition of the present invention is used for a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, etc. Is preferably used.
  • an ashing process may be performed using a gas such as O 2 or Ar after the cured resin pattern is formed.
  • a gas such as O 2 or Ar
  • organic residue in the cured resin pattern opening can be removed, and for example, the connection reliability of the electrode pad can be improved.
  • the ashing treatment include, but are not limited to, plasma treatment, reactive ion etching (RIE), and reverse sputtering.
  • the cured resin pattern of the present invention is particularly excellent in chemical resistance after O 2 ashing, a strongly acidic liquid having a pH of 2 or less, a strong alkaline liquid having a pH of 12 or more, a flux solution, an electrolytic plating solution, and an electroless plating solution. It is used suitably for manufacture of a semiconductor including the process processed with 1 or more types of liquids selected from these.
  • strongly acidic liquids having a pH of 2 or lower include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, and the like.
  • the zinc layer after the first zincate treatment is removed in the double zincate treatment in which zinc plating is performed on the surface of the aluminum pad in two steps as a pretreatment in the electroless plating on the aluminum pad. In doing so, a strong acid such as dilute nitric acid is used.
  • strong alkaline liquids having a pH of 12 or more examples include sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution, barium hydroxide aqueous solution, tetramethylammonium hydroxide aqueous solution, choline hydroxide aqueous solution and the like. It is not limited to.
  • the zincate treatment liquid described later is also widely used as a strong alkaline liquid having a pH of 12 or more.
  • the flux liquid examples include, but are not limited to, rosin flux, organic water-soluble flux, inorganic water-soluble flux, and the like.
  • the electrolytic plating solution and the electroless plating solution in the present invention include a solution for temporarily growing a metal or an alloy as a pretreatment step.
  • the alloy described in the present invention refers to a metal-like material composed of a plurality of metal elements or a metal element and a non-metal element, and there are various modes such as a solid solution, a eutectic, and an intermetallic compound. include.
  • a zincate treatment performed before electroless nickel plating on an aluminum surface can be mentioned.
  • Examples of the metal or alloy plated with the electrolytic plating solution include, but are not limited to, copper, nickel, gold, Sn-Ag, and the like.
  • Examples of the metal or alloy to be plated with the electroless plating solution and its pretreatment solution include, but are not limited to, zinc, nickel, tin, gold, and palladium.
  • a metal or alloy is plated and grown using an electrolytic plating solution or an electroless plating solution
  • the treatment is performed one or more times immediately after that or with one or more other types of solutions.
  • the cured resin pattern of the present invention is particularly excellent in adhesion reliability with an aluminum pad even in an electroless plating process after O 2 ashing, when the resin pattern of the cured film has an opening, the opening of the cured resin pattern Preferably, at least one of the parts is disposed on top of a pad having aluminum or an aluminum alloy.
  • electroless nickel / displacement gold plating in such an arrangement, excellent adhesion reliability between the aluminum pad and the cured resin pattern, excellent wettability with wire bonding and solder balls, and solder diffusion prevention effect of the nickel layer Can be formed on the pad having aluminum or aluminum alloy, and can be used as an electrode pad with high connection reliability.
  • the metal used as the under bump metal examples include, but are not limited to, nickel, nickel alloy, copper, copper alloy, chromium, titanium, titanium tungsten, gold, platinum, and palladium.
  • nickel or a nickel alloy is preferably used mainly because it is relatively inexpensive, and the preferable content of nickel element in the under bump metal is 60% by mass or more and 99.9% by mass or less, more preferably 70% by mass. % Or more and 99.9% by mass or less, more preferably 80% by mass or more and 99.9% by mass or less.
  • the under bump metal preferably has an element other than nickel, and the preferable content of nickel in the under bump metal is 99.9% by mass or less, more preferably 99.5% by mass or less. More preferably, it is 99.0 mass% or less.
  • the aluminum alloy include, but are not limited to, Al—Si, Al—Si—Cu, and the like.
  • the pad having the aluminum or aluminum alloy and the external electrode are connected through the under bump metal by any one of a solder bump, a gold wire, and a copper wire, which suppresses metal corrosion of the connection portion and is high. This is preferable from the viewpoint of obtaining connection reliability.
  • a silicon wafer was used as a model of the semiconductor element, and a metal layer was formed directly on the silicon wafer or by sputtering, and then a positive photosensitive resin composition was applied to form a resin film for evaluation. It was. Whether the resin film (including an uncured resin pattern and / or a cured resin pattern) is a resin film directly formed on a silicon wafer or a resin film formed on a metal layer formed by sputtering. When it is not necessary to distinguish between the two, the silicon wafer and the silicon wafer on which the metal layer is formed are collectively referred to as a substrate.
  • the film thickness of the resin film on the substrate was measured using a light interference film thickness measuring device (Lambda Ace VM-1030 manufactured by Dainippon Screen Mfg. Co., Ltd.). The refractive index was measured as 1.629 for polyimide.
  • Imido ring closure rate (R IM (%)
  • GBL ⁇ -butyrolactone
  • D-SPIN Dainippon Screen Mfg. Co., Ltd.
  • This wafer with a resin film was divided into two parts, and one of them was cleaned using a clean oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.) at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less) and then further increased. Warmed and cured at 320 ° C. for 1 hour. Infrared spectrophotometer (manufactured by HORIBA, Ltd.
  • TMAH tetramethylammonium hydroxide
  • the minimum exposure amount is 500 mJ / cm 2 or more is insufficient (B)
  • 300 mJ / cm 2 or more and less than 500 mJ / cm 2 is good (A)
  • the one with less than 300 mJ / cm 2 is very good (S).
  • Al sputtered substrate chemical resistance Sputtered substrate (hereinafter referred to as Al sputtered substrate) in which sputtering of Ti and Al was successively performed in this order on a 4-inch silicon wafer, and the lower layer Ti was formed with a thickness of 50 nm and the upper layer Al was formed with a thickness of 200 nm. Prepared).
  • the Al sputter substrate was used for chemical resistance against the zincate solution and the electroless Ni / substituted Au plating treatment, and a 4-inch silicon wafer was used as the substrate for chemical resistance against strong acid and flux solution.
  • the varnish is applied onto the substrate by spin coating using a spinner (Mikasa Co., Ltd.), then 3 minutes on a hot plate at 120 ° C.
  • a substrate with a resin film and a reticle with a cut pattern were set on a mask aligner (PEM-6M manufactured by Union Optics Co., Ltd.) and exposed with broadband light at an exposure amount of 500 mJ / cm 2 in terms of i-line.
  • PEM-6M manufactured by Union Optics Co., Ltd.
  • the film reduction due to the O 2 ashing process was about 0.4 ⁇ m.
  • the following chemical-resistance evaluation was performed using the board
  • an optical microscope of an optical interference film thickness measuring device (Lambda Ace VM-1030 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used.
  • the peripheral portion of the 100 ⁇ m square square-extracted pattern of the substrate after processing was observed, and the penetration width into the remaining pattern was measured.
  • the measurement was performed at five locations, and the average value of 20 ⁇ m or more was insufficient (B), 10 ⁇ m or more but less than 20 ⁇ m was good (A), and the average value less than 10 ⁇ m was very good (S).
  • a silicon substrate with a cured resin pattern that has been subjected to O 2 ashing treatment prepared by the above method (hereinafter referred to as a substrate in the description of the evaluation in this section) is 5% sulfuric acid at 40 ° C. It was immersed for a minute, washed by immersing it in pure water for 30 seconds, and dried by air blow. The substrate after the treatment was observed, the presence or absence of cracks on the surface of the resin film was observed, and those with cracks were judged as insufficient (B) and those without cracks as good (A).
  • a silicon substrate with a cured resin pattern subjected to O 2 ashing treatment prepared by the above method (hereinafter referred to as a substrate in the description of the evaluation in this section) is treated with a flux solution (Arakawa Chemical Industries, Ltd.) WHD-001) is applied, heated on a hot plate at 250 ° C. (HHP-170D manufactured by ASONE Co., Ltd.) for 1 minute, immersed in pure water, and then subjected to an ultrasonic cleaner (AU manufactured by Aiwa Medical Industry Co., Ltd.). -26C) and dried by air blow.
  • the substrate after the treatment was observed, the presence or absence of cracks on the surface of the resin film was observed, and those with cracks were judged as insufficient (B) and those without cracks as good (A).
  • HA diamine compound
  • MAP 3-aminophenol
  • DMFDMA N, N-dimethylformamide dimethylacetal
  • Synthesis Example 4 Synthesis of Alkali-Soluble Polyimide Precursor Resin (A-3) The acid dianhydride addition amount was changed to 4.36 g (0.02 mol) PMDA and 9.31 g (0.03 mol) ODPA, and DMFDMA was added. A polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the amount was changed to 9.53 g (0.08 mol) to obtain an alkali-soluble polyimide precursor resin (A-3) powder.
  • Synthesis Example 14 Synthesis of Alkali-Soluble Polyimide Precursor Resin (A′-13) The acid dianhydride was changed to 15.51 g (0.05 mol) of ODPA, and 26.60 g (0.044 mol) of diamine other than SiDA. The polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the powder was changed to) to obtain an alkali-soluble polyimide precursor resin (A′-13) powder.
  • Synthesis Example 15 Synthesis of Novolak Resin (A′-14) 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 37% by mass formaldehyde under a dry nitrogen stream 75.5 g of aqueous solution (0.93 mol of formaldehyde), 0.63 g (0.005 mol) of oxalic acid dihydrate and 264 g of methyl isobutyl ketone were charged, and then immersed in an oil bath, while the reaction solution was refluxed. A time polycondensation reaction was performed.
  • the reaction mixture was poured into 3 L of methanol, the precipitated polymer was dried, further dissolved in 1.6 L of acetone, 2 g of concentrated hydrochloric acid was added at 60 ° C., stirred for 7 hours, and then poured into water.
  • the polymer is precipitated by deprotection to convert pt-butoxystyrene into hydroxystyrene, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 24 hours to obtain an alkali-soluble polyhydroxystyrene resin. (A'-15) was obtained.
  • the thermal crosslinking agent (C-1) HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) used in the examples is shown below.
  • the thermal base generator (D-1) (R) -t-butyl-2- (hydroxymethyl) pyrrolidine-1-carboxylate (manufactured by Wako Pure Chemical Industries, Ltd.) used in the comparative example is shown below.
  • Example 4 shows the results of evaluating the photosensitivity and chemical resistance against zincate treatment using the prepared varnish by the above method.
  • Comparative Example 1 the photosensitive properties were insufficient.
  • Comparative Examples 2 to 9 the penetration depth into the remaining pattern during the zincate treatment was large, and the chemical resistance was insufficient.
  • Table 5 shows the results of chemical resistance evaluation with respect to strong acid treatment and flux treatment using varnishes W-1 to 7, 11, 12, 16, and 21 by the above methods. In Comparative Example 11, cracks occurred on the resin surface in any treatment.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention vise : à fournir une composition de résine photosensible de type positif, avec laquelle il est possible d'obtenir un motif de résine durci ayant une sensibilité élevée à la ligne i d'une lampe à mercure, une excellente résistance chimique aux solutions aqueuses fortement acides et aux solutions aqueuses fortement alcalines et, en particulier, une adhérence très fiable à des tampons d'aluminium, même dans une étape de dépôt autocatalytique après calcination d'O2 ; et à fournir un motif de résine à l'aide de la composition, et un procédé de fabrication d'un dispositif semi-conducteur l'utilisant. La composition de résine photosensible de type positif contient (a) une résine soluble dans un alcali et (b) un composé de quinonediazide, la résine soluble dans un alcali (a) comprenant : (a1) un précurseur de polyimide dans lequel le résidu d'un acide tétracarboxylique représenté par la formule générale (1) est présent dans une quantité de 5 à 50 % en moles par rapport à la quantité totale de résidu d'acide tétracarboxylique, le résidu d'une diamine représentée par la formule générale (2) est présent dans une quantité de 10 à 80 % en moles par rapport à la quantité totale de résidu de diamine, et le résidu d'une diamine représentée par la formule générale (3) est présent dans une quantité de 10 à 90 % en moles par rapport à la quantité totale de résidu de diamine ; et/ou (a2) un polyimide correspondant à (a1). (Dans la formule générale (1), A représente un groupe hydrocarboné aromatique monocyclique ou bicyclique tétravalent exempt d'hétéroatomes, et au moins deux types peuvent être utilisés.) (Dans la formule générale (2), B représente un groupe choisi parmi O, S, SO2, CH2, CH(CH3), C(CH3)2 et C(CF3)2, et au moins deux types de ces derniers peuvent être utilisés.)
PCT/JP2016/075352 2015-09-03 2016-08-30 Composition de résine photosensible de type positif, motif de résine non durci formé avec ladite composition de résine, motif de résine durci, dispositif semi-conducteur l'utilisant, et son procédé de fabrication WO2017038828A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201680049884.7A CN107924125B (zh) 2015-09-03 2016-08-30 正型感光性树脂组合物、由其形成的未固化及固化图案、使用其的半导体器件及其制造方法
JP2016555372A JP6760073B2 (ja) 2015-09-03 2016-08-30 ポジ型感光性樹脂組成物、その樹脂組成物により形成された未硬化の樹脂パターン、硬化樹脂パターン、およびそれを用いた半導体装置とその製造方法
KR1020187006706A KR102542820B1 (ko) 2015-09-03 2016-08-30 포지티브형 감광성 수지 조성물, 이 수지 조성물에 의해 형성된 미경화된 수지 패턴, 경화 수지 패턴, 및 이것을 사용한 반도체 장치와 그의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-173515 2015-09-03
JP2015173515 2015-09-03

Publications (1)

Publication Number Publication Date
WO2017038828A1 true WO2017038828A1 (fr) 2017-03-09

Family

ID=58187539

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/075352 WO2017038828A1 (fr) 2015-09-03 2016-08-30 Composition de résine photosensible de type positif, motif de résine non durci formé avec ladite composition de résine, motif de résine durci, dispositif semi-conducteur l'utilisant, et son procédé de fabrication

Country Status (5)

Country Link
JP (1) JP6760073B2 (fr)
KR (1) KR102542820B1 (fr)
CN (1) CN107924125B (fr)
TW (1) TW201718711A (fr)
WO (1) WO2017038828A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11687002B2 (en) 2020-07-30 2023-06-27 Lg Chem, Ltd. Binder resin, positive-type photosensitive resin composition, insulating film and semiconductor device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007114763A (ja) * 2005-09-21 2007-05-10 Toray Ind Inc ポジ型感光性樹脂組成物
JP2007183388A (ja) * 2006-01-06 2007-07-19 Toray Ind Inc 感光性樹脂組成物、耐熱性樹脂パターンの製造方法および有機電界発光素子
WO2009022732A1 (fr) * 2007-08-10 2009-02-19 Sumitomo Bakelite Co., Ltd. Composition de résine photosensible positive, film durci, film protecteur, film isolant et dispositif semi-conducteur
JP2011042701A (ja) * 2009-08-19 2011-03-03 Toray Ind Inc 樹脂およびポジ型感光性樹脂組成物
JP2011197362A (ja) * 2010-03-19 2011-10-06 Toray Ind Inc ポジ型感光性樹脂組成物

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6677099B1 (en) * 1999-11-30 2004-01-13 Nissan Chemical Industries, Ltd. Positive type photosensitive polyimide resin composition
EP1662319A3 (fr) * 2004-11-24 2009-05-27 Toray Industries, Inc. Composition de résine photosensible
JP2006206756A (ja) * 2005-01-28 2006-08-10 Sony Chem Corp ポリイミド化合物及びフレキシブル配線板
JP5260646B2 (ja) * 2008-05-29 2013-08-14 旭化成イーマテリアルズ株式会社 感光性樹脂組成物
JP5910109B2 (ja) 2012-01-26 2016-04-27 住友ベークライト株式会社 ポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜、半導体装置、および表示体装置
JP6065507B2 (ja) * 2012-10-03 2017-01-25 Jsr株式会社 感放射線性重合体組成物、絶縁膜および有機ｅｌ素子
KR101942150B1 (ko) * 2012-12-20 2019-01-24 도레이 카부시키가이샤 감광성 수지 조성물, 내열성 수지막의 제조 방법 및 표시 장치
JP6291718B2 (ja) 2013-04-18 2018-03-14 住友ベークライト株式会社 ポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜、半導体装置、および表示体装置
JP6255740B2 (ja) 2013-06-24 2018-01-10 住友ベークライト株式会社 ポジ型感光性樹脂組成物、硬化膜、保護膜、絶縁膜、半導体装置、表示体装置、およびポジ型感光性樹脂組成物の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007114763A (ja) * 2005-09-21 2007-05-10 Toray Ind Inc ポジ型感光性樹脂組成物
JP2007183388A (ja) * 2006-01-06 2007-07-19 Toray Ind Inc 感光性樹脂組成物、耐熱性樹脂パターンの製造方法および有機電界発光素子
WO2009022732A1 (fr) * 2007-08-10 2009-02-19 Sumitomo Bakelite Co., Ltd. Composition de résine photosensible positive, film durci, film protecteur, film isolant et dispositif semi-conducteur
JP2011042701A (ja) * 2009-08-19 2011-03-03 Toray Ind Inc 樹脂およびポジ型感光性樹脂組成物
JP2011197362A (ja) * 2010-03-19 2011-10-06 Toray Ind Inc ポジ型感光性樹脂組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11687002B2 (en) 2020-07-30 2023-06-27 Lg Chem, Ltd. Binder resin, positive-type photosensitive resin composition, insulating film and semiconductor device

Also Published As

Publication number Publication date
KR102542820B1 (ko) 2023-06-14
TW201718711A (zh) 2017-06-01
CN107924125A (zh) 2018-04-17
JP6760073B2 (ja) 2020-09-23
JPWO2017038828A1 (ja) 2018-06-14
KR20180048691A (ko) 2018-05-10
CN107924125B (zh) 2020-12-25

Similar Documents

Publication Publication Date Title
CN109642028B (zh) 树脂组合物
JP6848434B2 (ja) 樹脂および感光性樹脂組成物
JP6048257B2 (ja) 耐熱性樹脂及びその前駆体組成物
WO2016035593A1 (fr) Résine et composition de résine photosensible
KR102542822B1 (ko) 수지 조성물, 그의 경화 릴리프 패턴, 및 그것을 사용한 반도체 전자 부품 또는 반도체 장치의 제조 방법
JP4935272B2 (ja) ポジ型感光性樹脂組成物
WO2016152656A1 (fr) Composition de résine photosensible
JP6939553B2 (ja) 樹脂組成物
WO2018159384A1 (fr) Composition de résine, feuille de résine, motif durci, et composant électronique semi-conducteur ou dispositif semi-conducteur
JP6711273B2 (ja) 樹脂および感光性樹脂組成物
JP2009258634A (ja) ポジ型感光性樹脂組成物
JP2020033277A (ja) 化合物、それを用いた樹脂、樹脂組成物、硬化膜、有機ｅｌ表示装置装置、電子部品、半導体装置、電子部品または半導体装置の製造方法
JP5176600B2 (ja) ポジ型感光性樹脂組成物
WO2015137281A1 (fr) Composition de résine photosensible
WO2017081922A1 (fr) Dispositif à semi-conducteurs, et procédé de fabrication de celui-ci
JP2013205553A (ja) ポジ型感光性樹脂組成物
JP5919896B2 (ja) 硬化膜の処理方法および半導体装置の製造方法
WO2017038828A1 (fr) Composition de résine photosensible de type positif, motif de résine non durci formé avec ladite composition de résine, motif de résine durci, dispositif semi-conducteur l'utilisant, et son procédé de fabrication
JP2010072143A (ja) ポジ型感光性樹脂組成物
JP2022034533A (ja) 感光性樹脂組成物、硬化膜および有機ｅｌ表示装置
JP2015176962A (ja) 樹脂膜の製造方法
JP2010164986A (ja) ポジ型感光性樹脂組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2016555372

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16841859

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187006706

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 16841859

Country of ref document: EP

Kind code of ref document: A1