WO2014097633A1 - ポリイミド前駆体、該ポリイミド前駆体を含む感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 - Google Patents

ポリイミド前駆体、該ポリイミド前駆体を含む感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 Download PDF

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WO2014097633A1
WO2014097633A1 PCT/JP2013/007467 JP2013007467W WO2014097633A1 WO 2014097633 A1 WO2014097633 A1 WO 2014097633A1 JP 2013007467 W JP2013007467 W JP 2013007467W WO 2014097633 A1 WO2014097633 A1 WO 2014097633A1
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Prior art keywords
general formula
group
polyimide precursor
resin composition
photosensitive resin
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PCT/JP2013/007467
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English (en)
French (fr)
Japanese (ja)
Inventor
榎本　哲也
敬司 小野
匡之 大江
ケイ子 鈴木
和也 副島
越晴 鈴木
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HD MicroSystems Ltd
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Hitachi Chemical DuPont Microsystems Ltd
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Priority to US14/654,758 priority Critical patent/US9751984B2/en
Priority to KR1020157008796A priority patent/KR102214856B1/ko
Priority to CN201380066870.2A priority patent/CN104870523B/zh
Priority to JP2014552941A priority patent/JP6600943B2/ja
Publication of WO2014097633A1 publication Critical patent/WO2014097633A1/ja
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    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • 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
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/68—Organic materials, e.g. photoresists
    • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials

Definitions

  • the present invention relates to a polyimide precursor, a photosensitive resin composition containing the polyimide precursor, a method for producing a patterned cured film using the same, and a semiconductor device.
  • a protective film (cured film) using such a polyimide resin is obtained by heating and curing a resin film formed by applying and drying a polyimide precursor or a resin composition containing a polyimide precursor on a substrate. It is obtained with.
  • an interlayer insulating film called a low-k layer With the miniaturization of semiconductor integrated circuits, it is necessary to reduce the dielectric constant of an interlayer insulating film called a low-k layer.
  • a method of applying an interlayer insulating film having a hole structure In order to reduce the dielectric constant, for example, there is a method of applying an interlayer insulating film having a hole structure. However, this method has a problem that the mechanical strength is lowered.
  • a protective film on the interlayer insulating film In order to protect such an interlayer insulating film having low mechanical strength, there is a method of providing a protective film on the interlayer insulating film. In addition, in the region where the protruding external electrodes called bumps are formed, the stress acting on the interlayer insulating film is concentrated and the interlayer insulating film is not destroyed.
  • the polyimide resin used for forming the protective film is photosensitive, it is possible to easily form a pattern resin film (patterned resin film). By heating and curing such a patterned resin film, a pattern cured film (patterned cured film) can be easily formed.
  • a method for making the polyimide resin photosensitive there is a method for imparting photosensitivity to the polyimide.
  • a method for imparting photosensitivity to polyimide a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond, a method of using a soluble polyimide having a photopolymerizable olefin, a benzophenone skeleton, and nitrogen
  • a method using a self-sensitized polyimide having an alkyl group at the ortho position of an aromatic ring to which atoms are bonded is known (for example, Patent Document 5).
  • the method of introducing a methacryloyl group via an ester bond into a polyimide precursor allows the monomer used to be freely selected when synthesizing the polyimide precursor, and the methacryloyl group is chemically bonded. Therefore, it is characterized by excellent stability over time.
  • the low-stress polyimide resin when a large amount of aromatic ring units are introduced in order to make the molecular chain a rigid skeleton, a large amount of conjugated aromatic ring units are contained in the molecular chain.
  • the polyamic acid (polyimide precursor) which is a precursor of the compound has absorption in the ultraviolet region. Therefore, the transmittance of i-line (wavelength 365 nm) widely used in the exposure process for forming the patterned resin film tends to decrease, and the sensitivity and resolution tend to decrease. Further, when the protective film is made thicker, the i-line transmittance tends to be further lowered and the pattern resin film cannot be formed. In addition, when a flexible structure such as a siloxane structure is introduced, the heat resistance may decrease.
  • the objective of this invention is providing the polyimide precursor which shows the pattern cured film which shows the outstanding i ray transmittance, and is low stress, and the photosensitive resin composition using the same.
  • Another object of the present invention is to provide a method of forming a patterned cured film that exhibits excellent i-line transmittance and low stress.
  • the polyimide precursor which has 50 mol% or more of structural units represented by following General formula (1) with respect to all the structural units.
  • A is any one of tetravalent organic groups represented by the following general formulas (2a) to (2c).
  • B is a divalent organic group represented by the following general formula (3).
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group.
  • X and Y are each independently a divalent group that is not conjugated to the benzene ring to which they are bonded, or a single bond.
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 is a fluorine atom or a trifluoromethyl group.
  • the polyimide precursor of 1 which has a structural unit represented by following General formula (4).
  • D is a tetravalent organic group represented by the following General Formula (5).
  • B, R 1 and R 2 are the same as in the general formula (1), respectively.
  • a photosensitive resin composition comprising (a) the polyimide precursor according to any one of 1 to 4, (b) a compound that generates radicals upon irradiation with actinic rays, and (c) a solvent. 6). Furthermore, the photosensitive resin composition of 5 containing a tetrazole or a tetrazole derivative, or a benzotriazole or a benzotriazole derivative. 7). (B) The photosensitive resin composition of 5 or 6 in which a component contains an oxime ester compound. 8). 8. The photosensitive property according to 7, wherein the oxime ester compound is a compound represented by the following general formula (22), a compound represented by the following general formula (23), or a compound represented by the following general formula (24).
  • R 11 and R 12 are each an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group.
  • R 13 is —H, —OH, -COOH, -O (CH 2 ) OH, -O (CH 2 ) 2 OH, -COO (CH 2 ) OH or -COO (CH 2 ) 2 OH.
  • R 14 is an alkyl group having 1 to 6 carbon atoms
  • R 15 is NO 2 or ArCO (Ar represents an aryl group)
  • R 16 and R 17 are (Each is an alkyl group having 1 to 12 carbon atoms, a phenyl group, or tolyl.
  • R 18 is an alkyl group having 1 to 6 carbon atoms
  • R 19 is an organic group having an acetal bond
  • R 20 and R 21 are each an alkyl group having 1 to 12 carbon atoms. , Phenyl group or tolyl group.
  • a cured film obtained by heating the polyimide precursor according to any one of 9.1 to 4.
  • permeability which is excellent and gives the pattern cured film which is low stress, and the photosensitive resin composition using the same can be provided.
  • the formation method of the pattern cured film which shows the outstanding i ray transmittance and is low stress can be provided.
  • the polyimide precursor of this invention has 50 mol% or more of structural units represented by following General formula (1) with respect to all the structural units.
  • A is any one of tetravalent organic groups represented by the following general formulas (2a) to (2c).
  • B is a divalent organic group represented by the following general formula (3).
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group.
  • X and Y are each independently a divalent group that is not conjugated to the benzene ring to which they are bonded, or a single bond.
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 is a fluorine atom or a trifluoromethyl group.
  • a in the general formula (1) is a structure derived from tetracarboxylic dianhydride used as a raw material for the polyimide precursor, and any one of the tetravalent organic groups represented by the general formulas (2a) to (2c) It is.
  • Examples of the tetracarboxylic dianhydride that gives the structure of A include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, represented by the following general formulas (6) to (12). And tetracarboxylic dianhydride. During polymerization of the polyimide precursor, these may be used alone or in combination of two or more tetracarboxylic dianhydrides.
  • the tetracarboxylic dianhydride that gives the structure of A is pyromellitic dianhydride, tetracarboxylic dianhydride represented by the formulas (6) and (8). It is preferable to use pyromellitic dianhydride, more preferably tetracarboxylic dianhydride represented by the formula (6).
  • B in the general formula (1) is a structure derived from a diamine used as a raw material for the polyimide precursor, and is a divalent organic group represented by the general formula (3).
  • At least one of R 3 to R 10 in the general formula (3) is a fluorine atom or a trifluoromethyl group, preferably two or more of R 3 to R 10 are a fluorine atom or a trifluoromethyl group, and more preferably In R 2 to R 10 , two or more of R 3 to R 10 are trifluoromethyl groups.
  • the polyimide precursor has a hydrophobic group such as a fluorine atom or a trifluoromethyl group, the water absorption rate can be reduced.
  • the protective film is a film having a low water absorption rate.
  • a protective film can shorten the evacuation time and suppress the contamination of the vapor deposition apparatus in a high vacuum process such as metal thin film vapor deposition in the bump forming step, and can improve productivity.
  • Examples of the diamine that gives the structure of B include diamines represented by the following general formulas (13) to (19). During polymerization of the polyimide precursor, these may be used alone or in combination of two or more diamines.
  • diamines represented by formula (13), formula (18), and formula (19) are preferable from the viewpoint of i-line transmittance, and formula (18) and formula (19) from the viewpoint of reducing water absorption. It is more preferable to use a diamine represented by the formula (18), and a diamine represented by the formula (18) is particularly preferable.
  • the monovalent organic group of R 1 and R 2 in the general formula (1) has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms.
  • An acryloxyalkyl group includes a methacryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, n-decyl group, and n-dodecyl group. Groups and the like.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group and the like.
  • Examples of the acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include acryloxyethyl group, acryloxypropyl group, acryloxybutyl group and the like.
  • Examples of the methacryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.
  • Monovalent organic groups for R 1 and R 2, at least one of R 1 and R 2, is preferably a monovalent organic group having a carbon-carbon unsaturated double bond.
  • radical polymerization is performed by radicals of a compound that generates radicals upon irradiation with actinic rays such as i-line exposure, and crosslinking between molecular chains.
  • Examples of the monovalent organic group having a carbon-carbon unsaturated double bond include an acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms and a methacryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms. Can be mentioned.
  • the polyimide precursor of the present invention has a structure represented by the general formula (1) in an amount of 50 mol% or more based on the total structural unit, whereby the molecular chain of the polyimide becomes rigid and has low thermal expansion and low stress.
  • the structure represented by the general formula (1) is preferably 60 mol% or more with respect to all structural units, and more preferably 70 mol% or more with respect to all structural units.
  • the upper limit of the ratio of the structure represented by the general formula (1) in the polyimide precursor is not particularly limited, but is, for example, 95 mol% or less with respect to all structural units. In order to make the ratio of the structure represented by the general formula (1) within the above range, the blending amount of tetracarboxylic dianhydride and diamine during polymerization of the polyimide precursor may be adjusted as appropriate.
  • the polyimide precursor of the present invention is represented by the following general formula (4) in addition to the structure represented by the general formula (1) for the purpose of improving i-line transmittance, adhesion after curing, and mechanical properties. It may have a structure.
  • D is a tetravalent organic group represented by the following General Formula (5).
  • B, R 1 and R 2 are the same as in the general formula (1), respectively.
  • Z represents an ether bond (—O—) or a sulfide bond (—S—).
  • the part containing Z is a structure derived from the tetracarboxylic dianhydride which is a raw material of a polyimide precursor.
  • the tetracarboxylic dianhydride that gives the structure of the moiety containing Z include 4,4′-oxydiphthalic dianhydride and thioether diphthalic anhydride. From the viewpoint of adhesion after curing, 4,4′-oxydiphthalic dianhydride is preferred.
  • these tetracarboxylic dianhydrides may be used alone or in combination of two or more.
  • Formula (4) B, R 1 and R 2 in general formula (1) B, is the same as R 1 and R 2, B preferred group formula (1), R 1 and R 2 The same.
  • the polyimide precursor When the polyimide precursor has both the structural unit represented by the general formula (1) and the structural unit represented by the general formula (4), the polyimide precursor becomes a copolymer.
  • the copolymer of the polyimide precursor include a block copolymer and a random copolymer, but are not particularly limited.
  • the molar ratio of the structural unit represented by the formula (1) and the structural unit represented by the general formula (4) [formula (1) / formula (4)] is preferably 5/5 to 9/1, 4-9 / 1 is more preferable, and 7 / 3-9 / 1 is even more preferable.
  • the polyimide precursor of this invention may have structural units (other structural units) other than the structural unit represented by General formula (1) and the structural unit represented by General formula (4).
  • tetracarboxylic dianhydrides that give other structural units include 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1 2,3,4-cyclobutanetetracarboxylic dianhydride and the like.
  • diamines that give other structural units include paraphenylene diamine, 4,4′-oxydianiline, 2,2′-dimethylbenzidine, 4,4′-diaminodiphenylmethane, and the like.
  • the tetracarboxylic dianhydride providing other structural units is preferably 20 mol% or less based on the total amount of tetracarboxylic dianhydride used as a raw material for the polyimide precursor. More preferably, it is 10 mol% or less, but only tetracarboxylic dianhydrides giving structures of the general formulas (1) and (4) are used without using tetracarboxylic dianhydrides giving other structural units. More preferably, it is used.
  • the diamine giving other structure is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total amount of diamine, but it is further preferable to use only the diamine giving the structure of the general formula (3). preferable.
  • the molecular weight of the polyimide precursor of the present invention is preferably a weight average molecular weight in terms of polystyrene of 10,000 to 100,000, more preferably 15,000 to 100,000, and further preferably 20,000 to 85,000. From the viewpoint of sufficiently reducing the stress after curing, the weight average molecular weight of the polyimide precursor is preferably 10,000 or more. Further, from the viewpoint of improving the solubility in a solvent and the handleability of the solution, the weight average molecular weight of the polyimide precursor is preferably 100,000 or less. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and can be calculated
  • the polyimide precursor of the present invention can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine.
  • the molar ratio of tetracarboxylic dianhydride and diamine [tetracarboxylic dianhydride / diamine] used when synthesizing the polyimide precursor is usually 1.0, and for the purpose of controlling the molecular weight and terminal residue, It is preferable to carry out at a molar ratio in the range of 0.7 to 1.3. When the molar ratio is 0.7 to 1.3, the molecular weight of the obtained polyimide precursor becomes appropriate, and the stress after curing tends to be sufficiently lower.
  • the polyimide precursor of the present invention is derived from a tetracarboxylic dianhydride as a raw material into a diester derivative represented by the following general formula (20), and then an acid chloride represented by the following general formula (21) And can be synthesized by condensation in the presence of a diamine and a basic compound.
  • E is a tetravalent organic group.
  • R 1 and R 2 are the same as R 1 and R 2 in general formula (1).
  • E is a tetravalent organic group.
  • R 1 and R 2 are the same as R 1 and R 2 in general formula (1).
  • E corresponds to A in the general formula (1) or Z in the general formula (4) and two benzene ring structure portions.
  • the diester derivative represented by the formula (20) can be synthesized by reacting at least 2 molar equivalents of alcohol in the presence of a basic catalyst with respect to 1 mol of tetracarboxylic dianhydride as a raw material. it can.
  • the diester derivative represented by the formula (20) is converted into the acid chloride represented by the formula (21), if the unreacted alcohol remains, the chlorinating agent is converted to the unreacted alcohol. There is concern that the conversion to acid chloride will not proceed sufficiently.
  • the equivalent of alcohol is preferably 2.0 to 2.5 molar equivalent, more preferably 2.0 to 2.3 molar equivalent, relative to 1 mole of tetracarboxylic dianhydride. More preferably, it is 2.0 to 2.2 molar equivalent.
  • Examples of alcohols to be reacted with tetracarboxylic dianhydride include alcohols having an alkyl group having 1 to 20 carbon atoms, alcohols having a cycloalkyl group having 3 to 20 carbon atoms, and acrylates having an alkyl group having 1 to 10 carbon atoms. Alcohols having a roxyalkyl group and alcohols having a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group can be used.
  • Basic catalysts used for the reaction of tetracarboxylic dianhydride with alcohols include 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona. -5-ene or the like can be used.
  • each tetracarboxylic dianhydride may be separately led to an ester derivative, and these ester derivatives may be mixed and used. Moreover, after mixing 2 or more types of tetracarboxylic dianhydride beforehand, you may guide
  • the diester derivative represented by the formula (20) into the acid chloride represented by the formula (21), it is usually used by reacting 1 mol of the diester derivative with 2 mol equivalent of a chlorinating agent.
  • the equivalent may be appropriately adjusted.
  • the chlorinating agent thionyl chloride or dichlorooxalic acid can be used, and the equivalent amount of the chlorinating agent is preferably 1.5 to 2.5 molar equivalents, more preferably 1.6 to 2.4 molar equivalents, A molar equivalent of 1.7 to 2.3 is more preferred. From the viewpoint of adjusting the molecular weight of the polyimide precursor to be high and improving the stress after curing, 1.5 to 2.5 molar equivalents are preferable.
  • the polyimide precursor of this invention is obtained by adding the raw material diamine to the acid chloride represented by the formula (21) in the presence of a basic compound.
  • the basic compound is used for the purpose of capturing hydrogen chloride generated when the acid chloride and diamine react.
  • pyridine, 4-dimethylaminopyridine, triethylamine or the like can be used, and it is preferably used in an amount of 1.5 to 2.5 times (mole) relative to the amount of the chlorinating agent.
  • the amount is more preferably 7 to 2.4 times, and even more preferably 1.8 to 2.3 times. From the viewpoint of increasing the molecular weight of the resulting polyimide precursor and improving the stress after curing, it is preferably 1.5 to 2.5 times.
  • the addition polymerization, condensation reaction, diester derivative synthesis, and acid chloride synthesis are preferably carried out in an organic solvent.
  • the organic solvent used is preferably a polar solvent that completely dissolves the synthesized polyimide precursor.
  • the polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, ⁇ -butyrolactone, and the like.
  • the photosensitive resin composition of the present invention contains the following components (a) to (c): (A) Polyimide precursor of the present invention (b) Compound that generates radicals upon irradiation with actinic rays (c) Solvent
  • the polyimide precursor of the present invention as component (a) is as described above.
  • the polyimide precursor is preferably contained in the photosensitive resin composition in an amount of 20 to 60% by mass, more preferably 25 to 55% by mass, and further preferably 30 to 55% by mass.
  • Examples of compounds that generate radicals upon irradiation with actinic rays as component (b) include N, such as an oxime ester compound, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), which will be described later.
  • N such as an oxime ester compound, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), which will be described later.
  • N′-Tetraalkyl-4,4′-diaminobenzophenone 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl
  • An aromatic ketone such as 2-morpholino-propanone-1; a quinone fused with an aromatic ring such as alkylanthraquinone; a benzoin ether compound such as benzoin alkyl ether; a benzoin compound such as benzoin or alkylbenzoin; a benzyldimethyl ketal Of the benzyl derivative.
  • an oxime ester compound is preferable because it is excellent in sensitivity and gives a good pattern.
  • the oxime ester compound is represented by the following formula (22), the following formula (23), and the following formula (24) from the viewpoint of obtaining good sensitivity and remaining film ratio. It is preferable that it is any one of the following compounds.
  • R 11 and R 12 each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, an alkyl group having 1 to 8 carbon atoms, It is preferably a cycloalkyl group having 4 to 6 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms or a phenyl group, and a methyl group, cyclopentyl group or More preferably, it is a phenyl group.
  • R 13 represents —H, —OH, —COOH, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH or —COO (CH 2 ) 2 OH; H, —O (CH 2 ) OH, —O (CH 2 ) 2 OH, —COO (CH 2 ) OH or —COO (CH 2 ) 2 OH are preferred, —H, —O (CH 2 ) More preferably, it is 2 OH or —COO (CH 2 ) 2 OH.
  • each R 14 represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.
  • R 15 represents NO 2 or ArCO (wherein Ar represents an aryl group), and Ar is preferably a tolyl group.
  • R 16 and R 17 each represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, and is preferably a methyl group, a phenyl group, or a tolyl group.
  • R 18 represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
  • R 19 is an organic group having an acetal bond, and is preferably a substituent corresponding to R 19 in a compound represented by formula (24-1) described later.
  • R 20 and R 21 each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group.
  • Examples of the compound represented by the formula (22) include a compound represented by the following formula (22-1) and a compound represented by the following formula (22-2).
  • a compound represented by the following formula (22-1) is available as IRGACURE OXE-01 (trade name, manufactured by BASF Corporation).
  • Examples of the compound represented by the above formula (23) include a compound represented by the following formula (23-1). This compound is available as DFI-091 (trade name, manufactured by Daitokemix Co., Ltd.).
  • Examples of the compound represented by the above formula (24) include a compound represented by the following formula (24-1). It is available as Adekaoptomer N-1919 (trade name, manufactured by ADEKA Corporation).
  • oxime ester compounds As other oxime ester compounds, the following compounds are preferably used. These compounds that generate radicals upon irradiation with actinic rays may be used alone or in combination of two or more.
  • the content of the compound that generates radicals upon irradiation with actinic rays is preferably 0.01 to 10 parts by weight, and 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyimide precursor (a). More preferred is 0.05 to 3 parts by weight.
  • the blending amount is 0.01 parts by weight or more, crosslinking of the exposed part proceeds more sufficiently, and the photosensitive properties (sensitivity, resolution) of the composition tend to be better, and when it is 10 parts by weight or less.
  • the heat resistance of the cured film obtained can be made better.
  • the solvent is preferably a polar solvent that completely dissolves the polyimide precursor as component (a).
  • the polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone and the like. These may be used alone or in combination of two or more.
  • the content of the solvent is preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and further preferably 45 to 70% by mass in the photosensitive resin composition.
  • the photosensitive resin composition of the present invention may contain (a) a polyimide precursor, (b) a compound that generates radicals upon irradiation with actinic rays, and (c) a solvent, and may further contain the following other components. .
  • the photosensitive resin composition of the present invention may contain (d) an organosilane compound in order to improve adhesion to a cured silicon substrate or the like.
  • Organic silane compounds include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ -glycidoxypropyltrimethoxy.
  • Silane ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) ) -3-Aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Can be
  • the content of the organosilane compound is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyimide precursor from the viewpoint of adhesion after curing. It is preferably 0.5 to 15 parts by weight, more preferably 0.5 to 10 parts by weight.
  • the photosensitive resin composition of the present invention may contain (e) an addition polymerizable compound as required.
  • addition polymerizable compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate.
  • the content of the addition polymerizable compound is 100 parts by weight of the polyimide precursor from the viewpoint of solubility in a developer and heat resistance of the resulting cured film.
  • it is preferably 1 to 100 parts by weight, more preferably 1 to 75 parts by weight, and still more preferably 1 to 50 parts by weight.
  • the photosensitive resin composition of the present invention may contain (f) a radical polymerization inhibitor or a radical polymerization inhibitor in order to ensure good storage stability.
  • radical polymerization inhibitors or radical polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N- Examples include phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, and the like. These may be used alone or in combination of two or more.
  • the content of the radical polymerization inhibitor or the radical polymerization inhibitor depends on the storage stability of the photosensitive resin composition and the cured film obtained. From the viewpoint of heat resistance, it is preferably 0.01 to 30 parts by weight, more preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the polyimide precursor. More preferably.
  • the photosensitive resin composition of the present invention when used on a copper substrate, the photosensitive resin composition preferably contains (g) tetrazole or a tetrazole derivative, or benzotriazole or a benzotriazole derivative.
  • the composition is an oxime ester compound represented by the above formula (22) (for example, IRGACURE OXE- 01 (made by BASF Corporation, trade name)), a polyimide residue may be formed in the opening when the pattern cured film is formed.
  • a specific oxime ester compound produces a radical at the time of pre-baking, and also hardens an unexposed part.
  • (g) component When (g) component is contained, it can suppress that a polyimide residue arises in an opening part. Although the detailed mechanism for achieving the above effect is not clear, the (g) component forms a thin film on the copper substrate and prevents the active metal surface and the resin composition from coming into direct contact with each other. It is presumed that the necessary photoinitiator decomposition and radical polymerization reaction were suppressed, and it was possible to ensure the photosensitive properties on the copper substrate.
  • Examples of the tetrazole and tetrazole derivatives include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5′-bis- Examples thereof include 1H-tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-mercapto-tetrazole, 1-carboxymethyl-5-mercapto-tetrazole and the like. Among these, 1H-tetrazole or 5-amino-1H-tetrazole is preferable.
  • benzotriazole and benzotriazole derivatives examples include benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, mercaptobenzoxazole, and the like. Among these, benzotriazole is preferable.
  • a component may be used independently and may be used in combination of 2 or more types. These are usually 0.1 to 10 parts by weight per one type with respect to 100 parts by weight of component (a), and a total of 0.1 to 10 parts by weight when two or more types are combined. More preferably, it is 0.2 to 5 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the adhesion to the metal layer tends to decrease.
  • the photosensitive resin composition of the present invention may contain at least one selected from the components (a) to (c) and optionally the components (d) to (g), and may be substantially composed of these components. Well, it may consist only of these components.
  • the term “substantially” means that, for example, the total amount of components (a) to (c) and components (d) to (g) in the photosensitive resin composition is 95% by weight or more, 97 It means that it is not less than wt%, not less than 98 wt%, or not less than 99 wt%.
  • a cured film can be obtained by heat-treating the polyimide precursor of the present invention to advance imidization.
  • the heating temperature for converting the polyimide precursor to polyimide is preferably 80 to 450 ° C, more preferably 100 to 450 ° C, and further preferably 200 to 400 ° C. If it is less than 80 ° C., imidization does not proceed sufficiently and heat resistance may be lowered, and if heat treatment is performed at a temperature higher than 450 ° C., there is a possibility that a polyimide obtained by curing is deteriorated.
  • the residual stress of the cured film obtained by curing the polyimide precursor of the present invention is preferably 30 MPa or less, more preferably 27 MPa or less, and further preferably 25 MPa or less.
  • the resulting cured film has a residual stress of more than 30 MPa, when the cured film is formed thick so that the film thickness after curing is 10 ⁇ m, the warpage of the wafer becomes large, and there is a problem in transporting and fixing the wafer. May occur.
  • the residual stress of the cured film can be calculated from the following formula (I) using the amount of change in the radius of curvature of the silicon wafer before and after the polyimide film is formed.
  • the curvature radius of the silicon wafer is calculated from the reflection angle of the laser that scans the silicon wafer, and can be measured using a thin film stress measuring device (for example, FLX-2320 manufactured by KLA Tencor).
  • ⁇ Residual stress (Pa) E / (1- ⁇ ): Biaxial elastic modulus of silicon wafer (Pa) h: thickness of silicon wafer (m) t: Polyimide film thickness (m)
  • R Change amount of curvature radius of silicon wafer (m)
  • the polyimide precursor of the present invention is formed with a thickness of about 20 ⁇ m.
  • the i-line transmittance of the resin film is preferably 5% or more, more preferably 8% or more. More preferably, it is more preferably 15% or more, and particularly preferably 30% or more. If the i-line transmittance is less than 5%, the i-line does not reach the deep part, and radicals are not sufficiently generated, so that the photosensitive characteristics may be deteriorated.
  • the i-line transmittance can be measured by, for example, forming a resin film by applying and drying a polyimide precursor on a glass plate, and measuring with an ultraviolet-visible spectrophotometer.
  • the cured pattern film of the present invention can be obtained by exposing and heating the photosensitive resin composition of the present invention.
  • the patterned cured film of the present invention is preferably used as a protective layer of a Low-K material that is an interlayer insulating film.
  • the Low-K material include porous silica, benzocyclobutene, hydrogen silsesquioxane, polyallyl ether, and the like.
  • the method for producing a cured pattern film of the present invention includes a step of applying the photosensitive resin composition of the present invention on a substrate and drying to form a coating film, and irradiating the formed coating film with an actinic ray to expose the pattern A step of removing an unexposed portion other than the exposed portion by development to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
  • the method of applying the photosensitive resin composition onto the substrate includes dipping, spraying, and screening. Examples thereof include a printing method and a spin coating method.
  • the substrate include a silicon wafer, a metal substrate, and a ceramic substrate. Since the photosensitive resin composition containing the polyimide precursor of the present invention can form a low-stress cured film, it is particularly suitable for application to a silicon wafer having a large diameter of 12 inches or more.
  • the solvent is removed (dried) by heating to form a coating film (resin film) with less adhesiveness.
  • the heating temperature during drying is preferably 80 to 130 ° C., and the drying time is preferably 30 to 300 seconds. Drying is preferably performed using an apparatus such as a hot plate.
  • the pattern exposure is performed on the obtained coating film.
  • actinic rays are irradiated through a mask on which a desired pattern is drawn.
  • the photosensitive resin composition of the present invention is suitable for i-line exposure, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays and the like can be used as the active rays to be irradiated.
  • a desired pattern can be obtained by dissolving and removing the unexposed portion with an appropriate developer after exposure.
  • the developer is not particularly limited, but a flame retardant solvent such as 1,1,1-trichloroethane; an alkali aqueous solution such as an aqueous sodium carbonate solution or an aqueous tetramethylammonium hydroxide solution; N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, ⁇ -butyrolactone, and acetic acid esters; these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used.
  • a poor solvent for example, water, ethanol, 2-propanol
  • the resulting pattern resin film is heated at, for example, 80 to 400 ° C. for 5 to 300 minutes to advance imidization of the polyimide precursor contained in the photosensitive resin composition.
  • a cured pattern film can be obtained.
  • a curing furnace that can be cured at a low oxygen concentration of 100 ppm or less, for example, an inert gas oven or a vertical diffusion furnace. Can do.
  • the cured film or pattern cured film of the present invention can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer, or the like of a semiconductor device.
  • the semiconductor device include logic semiconductors such as MPU and memory semiconductors such as DRAM and NAND flash.
  • FIG. 1 is a schematic cross-sectional view of a semiconductor device having a rewiring structure according to an embodiment of the present invention.
  • the semiconductor device of this embodiment has a multilayer wiring structure.
  • An Al wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the Al wiring layer 2, and a surface protective layer of the device A (surface protective film) 4 is formed.
  • a rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to an upper portion of the core 8 which is a connection portion with the conductive ball 7 formed of solder, gold or the like as an external connection terminal.
  • a cover coat layer 9 is formed on the surface protective layer 4.
  • the rewiring layer 6 is connected to the conductive ball 7 through the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7.
  • an underfill 12 may be interposed in order to further relieve stress.
  • the cured film or pattern cured film of the present invention can be used for so-called package applications such as the cover coat material, the core material for rewiring, the color material for balls such as solder, the underfill material, and the like.
  • the cured film or pattern cured film of the present invention has the cured film or pattern cured film of the present invention because it has excellent adhesion to a metal layer, a sealant, and the like, as well as excellent copper migration resistance and a high stress relaxation effect.
  • the semiconductor element is extremely excellent in reliability.
  • Example 1-6 and Comparative Example 1-5 [Synthesis and evaluation of polyamic acid]
  • tetracarboxylic dianhydride 1 shown in Table 1 and, if necessary, tetracarboxylic acid 2 were dissolved with stirring at room temperature.
  • the diamine 1 shown in Table 1 and the diamine 2 as needed were added, and it stirred at room temperature for 1 hour, and obtained the polyamic-acid solution (polyimide precursor solution).
  • the following evaluation was performed about the obtained polyimide precursor. The results are shown in Table 1.
  • Weight average molecular weight The weight average molecular weight of the obtained polyamic acid was calculated
  • required by standard polystyrene conversion by the gel permeation chromatography (GPC) method. The results are shown in Table 1. Specifically, it measured by GPC method on the following measuring conditions using the solution [THF / DMF 1/1 (volume ratio)] 1 ml with respect to 0.5 mg of polyamic acids. Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd. Pump: Hitachi Ltd.
  • i-line transmittance The obtained polyamic acid solution was spin-coated on a glass plate and heat-treated on a hot plate at 100 ° C. for 3 minutes to form a coating film having a thickness of 20 ⁇ m.
  • the 365 nm i-line transmittance was measured and evaluated according to the following criteria. The results are shown in Table 1.
  • i-line transmittance is 20% or more: ⁇ i-line transmittance of 10% or more and less than 20%: ⁇ i-line transmittance is less than 10%: ⁇
  • the i-line transmittance was measured by a cast film method using a visible ultraviolet spectrophotometer U-3310 manufactured by Hitachi High-Technologies Corporation.
  • Residual stress is 30 MPa or less: ⁇ Residual stress is more than 30 MPa and less than 35 MPa: ⁇ Residual stress exceeds 35 MPa: ⁇
  • the residual stress of the cured film was measured at room temperature using a thin film stress measuring apparatus FLX-2320 manufactured by KLA Tencor.
  • PMDA pyromellitic dianhydride s-BPDA: 4,4′-biphenyltetracarboxylic dianhydride
  • NTCA 2,3,6,7-naphthalenetetracarboxylic dianhydride
  • MMXDA 9,9′-dimethyl- 2,3,6,7-xanthenetetracarboxylic dianhydride
  • ODPA 4.4'-oxydiphthalic dianhydride
  • TFDB 2,2'-bis (trifluoromethyl) benzidine
  • DMAP 2,2'-dimethylbenzidine
  • Example 1-6 shows an i-line transmittance of 20% or more and a stress of 30 MPa or less.
  • Comparative Example 1 using a diamine not containing a fluorine atom and Comparative Examples 2 and 5 using a diamine containing a fluorine atom and a diamine not containing a fluorine atom show a stress of 30 MPa or less, but i-line transmission It can be seen that the rate is low.
  • i-line transmittance is 20% or more, but high stress of 35 MPa or more. I understand that.
  • Examples 7-12 and Comparative Examples 6-9 Synthesis and evaluation of polyamic acid ester (polyimide precursor)] The following polyamic acid ester synthesis method 1 using tetracarboxylic dianhydride 1, alcohol compound 1 and diamine 1 shown in Table 2, and tetracarboxylic dianhydride 2, alcohol compound 2 and diamine 2 as required. Alternatively, a polyamic acid ester was synthesized by the polyamic acid ester synthesis method 2. The polyimide precursor that was the obtained polyamic acid ester was evaluated in the same manner as in Example 1-6 and Comparative Example 1-5. The results are shown in Table 2.
  • the tetracarboxylic dianhydride component 2 the alcohol compound 2 and the catalytic amount of DBU shown in Table 2 were added in a weight ratio of 4 times the amount of tetracarboxylic dianhydride 2 to N-methyl- Dissolved in 2-pyrrolidone and stirred for 48 hours at room temperature to give ester solution 2.
  • ester solution 2 After mixing the obtained ester solution 1 and ester solution 2, while cooling in an ice bath, 2.2 times molar equivalent of the total amount of tetracarboxylic dianhydride 1 and tetracarboxylic dianhydride 2 After dropwise addition of thionyl chloride, the mixture was stirred for 1 hour to prepare an acid chloride solution.
  • diamine 1 shown in Table 2 and, if necessary, diamine 2 and pyridine equivalent to twice the molar equivalent of thionyl chloride are dissolved in 4 times the amount of diamine 1 and diamine 2 by weight in N-methyl-2-pyrrolidone.
  • the solution was prepared and added dropwise to the previously prepared acid chloride solution while cooling in an ice bath. After completion of dropping, the reaction solution was added dropwise to distilled water. After completion of the dropwise addition, the precipitate was collected by filtration, washed several times with distilled water, and then vacuum dried to obtain a polyamic acid ester. 100 parts by weight of the resulting polyamic acid ester was dissolved in 150 parts by weight of N-methyl-2-pyrrolidone to prepare a polyamic acid ester solution.
  • (Ii) Polyamic acid ester synthesis method 2 The polyamic acid ester was prepared in the same manner as in the polyamic acid ester synthesis method 1 except that the esterification of the tetracarboxylic dianhydride 1 and the tetracarboxylic dianhydride 2 was not carried out separately but in the same reaction vessel. An ester was obtained. 100 parts by weight of the resulting polyamic acid ester was dissolved in 150 parts by weight of N-methyl-2-pyrrolidone to prepare a polyamic acid ester solution.
  • the polyamic acid ester of Examples 7-12 has both an i-line transmittance of 20% or more and a stress of 30 MPa or less.
  • Comparative Example 6 using a diamine containing no fluorine atom and the polyamic acid esters of Comparative Example 7 and Comparative Example 9 using a diamine containing a fluorine atom and a diamine containing no fluorine atom a stress of 30 MPa or less is exhibited. It can be seen that the i-line transmittance is low.
  • Examples 13-17 and Comparative Examples 10-13 [Preparation and Evaluation of Photosensitive Resin Composition] 100 parts by weight of any of the polyamic acid esters obtained in Example 7-11 and Comparative Example 6-9, 20 parts by weight of tetraethylene glycol dimethacrylate, and 1,2-octanedione-1- [4- (phenylthio)
  • the photosensitive resin composition was prepared by stirring 2 parts by weight of phenyl-2- (O-benzoyloxime)] until uniformly dissolved in 150 parts by weight of N-methyl-2-pyrrolidone, followed by pressure filtration using a 1 ⁇ m filter. I got a thing. About the obtained photosensitive resin composition, the photosensitive characteristic, the residual stress, and the water absorption were evaluated. The results are shown in Table 3. The photosensitive characteristics were evaluated by the method described later, and the residual stress and water absorption were evaluated in the same manner as in Example 1.
  • Example 18 [Preparation and Evaluation of Photosensitive Resin Composition] 100 parts by weight of the polyamic acid ester obtained in Example 12, 20 parts by weight of tetraethylene glycol dimethacrylate, 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] 2
  • the photosensitive resin composition was obtained by stirring until 1 part by weight and 3 parts by weight of benzotriazole were uniformly dissolved in 150 parts by weight of N-methyl-2-pyrrolidone and then filtered under pressure using a 1 ⁇ m filter.
  • the obtained photosensitive resin composition was evaluated in the same manner as in Examples 13-17 and the residue on the copper substrate. The results are shown in Table 3. The residue on the copper substrate was evaluated by the method described later.
  • Example 19 [Preparation and Evaluation of Photosensitive Resin Composition] 100 parts by weight of the polyamic acid ester obtained in Example 12, 20 parts by weight of tetraethylene glycol dimethacrylate, 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (O-benzoyloxime)] 2 A photosensitive resin composition was obtained by stirring until 3 parts by weight of tetrazole and 3 parts by weight of tetrazole were uniformly dissolved in 150 parts by weight of N-methyl-2-pyrrolidone, followed by pressure filtration using a 1 ⁇ m filter. The obtained photosensitive resin composition was evaluated in the same manner as in Example 18. The results are shown in Table 3.
  • Example 20 [Preparation and Evaluation of Photosensitive Resin Composition] 100 parts by weight of the polyamic acid ester obtained in Example 12, 20 parts by weight of tetraethylene glycol dimethacrylate, 2 parts by weight of the compound represented by the above formula (22-2) and 2 parts by weight of benzotriazole were added to N-methyl-2. A photosensitive resin composition was obtained by stirring until dissolved in 150 parts by weight of pyrrolidone and then filtering under pressure using a 1 ⁇ m filter. The obtained photosensitive resin composition was evaluated in the same manner as in Example 18. The results are shown in Table 3.
  • Example 21 [Preparation and Evaluation of Photosensitive Resin Composition] 100 parts by weight of the polyamic acid ester obtained in Example 12, 20 parts by weight of tetraethylene glycol dimethacrylate and 2 parts by weight of the compound represented by the above formula (25) are uniformly added to 150 parts by weight of N-methyl-2-pyrrolidone. After stirring until dissolved, a photosensitive resin composition was obtained by pressure filtration using a 1 ⁇ m filter. The obtained photosensitive resin composition was evaluated in the same manner as in Examples 13-17. The results are shown in Table 3.
  • the development time is set to twice the time until an unexposed coating film having the same thickness is completely dissolved by being immersed in cyclopentanone, and the wafer after exposure is immersed in cyclopentanone for paddle development. Thereafter, rinsing with isopropanol was performed.
  • the sensitivity is defined as the minimum exposure amount at which the amount of the coating film dissolved in the exposed area is less than 10% of the initial film thickness, and the minimum value of the mask dimension of the square hole-shaped opening is defined as the resolution. Characteristics were evaluated.
  • (A-1) Sensitivity Sensitivity is 300 mJ / cm 2 or less: ⁇ Sensitivity is more than 300 mJ / cm 2 and 500 mJ / cm 2 or less: ⁇ Sensitivity is over 500 mJ / cm 2 : ⁇ (A-2) Resolution Resolution is 10 ⁇ m or less: ⁇ Resolution over 10 ⁇ m and below 30 ⁇ m: ⁇ Resolution over 30 ⁇ m: ⁇
  • the photosensitive resin composition of Example 13-21 showed good sensitivity and resolution, and the cured film obtained from the photosensitive resin composition of Example 13-21 had a viscosity of 30 MPa or less. It can be seen that the stress is low. On the other hand, in the resin composition of Comparative Example 10, peeling occurred during development, and the sensitivity and resolution could not be evaluated. In the resin compositions of Comparative Example 11 and Comparative Example 13, it can be seen that since the i-line transmittance of the polyamic acid ester is low, the resolution is lowered. The resin composition of Comparative Example 12 shows good sensitivity and resolution, but it can be seen that the residual stress of the obtained cured film is higher than 35 MPa.
  • the resin composition containing the polyimide precursor of the present invention can be suitably used as a protective film material or pattern film forming material for electronic parts such as semiconductor devices.

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PCT/JP2013/007467 2012-12-21 2013-12-19 ポリイミド前駆体、該ポリイミド前駆体を含む感光性樹脂組成物、それを用いたパターン硬化膜の製造方法及び半導体装置 Ceased WO2014097633A1 (ja)

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US14/654,758 US9751984B2 (en) 2012-12-21 2013-12-19 Polyimide precursor, photosensitive resin composition containing said polyimide precursor, and cured-pattern-film manufacturing method and semiconductor device using said photosensitive resin composition
KR1020157008796A KR102214856B1 (ko) 2012-12-21 2013-12-19 폴리이미드 전구체, 그 폴리이미드 전구체를 포함하는 감광성 수지 조성물, 그것을 사용한 패턴 경화막의 제조 방법 및 반도체 장치
CN201380066870.2A CN104870523B (zh) 2012-12-21 2013-12-19 聚酰亚胺前体、包含该聚酰亚胺前体的感光性树脂组合物、使用其的图案固化膜的制造方法和半导体装置
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