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WO2015011893A1 - Composition de résine, procédé de formation d'un motif en l'utilisant, et composant électronique - Google Patents

Composition de résine, procédé de formation d'un motif en l'utilisant, et composant électronique Download PDF

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Publication number
WO2015011893A1
WO2015011893A1 PCT/JP2014/003713 JP2014003713W WO2015011893A1 WO 2015011893 A1 WO2015011893 A1 WO 2015011893A1 JP 2014003713 W JP2014003713 W JP 2014003713W WO 2015011893 A1 WO2015011893 A1 WO 2015011893A1
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Prior art keywords
group
formula
carbon atoms
resin composition
component
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English (en)
Japanese (ja)
Inventor
敬司 小野
榎本　哲也
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 JP2015528134A priority Critical patent/JP6414060B2/ja
Publication of WO2015011893A1 publication Critical patent/WO2015011893A1/fr
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    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

  • the present invention relates to a resin composition, a pattern forming method using the resin composition, and an electronic component.
  • an interlayer insulating film called a low-k layer is required to reduce the dielectric constant. Since the low-k layer has a pore structure, there is a problem that the mechanical strength is lowered.
  • a cured film formed of a polyimide resin is used. The cured film is required to have properties such as thick film formability and high elastic modulus.
  • properties such as thick film formability and high elastic modulus.
  • the stress after curing increases, and the warpage of the semiconductor wafer increases, which may cause problems when transporting or fixing the wafer. Development is desired.
  • Patent Document 3 a resin composition using 3-isocyanatopropyltriethoxysilane has been reported (for example, Patent Document 3).
  • Patent Document 3 since it has a highly reactive isocyanate group, there is a problem that the storage stability of the resin composition is deteriorated.
  • the rigid polyimide precursor which has a low CTE after curing, generates a stress with the silicon wafer when it is applied to the silicon wafer and heated before exposure (when it is made into a resin film). There is a problem that the film is easily peeled off from the silicon wafer.
  • adhesion after curing is also required. If the adhesiveness after curing is poor, the cured film peels off from the substrate, causing a defect in the next process.
  • Japanese Patent No. 2826940 Japanese Patent No. 4144110 Japanese Patent Laid-Open No. 11-338157
  • a resin composition containing (a) a polyimide precursor, (b) an alkoxysilane compound, (c) a photoinitiator and (d) a solvent,
  • the component (a) has a structural unit represented by the following formula (1),
  • the component (b) contains one or more of a compound represented by the following formula (4-1) and a compound represented by the following formula (4-2),
  • the component (c) is a resin composition containing an oxime ester compound.
  • A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d)
  • B is a divalent organic group represented by the following formula (3)
  • R 1 and R 2 are each independently a hydrogen atom, a monovalent organic group, or a group having a carbon-carbon unsaturated double bond, and at least one of R 1 and R 2 is a carbon-carbon unsaturated double bond.
  • a group having a bond is any one of tetravalent organic groups represented by the following formulas (2a) to (2d)
  • B is a divalent organic group represented by the following formula (3)
  • R 1 and R 2 are each independently a hydrogen atom, a monovalent organic group, or a group having a carbon-carbon unsaturated double bond, and at least one of R 1 and R 2 is a carbon-carbon unsaturated double bond.
  • a group having a bond is any one of tetravalent organic groups represented by the following formulas (2a) to (2d)
  • B is a divalent organic group represented
  • X and Y are each independently a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent organic group, provided that R 3 to R 10 are a monovalent organic group having a halogen atom and a halogen atom. is not.
  • each R 11 is independently an alkyl group having 1 to 4 carbon atoms
  • Each R 12 independently represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms; a is an integer of 1 to 3, n is an integer from 1 to 6,
  • R 13 is a group of the following formula (5) or (6).
  • R 14 is an alkyl group having 1 to 10 carbon atoms or a monovalent organic group derived from hydroxyalkylsilane.
  • R 15 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group. R 14 and R 15 may each have a substituent.
  • each R 11 is independently an alkyl group having 1 to 4 carbon atoms
  • Each R 12 independently represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms
  • a is an integer of 1 to 3
  • n is an integer from 1 to 6
  • R 13 is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group.
  • R 16 to R 22 are each independently a hydrogen atom or a monovalent group.
  • 4 The resin composition according to any one of 1 to 3, wherein the component (a) further has a structural unit represented by the following formula (9).
  • D is a tetravalent organic group represented by the following formula (10)
  • B, R 1 and R 2 are the same as those in the formula (1).
  • Z is an oxygen atom or a sulfur atom.
  • A applying the resin composition according to any one of 1 to 4 on a substrate and drying to form a coating film;
  • B a step of irradiating the coating film formed in the step (a) with an actinic ray to expose it in a pattern;
  • C removing unexposed portions other than the exposed portions by development;
  • D A process for producing a cured pattern film, comprising a step of heat-treating the pattern obtained in the step (c) to form a polyimide pattern.
  • 6. A cured film obtained by curing the resin composition according to any one of 1 to 4.
  • the obtained cured film has low stress, and has excellent adhesion at the time of development with the substrate and excellent adhesion after curing in the post-development film, and the resin composition.
  • a method for producing a patterned cured film is provided.
  • the resin composition of the present invention contains (a) a polyimide precursor, (b) an alkoxysilane compound, (c) a photoinitiator and (d) a solvent,
  • the component (a) has a structural unit represented by the following formula (1),
  • the component (b) contains one or more of a compound represented by the following formula (4-1) and a compound represented by the following formula (4-2),
  • the component (c) contains an oxime ester compound.
  • A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d)
  • B is a divalent organic group represented by the following formula (3)
  • R 1 and R 2 are each independently a hydrogen atom, a monovalent organic group, or a group having a carbon-carbon unsaturated double bond, and at least one of R 1 and R 2 is a carbon-carbon unsaturated double bond.
  • a group having a bond is any one of tetravalent organic groups represented by the following formulas (2a) to (2d)
  • B is a divalent organic group represented by the following formula (3)
  • R 1 and R 2 are each independently a hydrogen atom, a monovalent organic group, or a group having a carbon-carbon unsaturated double bond, and at least one of R 1 and R 2 is a carbon-carbon unsaturated double bond.
  • a group having a bond is any one of tetravalent organic groups represented by the following formulas (2a) to (2d)
  • B is a divalent organic group represented
  • X and Y are each independently a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent organic group, provided that R 3 to R 10 are a monovalent organic group having a halogen atom and a halogen atom. is not.
  • each R 11 is independently an alkyl group having 1 to 4 carbon atoms
  • Each R 12 independently represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms
  • a is an integer of 1 to 3
  • n is an integer from 1 to 6
  • R 13 is a group of the following formula (5) or (6).
  • R 14 is an alkyl group having 1 to 10 carbon atoms or a monovalent organic group derived from hydroxyalkylsilane.
  • R 15 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group.
  • R 14 and R 15 may each have a substituent.
  • each R 11 is independently an alkyl group having 1 to 4 carbon atoms
  • Each R 12 independently represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms
  • a is an integer of 1 to 3
  • n is an integer from 1 to 6
  • R 13 is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group.
  • A Component: Polyimide precursor
  • the polyimide precursor used by this invention has a structural unit represented by the said Formula (1).
  • a in the formula (1) is a structure derived from tetracarboxylic dianhydride used as a raw material for the polyimide precursor.
  • A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d).
  • X and Y are each independently a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.
  • Examples of the “divalent group that is not conjugated with the benzene ring to which each is bonded” include —O—, —C (CH 3 ) 2 —, —C (CH 3 ) (CF 3 ) —, —C (CF 3 ) 2- , -Si (CH 3 ) 2- and the like.
  • Examples of tetracarboxylic dianhydrides that give tetravalent organic groups represented by the formulas (2a) to (2d) include pyromellitic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride. 4,4′-biphenyltetracarboxylic dianhydride, 9,9′-dimethyl-2,3,6,7-xanthenetetracarboxylic dianhydride, represented by the following formulas (11) to (17) A tetracarboxylic dianhydride is mentioned.
  • any of these may be used alone, or two or more kinds of tetracarboxylic dianhydrides may be used in combination.
  • pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, tetracarboxylic acid diacids represented by the formulas (11) and (13) are used from the viewpoint of reducing the thermal expansion of the cured film.
  • anhydride more preferably pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the formula (11), It is particularly preferable to use merit acid dianhydride, 4,4′-biphenyltetracarboxylic dianhydride.
  • B in Formula (1) is a structure derived from a diamine used as a raw material for the polyimide precursor. From the viewpoint of low stress and i-line transmittance, B is a divalent organic group represented by the following formula (3).
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent organic group. However, the case where it is a monovalent organic group having a halogen atom and a halogen atom is excluded. In the case of a halogen atom or a monovalent organic group containing a halogen atom, when the cured film is subjected to plasma treatment, the bond between carbon-halogen atoms may be broken and the cured film may be deteriorated.
  • the monovalent organic group include an alkyl group having 1 to 20 carbon atoms (such as a methyl group) and an alkoxy group having an alkyl group having 1 to 20 carbon atoms (such as a methoxy group).
  • Examples of the diamine used as a raw material for the polyimide precursor include 2,2′-diaminobenzidine, 3,3′-diaminobenzidine, 2,2 ′, 3,3′-tetramethylbenzidine, and 2,2′-dimethoxybenzidine. 3,3′-dimethoxybenzidine and the like can be used.
  • 2,2'-diaminobenzidine and 3,3'-diaminobenzidine are preferred, and 2,2'-diaminobenzidine is more preferred from the viewpoint of reducing stress.
  • R 1 and R 2 are each independently a hydrogen atom, a monovalent organic group, or a group having a carbon-carbon unsaturated double bond. At least one of R 1 and R 2 is a group having a carbon-carbon unsaturated double bond.
  • Examples of the monovalent organic group represented by R 1 and R 2 include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms.
  • Examples of the group having a carbon-carbon unsaturated double bond as R 1 and R 2 include an acryloxyalkyl group having 1 to 10 carbon atoms and a methacryloxyalkyl group.
  • the polyimide precursor has a monovalent organic group having a carbon-carbon unsaturated double bond at least in part, so that it is combined with a compound that generates radicals upon irradiation with actinic rays (for example, i-line exposure), and radical polymerization. It is possible to crosslink between the molecular chains by the above, and it becomes easy to obtain a negative resin composition.
  • alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, n-hexyl, n-heptyl, and n-decyl. Group, n-dodecyl group and the like.
  • cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
  • 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.
  • R 1 and R 2 are preferably not a hydrogen atom but a group introduced by an ester bond.
  • R 1 and R 2 are preferably an acryloxyethyl group, an acryloxybutyl group, a methacryloxyethyl group, or a methacryloxyethyl group introduced by an ester bond.
  • the polyimide precursor has a structural unit represented by the formula (1) of 10 mol% or more with respect to all the structural units of the polyimide precursor, and 20 mol% or more. More preferably.
  • the polyimide precursor used in the resin composition of the present invention further has a structural unit represented by the following formula (9) from the viewpoint of improving i-line transmittance, improving adhesion after curing, and improving mechanical properties. You may do it.
  • D is a tetravalent organic group represented by the following formula (10)
  • B, R 1 and R 2 are identical to those in the formula (1).
  • Z represents an oxygen atom (ether bond: —O—) or a sulfur atom (sulfide bond: —S—).
  • Examples of tetracarboxylic dianhydrides that give the structure of formula (10) include 4,4'-oxydiphthalic dianhydride and thioether diphthalic anhydride. When synthesizing the polyimide precursor, these may be used alone or in combination of two. From the viewpoint of adhesion after curing, 4,4'-oxydiphthalic dianhydride is preferably used.
  • the polyimide precursor has both the structural unit represented by the formula (1) and the structural unit represented by the formula (9), the polyimide precursor is copolymerized.
  • the copolymer include a block copolymer and a random copolymer, but are not particularly limited.
  • the formula (1) and the formula (9) are preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and more preferably 2/8 to More preferably, it is 7/3.
  • the polyimide precursor of component (a) may have a structural unit other than the structural unit represented by the formula (1) and the unit represented by the formula (9).
  • Examples of the tetracarboxylic dianhydride that gives a polyimide precursor having a structural unit other than the structural unit represented by the formula (1) and the unit represented by the formula (9) include 3,3 ′, 4,4, for example.
  • Examples of the diamine that gives a polyimide precursor having a structural unit other than the structural unit represented by the formula (1) and the formula (9) include 4,4′-oxydianiline, 4,4 ′ -Diaminodiphenylmethane, 1,4-cyclohexanediamine, 1,3'-bis (3-aminophenoxy) benzene and the like.
  • these tetracarboxylic dianhydrides and diamines are preferably 20 mol% or less, preferably 10 mol% or less, based on the total amount of tetracarboxylic dianhydrides and diamines used as raw materials.
  • these tetracarboxylic dianhydrides and diamines are preferably 20 mol% or less, preferably 10 mol% or less, based on the total amount of tetracarboxylic dianhydrides and diamines used as raw materials.
  • the molecular weight of the component (a) polyimide precursor is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and still more preferably 20,000 to 85,000 in terms of polystyrene. If the weight average molecular weight is less than 10,000, the stress after curing may not be sufficiently reduced, and if it is greater than 100,000, the solubility in a solvent may be reduced, or the viscosity of the solution may be increased and the handleability may be reduced. There is a risk.
  • a weight average molecular weight can be measured by the gel permeation chromatography method, and is calculated
  • the resin composition of the present invention preferably contains 20 to 60% by mass, more preferably 25 to 55% by mass, and more preferably 30 to 55% by mass of the polyimide precursor of component (a) in the total resin composition. It is more preferable to contain.
  • the polyimide precursor of component (a) can be synthesized by a conventionally known method.
  • the alkoxysilane compound (b) is used as a component that improves the adhesion between the film and the substrate.
  • the resin composition of the present invention contains (b1) a compound represented by the following formula (4-1) as the component (b) from the viewpoint of improving the adhesion of the resulting cured film to the substrate. Is preferred.
  • R 11 is an alkyl group having 1 to 4 carbon atoms
  • R 12 are each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms
  • a is an integer of 1 to 3
  • n is an integer from 1 to 6
  • R 13 is a group of the following formula (5) or (6).
  • R 14 is an alkyl group having 1 to 10 carbon atoms or a monovalent organic group derived from hydroxyalkylsilane.
  • R 15 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group. R 14 and R 15 may each have a substituent.
  • the resin composition of the present invention preferably contains (b2) a compound represented by the following formula (4-2) as the component (b).
  • each R 11 is independently an alkyl group having 1 to 4 carbon atoms
  • Each R 12 independently represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms
  • a is an integer of 1 to 3
  • n is an integer from 1 to 6
  • R 13 is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group.
  • component (b1) and the component (b2) are preferable to use in terms of increasing the adhesiveness during development with the substrate and the adhesiveness after curing in the post-development film.
  • the resin composition of the present invention can exhibit good adhesion to a substrate when used as a cured film. This is because, in the heat curing step of the resin film, the isocyanate protecting group of the compound represented by the formula (4-1) is eliminated, and the highly reactive isocyanate group is regenerated, so that the carboxyl at the terminal of the polymer (polyimide precursor) is recovered. It is thought to react with acids and amines to form chemical bonds.
  • the resin composition of the present invention can exhibit good storage stability by containing the component (b1). This is presumably because the protected isocyanate of the compound represented by the formula (4-1) is in a low-reactive state in which the protective group is not eliminated before the heat curing step.
  • the compound represented by the formula (4-1) can be obtained by mixing the compound represented by the formula (21) with a compound having a hydroxyl group or an amino group and subjecting it to an addition reaction.
  • R 29 is an alkyl group having 1 to 4 carbon atoms
  • R 30 each independently represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms
  • b is an integer of 1 to 3
  • R 28 is an alkylene group having 1 to 6 carbon atoms.
  • Examples of the compound represented by the formula (21) include 1-isocyanatomethyltrimethylsilane, 1-isocyanatemethyltriethylsilane, 1-isocyanatemethyltripropylsilane, 1-isocyanatemethyltributylsilane, 1-isocyanatemethyltrimethylsilane.
  • the compound in which R 13 is represented by the formula (5) can be obtained by reacting the compound of the formula (21) with a compound having a hydroxyl group and a compound having a hydroxyalkylsilane.
  • This reaction formula is shown in the following formula (22).
  • R is —R 28 —Si (OR 29 ) b (R 30 ) 3-b ;
  • R 28 , R 29 , R 30 and b are the same as in formula (21),
  • R ′ is an alkyl group having 1 to 10 carbon atoms.
  • R ' is reacted with the formula (21) compounds is an alkyl group having 1 to 10 carbon atoms
  • the compound R 14 in the formula (5) is an alkyl group having 1 to 10 carbon atoms is obtained.
  • the compound having 1 to 10 carbon atoms having a hydroxyl group include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, hexanol, heptanol, octanol, nonal, decanol, 2- Methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl- Examples include 1-hexanol, 2,2-dimethyl-1-propanol, and cyclohexanol
  • hydroxyalkylsilane compound examples include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, N- (Hydroxymethyl) -N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropoxy-5-hydroxyflavone, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, 2-hydroxy-4- ( 3-methyldiethoxysilylpropoxy) diphenyl ketone, 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane, 3- (N-acety
  • the compound in which R 13 is represented by formula (6) is a compound of formula (21), ammonia, a compound having 1 to 10 carbon atoms having an amino group, an aminoalkylsilane compound Alternatively, it can be obtained by reacting a heterocyclic compound having an amino group.
  • This reaction formula is shown in the following formula (23).
  • R is —R 28 —Si (OR 29 ) b (R 30 ) 3-b ;
  • R 28 , R 29 , R 30 and b are the same as in formula (21),
  • R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R ' is reacted with the formula (21) a compound having a hydrogen atom
  • a compound R 15 of formula (6) is a hydrogen atom
  • An example of such a compound is ammonia.
  • R ′ is an alkyl group having 1 to 10 carbon atoms
  • formula (21) a compound in which R 15 in formula (6) is an alkyl group having 1 to 10 carbon atoms is obtained.
  • Examples of the compound having 1 to 10 carbon atoms having an amino group include aminomethane, aminoethane, aminopropane, aminobutane, aminopentane, aminohexane, aminoheptane, aminooctane, aminononane, aminodecane, and 2-ethylaminohexane.
  • aminoalkylsilane compounds include 4-aminobutyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysiloxane, N- (2-aminoethyl) -3-aminopropylmethyl-dimethoxysilane, N- ( 2-aminoethyl) -4-aminopropylmethyl-triethoxysilane and the like.
  • heterocyclic compound having an amino group When the heterocyclic compound having an amino group is reacted with the compound of the formula (21), a compound in which R 15 of the formula (6) is a heterocyclic group is obtained.
  • the heterocyclic compound having an amino group include 5-aminotetrazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-aminopyridine, 2-aminopyridine, 3 -Aminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2-aminothiazole, 2-aminobenzothiazole and the like.
  • the reactions of the formulas (22) and (23) may be performed at room temperature or in a temperature range between 50 ° C. and 100 ° C. Further, the raw materials may be directly mixed or a solvent such as dimethylformamide, 1,2-diethoxyethane, N-methylpyrrolidone may be used.
  • the component (b1) preferably contains at least one of the following compounds from the viewpoint of providing better adhesion and better storage stability.
  • the content of the component (b1) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and further preferably 1 to 6 parts per 100 parts by mass of the component (a).
  • it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
  • the resin composition of the present invention preferably contains the component (b2) from the viewpoint of improving the adhesion between the film during development and the silicon wafer.
  • the epoxy group or the hydroxyl group reacts with the carboxyl group or amino group present at the terminal in the component (a) at the stage of performing the pre-exposure heating. It is thought that it has peeling of.
  • the compounds used as component (b2) include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis (2- Hydroxyethyl) -3-aminopropyl-triethoxysilane. Particularly preferred is bis (2-hydroxyethyl) -3-aminopropyl-triethoxysilane.
  • the content of component (b2) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 3 with respect to 100 parts by mass of component (a).
  • component (a) is preferably 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
  • the component (b1) and the component (b2) may be used alone or in combination.
  • the content of component (b1) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 to 3 parts per 100 parts by weight of component (a).
  • the content of the component (b2) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and still more preferably 1 to 3 with respect to 100 parts by weight of the component (a).
  • the total content of the component (b1) and the component (b2) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, and further preferably 3 to 6 with respect to 100 parts by weight of the component (a). preferable.
  • it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.
  • alkoxysilane compounds other than the above may be included.
  • alkoxysilane compounds other than the above ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propyl Succinic anhydride, phenyltriethoxys
  • the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor from the viewpoint of adhesion after curing, and preferably 0.5 to 15 parts by mass.
  • the amount is more preferably part by mass, and further preferably 0.5 to 10 parts by mass.
  • Photoinitiator (c) A component contains an oxime ester compound. Specifically, a compound having a structure represented by the formula (7) is preferable. (In the formula (7), R 16 to R 22 are each independently a hydrogen atom or a monovalent group.)
  • R 16 represents a phenyl group (an alkyl group having 1 to 10 carbon atoms, a phenyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl mercapto group, or an alkyl group having 1 to 10 carbon atoms).
  • An alkyl group having 1 to 20 carbon atoms (provided that the alkyl group has 2 to 20 carbon atoms, one or more oxygen atoms between main chain carbon atoms) And / or may be substituted with one or more hydroxyl groups), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (provided that the carbon number is 1 to 6)
  • it may have one or more oxygen atoms between main chain carbon atoms and / or may be substituted with one or more hydroxyl groups)
  • a cyano group a nitro group, a carbon number of 1 to 4 A
  • R 17 is an alkanoyl group having 2 to 12 carbon atoms (which may be substituted with one or more halogen atoms or a cyano group), an ⁇ or ⁇ 4 to 6 carbon atom having no unsaturated carbonyl structure.
  • Alkenoyl group, benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, phenyl group, alkoxyl group, thioether group, dialkylamino group), alkoxycarbonyl group having 2 to 6 carbon atoms, phenoxycarbonyl
  • One of the groups (which may be substituted with one or more alkyl group having 1 to 6 carbon atoms or a halogen atom).
  • R 18 , R 19 , R 20 , R 21 and R 22 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (however, a hydroxyl group, a mercapto group) Group, an alkoxyl group having 1 to 12 carbon atoms and an alkyl mercapto group (provided that at least one hydrogen atom in the alkyl chain is a hydroxyl group, a mercapto group, a cyano group, an alkoxyl group having 1 to 4 carbon atoms, a carbon number of 3 -6 alkenyloxy group, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, alkylcarbonyloxy group having 2 to 5 carbon atoms, phenylcarbonyloxy group, carboxyl group, 2
  • a carbonyl group (provided that when the alkoxyl group has 2 to 11 carbon atoms, the alkoxyl group has one or more oxygen atoms between main chain carbon atoms and / or is substituted with one or more hydroxyl groups)
  • a phenoxycarbonyl group, a phenoxy group, and a phenylthio group (provided that at least one hydrogen atom on the phenyl ring is a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, or an alkyl mercapto group having 1 to 6 carbon atoms).
  • Alkyl group having 1 to 12 carbon atoms carboxyl group, hydroxymethyloxycarbonyl group, hydroxyethyloxycarbonyl group, Optionally substituted with either a droxyethyloxy group or a hydroxypropyloxy group), an alkylsulfinyl group having 1 to 6 carbon atoms and an alkylsulfonyl group, an arylsulfinyl group and an arylsulfonyl group (provided that the aryl group is a carbon atom)
  • An aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms), an alkoxysulfonyl group having 1 to 6 carbon atoms, an aryloxysulfonyl group having 6 to 10 carbon atoms, Any one of dialkylamino groups having two alkyl groups having 1 to 10.
  • an alkyl mercapto group having 1 to 12 carbon atoms (provided that at least one or more hydrogen atoms in the alkyl chain are Hydroxyl group, mercapto group, cyano group, alkoxyl group having 1 to 4 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, 2- Anoethoxy group, C4-C7 2- (alkoxycarbonyl) ethoxy group, C2-C5 alkylcarbonyloxy group, phenylcarbonyloxy group, carboxyl group, C2-C5 alkoxylcarbonyl group, main chain carbon A C2-C6 alkoxyl group having one or more oxygen atoms between atoms, a C2-C8 alkylcarbonyloxy group, and a phenyl group (which may be substituted), a phenylthio group (however, At least one hydrogen atom on the phenyl ring is a hydroxyl group, an alkylthio group (however, At
  • R 16 is preferably an alkyl group having 1 to 10 carbon atoms. Any one of R 18 , R 19 , R 20 , R 21 and R 22 is an alkyl mercapto group having 1 to 12 carbon atoms (provided that at least one hydrogen atom in the alkyl chain is a hydroxyl group, a mercapto group; Cyano group, alkoxy group having 1 to 4 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, and 2 to 5 carbon atoms An alkylcarbonyloxy group, a phenylcarbonyloxy group, a carboxyl group, an alkoxylcarbonyl group having 2 to 5 carbon atoms, an alkoxyl group having 2 to 6 carbon atoms having one or more oxygen atoms between main chain carbon atoms, and 2 to 8 alkylcarbonyloxy groups, which may be
  • R 16 is more preferably a hexyl group. More preferably, R 18 , R 19 , R 20 and R 17 are hydrogen atoms and R 15 is a phenylthio group. Among them, the compound represented by the formula (8) (1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime)) is more preferable. (In Formula (8), the aromatic ring may have a substituent.)
  • the content of the component (c) is preferably 0.1 to 20 parts by mass and preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor as the component (a). More preferably, it is 0.5 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, and particularly preferably 1 to 5 parts by mass.
  • the blending amount is 0.1 parts by mass or more, crosslinking of the exposed part proceeds more sufficiently and the photosensitive properties (sensitivity, resolution) tend to be better, and when it is 20 parts by mass or less, the cured film The heat resistance of can be made better.
  • the resin composition of the present invention is excellent in photosensitive characteristics by combining the component (a) and the component (c), and the stress of the cured film to be formed becomes low.
  • a polyimide precursor having a structural unit represented by the formula (1) is used as the component (a) and a compound represented by the formula (7) is used as the component (c), it is represented by the formula (7). Since the compound exhibits high activity particularly when irradiated with an electron beam such as i-line, good photosensitive characteristics can be realized. Furthermore, when it becomes a polyimide by heat treatment, it has a feature of exhibiting low stress due to its rigid skeleton.
  • (D) Component Solvent
  • a polar solvent that completely dissolves the polyimide precursor as the component (a) is preferable.
  • the solvent is preferably contained in the resin composition in an amount of 40 to 80% by mass, more preferably 45 to 75% by mass, and further preferably 45 to 70% by mass.
  • an addition polymerizable compound may be blended as necessary.
  • the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane.
  • Triacrylate trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, Intererythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2 -Hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, m
  • the content is preferably 1 to 100 parts by mass with respect to 100 parts by mass 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 75 parts by mass, more preferably 1 to 50 parts by mass.
  • the resin composition of the present invention may contain 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, Examples thereof include N-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 is preferably from about 0.1 parts by mass with respect to 100 parts by mass of the polyimide precursor from the viewpoint of the storage stability of the resin composition and the heat resistance of the resulting cured film.
  • the amount is preferably 01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.05 to 5 parts by mass.
  • the resin composition of the present invention comprises, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, and 100% by weight of the above components (a) to (d) and optionally other components described above. It may consist of at least one of the following.
  • the pattern cured film of the present invention can be obtained by heating the above-described 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 patterned cured film of the present invention comprises (a) a step of applying the resin composition of the present invention on a substrate and drying to form a resin film, and (b) a coating film formed in the step (a). Irradiating with actinic rays to expose to a pattern, (c) removing unexposed portions other than the exposed portions by development, and (d) heating the pattern obtained in the step (c) And forming a polyimide pattern.
  • the step (a) of applying a resin composition on a substrate and drying to form a coating film will be described.
  • Examples of the method for applying the resin composition of the present invention on a substrate include an immersion method, a spray method, a screen printing method, and a spin coating method.
  • the substrate examples include a silicon wafer, a metal substrate, and a ceramic substrate. Since the resin composition 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 by heating (drying), whereby a coating film (resin film) with less adhesiveness can be formed.
  • 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 step (b) of irradiating the coating film with actinic rays and exposing it in a pattern and the step (c) of removing an unexposed portion other than the exposed portion by development to obtain a patterned resin film will be described.
  • the coating film obtained by the above method is exposed in a pattern by irradiating actinic rays through a mask on which a desired pattern is drawn.
  • the 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 resin film can be obtained by dissolving and removing the unexposed portion with an appropriate developer.
  • the developer is not particularly limited, but is a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous alkali solution such as an aqueous solution of sodium carbonate and an aqueous solution of tetramethylammonium hydroxide, N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, ⁇ -butyrolactone, and acetic acid esters, and these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used. After development, rinsing with a poor solvent (for example, water, ethanol, 2-propanol) or the like is performed as necessary.
  • a poor solvent for example, water, ethanol, 2-propanol
  • the process (d) of heat-processing a pattern resin film is demonstrated.
  • the imidization of the polyimide precursor contained in the resin composition proceeds to obtain a pattern cured film.
  • 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 patterned cured film of the present invention thus obtained can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer or the like of a semiconductor device.
  • Examples of the semiconductor device of the present invention include Logic semiconductor devices such as MPU and memory semiconductor devices 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, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the Al wiring layer 2.
  • 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 a conductive ball 7 formed of solder, gold or the like as an external connection terminal. Further, 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 provided 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.
  • the electronic component of the present invention is particularly limited except that it has a cover coat using the cured film or pattern cured film of the present invention, a core for rewiring, a ball collar such as solder, an underfill used in flip chips, etc. Instead, it can take various structures.
  • tetracarboxylic dianhydride component 2 shown in Table 1 or 2 2-hydroxyethyl methacrylate (2 equivalents relative to tetracarboxylic dianhydride 2), and a catalytic amount Of DBU was dissolved in N-methyl-2-pyrrolidone (4 times the amount of tetracarboxylic dianhydride 2 by mass) and stirred at room temperature for 48 hours to obtain an ester solution 2.
  • 2.2 equivalents of thionyl chloride was added dropwise to the total amount of tetracarboxylic dianhydrides 1 and 2 while cooling in an ice bath, followed by stirring for 1 hour.
  • an acid chloride solution was prepared.
  • a predetermined amount of diamine 1 shown in Table 1 or 2 and, if necessary, a predetermined amount of diamine 2 and pyridine (twice equivalent of thionyl chloride) were added to N-methyl-2-pyrrolidone (mass ratio of diamine 1). And 4 times the total amount of 2) were prepared and added dropwise to the previously prepared acid chloride solution while cooling in an ice bath. After completion of the dropping, the reaction solution was dropped into distilled water, and the resulting precipitate was collected by filtration, washed several times with distilled water, and then vacuum dried to obtain a polyamic acid ester.
  • the weight average molecular weight of the obtained polyamic acid ester was determined in terms of standard polystyrene by gel permeation chromatography (GPC).
  • reaction solution After completion of dropping, the reaction solution was heated in a 60 ° oil bath for 3 hours. From the IR spectrum of the reaction solution after heating, the disappearance of the peak of the isocyanate group near 2260 cm -1, and a peak due to NH group near 3370cm -1 were observed.
  • reaction product was confirmed by the disappearance of KBE-9007 by thin layer column chromatography on carrier silica gel (developing solvent was hexane, color former was iodine). From these, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane addition product (b1-1), ethanol and 3-isocyanatopropyltriethoxysilane It was confirmed that the addition product (b1-3) was obtained.
  • alkoxysilane compounds b3 3-isocyanatopropyltriethoxysilane (KBE-9007: manufactured by Shin-Etsu Silicone)
  • b4 3-isocyanatopropyltrimethoxysilane (Y-5187: manufactured by MOMENTIVE performance materials)
  • b5 Phenyltrimethoxysilane (KBM-103: manufactured by Shin-Etsu Silicone)
  • a polyamic acid ester solution obtained by dissolving 100 parts by mass of the obtained polyamic acid ester in 150 parts by mass of N-methyl-2-pyrrolidone was spin-coated on a glass plate, and then heated at 100 ° C. on a hot plate. Then, a heat treatment was performed for 3 minutes to prepare a film having a film thickness of 20 ⁇ m, and the transmittance at 365 nm was measured.
  • the i-line transmittance was measured by a cast film method using a visible ultraviolet spectrophotometer U-3310 manufactured by Hitachi High-Technologies Corporation and evaluated according to the following criteria.
  • the obtained photosensitive resin composition was applied on a 6-inch silicon wafer by a spin coating method and dried on a hot plate at 100 ° C. for 3 minutes to form a resin film having a thickness of 10 ⁇ m.
  • the resin film is exposed through a photomask using a Canon i-line stepper FPA-3000iW to irradiate a predetermined pattern with 50 to 500 mJ / cm 2 of i-line in increments of 50 mJ / cm 2. It was.
  • the development time is set to twice the time until an unexposed coating film of the same thickness is immersed in cyclopentanone and completely dissolved, and the wafer after exposure is immersed in cyclopentanone and paddle developed.
  • the minimum exposure amount at which the amount of coating film dissolved in the exposed portion was less than 10% of the initial film thickness was evaluated as sensitivity, and the minimum value of the mask dimension of the square hole-shaped opening was evaluated as resolution.
  • the sensitivity was evaluated according to the following criteria. 300 mJ / cm 2 or less: ⁇ More than 300 mJ / cm 2 and 500 mJ / cm 2 or less: ⁇ Greater than 500 mJ / cm 2 : ⁇
  • the obtained photosensitive resin composition was applied to a 6-inch silicon wafer having a thickness of 625 ⁇ m and spin-coated so that the film thickness after curing was 10 ⁇ m. This was heat-cured at 375 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Lindberg to obtain a polyimide film (cured film).
  • the residual stress of the cured polyimide film was measured at room temperature using a thin film stress measuring apparatus FLX-2320 manufactured by KLA Tencor and evaluated based on the following criteria. Stress of 30 MPa or less: ⁇ Stress greater than 30 MPa and less than 35 MPa: ⁇ Stress greater than 35 MPa: x
  • the silicon wafer with a cured film prepared for measuring the residual stress was immersed in NMP at 70 ° C. for 20 minutes, then washed with pure water to wipe off moisture adhering to the surface of the cured film. Then, it was air-dried and evaluated according to the following criteria.
  • the rate of change of the thickness of the cured film after air drying with respect to the initial film thickness is within ⁇ 10%: More than ⁇ 10% and less than ⁇ 20%: ⁇ More than ⁇ 20%: ⁇
  • Component (c)) c1 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime) (trade name “IRGACURE OXE-01” manufactured by BASF AG)
  • c2 Ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (BASF, trade name “IRGACURE OXE-02”)
  • c3 4,4′-bis (diethylamino) benzophenone
  • c4 bis [4- (2-hydroxy-2-methylpropionyl) phenyl] methane
  • c5 bis ( ⁇ 5 -cyclopentadienyl) bis [2,6-difluoro -3- (1H-pyr-1-yl)] phenyltitanium
  • the cured film has excellent adhesion to the substrate, and the component (b2) is used.
  • the adhesion of the developed film is improved.
  • the resin composition of the present invention can be used as a protective film material or pattern film forming material for electronic parts such as semiconductor devices.

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Abstract

L'invention concerne une composition de résine qui comporte (a) un précurseur de polyimide, (b) au moins un composé d'alcoxysilane, (c) un photo-initiateur et (d) un solvant, le constituant (a) comportant une unité structurale représentée par la formule (1), le constituant (b) comportant un ou plusieurs composés parmi des composés représentés par la formule (4-1) et des composés représentés par la formule (4-2), et le constituant (c) comportant un composé d'ester d'oxime.
PCT/JP2014/003713 2013-07-23 2014-07-14 Composition de résine, procédé de formation d'un motif en l'utilisant, et composant électronique Ceased WO2015011893A1 (fr)

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CN109946925A (zh) * 2019-04-08 2019-06-28 深圳先进技术研究院 一种化合物在促进聚酰亚胺低温固化中的应用、聚酰亚胺前体组合物及其用途
WO2020080217A1 (fr) * 2018-10-19 2020-04-23 富士フイルム株式会社 Composition de résine, film durci ainsi que procédé de fabrication de celui-ci, stratifié, et dispositif à semi-conducteurs
KR20230005356A (ko) * 2020-06-03 2023-01-09 후지필름 가부시키가이샤 경화성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 및, 반도체 디바이스

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