KR102215890B1 - Photosensitive resin composition, and cured-pattern-film manufacturing method and semiconductor device using said photosensitive resin composition - Google Patents

Abstract

A resin composition containing the following components (a) to (c).
(a) a polyimide precursor having a structural unit represented by the following general formula (1) (wherein A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d), and B is the following general It is a divalent organic group represented by formula (3).) (b) oxime ester compound (c) solvent

Description

A photosensitive resin composition, a method of manufacturing a pattern cured film using the same, and a semiconductor device TECHNICAL FIELD [0001]

The present invention relates to a photosensitive resin composition exhibiting excellent photosensitive properties, a method for producing a patterned cured film using the same, and a semiconductor device.

In recent years, as a material for a protective film of a semiconductor integrated circuit, an organic material having high heat resistance such as a polyimide resin has been widely applied. In addition, in forming a pattern on a semiconductor integrated circuit, a method of forming a required pattern by exposing and developing a photosensitive material is applied from the viewpoint of process simplification.

As a method of imparting photosensitivity to a polyimide, a method of introducing a methacryloyl group to a polyimide precursor through an ester bond or an ionic bond, a method of using a soluble polyimide having a photopolymerizable olefin, having a benzophenone skeleton, and A method of using a self-sensitizing polyimide having an alkyl group at the ortho position of the aromatic ring to which the nitrogen atom is bonded is known. Among them, in a method of introducing a methacryloyl group to a polyimide precursor through an ester bond or an ionic bond, the degree of freedom of monomer selection is high, and it is actively studied.

However, in a method in which a tertiary amine having a methacryloyl group is added to a polyamic acid, a carboxyl group in the polyamic acid is formed, and a quaternary ammonium salt is formed, and a methacryloyl group is introduced through an ionic bond, the bonding strength is weak. Therefore, when stored at room temperature, there is a problem in that depolymerization of polyamic acid easily occurs, resulting in a low molecular weight, resulting in a decrease in viscosity. Further, even if methacryloyl groups are crosslinked by photopolymerization by exposure, the effect of lowering the dissolution rate of the polyamic acid is weak, and thus there is a problem in that the photosensitive property is lowered (for example, see Patent Document 1).

On the other hand, with miniaturization of semiconductor integrated circuits, it is necessary to reduce the dielectric constant of an interlayer insulating film called a low-k layer. In order to reduce the dielectric constant, for example, there is a method of applying an interlayer insulating film having a pore structure. However, this method has a problem that the mechanical strength is lowered. In order to protect the interlayer insulating film having weak mechanical strength, there is a method of forming a protective film on the interlayer insulating film.

In addition, in a region where a protruding external electrode called a bump is formed, the stress acting on the interlayer insulating film is concentrated, so that the interlayer insulating film is not destroyed, the protective film has a thick film formation property ( There is a growing demand for high elasticity (eg, 5 μm or more) and high elastic modulus (eg, 4 GPa or more). However, by thickening the protective film and increasing the modulus of elasticity, the stress of the protective film increases, the warpage of the semiconductor wafer increases, and a problem may occur during transportation or fixing the wafer. Therefore, the development of a low-stress polyimide resin is desired (for example, see Patent Document 2).

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2011-174020 Patent Document 2: Japanese Unexamined Patent Application Publication No. 2012-2917

Summary of the invention

When the cured film obtained by heating the resin composition containing the polyimide resin is a thick film, the transmittance of the i-line (wavelength 365 nm) used in the exposure step decreases. As a result, there was a problem that the photosensitive characteristics (sensitivity and resolution) were deteriorated. For this reason, it was difficult to simultaneously achieve good photosensitive characteristics and low stress.

It is an object of the present invention to provide a resin composition having good photosensitive properties and low stress of a cured film to be formed, and a method for forming a patterned cured film using the same.

According to this invention, the following resin composition etc. are provided.

1. A resin composition containing the following components (a) to (c).

(a) a polyimide precursor having a structural unit represented by the following general formula (1)

(b) oxime ester compound

(c) solvent

(In general formula (1), A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following general 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 group having a carbon-carbon unsaturated double bond.)

(In general formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which each is bonded.)

(In General Formula (3), R ³ to R ¹⁰ are each independently hydrogen or a monovalent organic group. However, R ³ to R ¹⁰ are not monovalent organic groups having a halogen atom and a halogen atom.)

2. The resin composition according to 1, wherein the component (b) is a compound represented by the following general formula (4), a compound represented by the general formula (5), or a compound represented by the general formula (6).

(In formula (4), 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.

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.)

(In formula (5), R ₁₄ represents an alkyl group having 1 to 6 carbon atoms, respectively, R ₁₅ represents NO ₂ or ArCO (here, Ar represents an aryl group), and R ₁₆ and R ₁₇ each represent It represents a C1-C12 alkyl group, a phenyl group, or a tolyl group.)

(In formula (6), R ₁₈ represents an alkyl group having 1 to 6 carbon atoms, R ₁₉ represents an organic group having an acetal bond, and R ₂₀ and R ₂₁ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group. Show.)

3. The resin composition according to 1 or 2, wherein the polyimide precursor of the component (a) further has a structural unit represented by the following general formula (7).

(In general formula (7), D is a tetravalent organic group represented by the following general formula (8), and B, R ¹ And R ² is the same as in General Formula (1).)

(In general formula (8), Z is an ether bond (-O-) or a sulfide bond (-S-).)

4. The resin composition according to any one of 1 to 3, further containing a tetrazole derivative or a benzotriazole derivative.

5. A step of applying the resin composition according to any one of 1 to 4 on a substrate and drying it to form a coating film;

A step of exposing the coating film formed in the above step to light in a pattern by irradiating actinic light,

A method for producing a patterned cured film comprising a step of removing an unexposed part other than the exposed part by developing, and a step of heat-treating the pattern obtained in the step to form a polyimide pattern.

6. A semiconductor device having a patterned cured film obtained by the method for producing a patterned cured film according to 5.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has favorable photosensitive characteristics and the stress of the cured film to be formed is low, and a pattern cured film formation method using the same can be provided.

1 is a schematic cross-sectional view of a semiconductor device having a rewiring structure according to an embodiment of the present invention.

(Resin composition)

The resin composition of the present invention is characterized by containing the following components (a) to (c).

(a) a polyimide precursor having a structural unit represented by the following general formula (1)

(b) oxime ester compound

(c) solvent

(In general formula (1), A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following general 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 group having a carbon-carbon unsaturated double bond.)

(In general formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which each is bonded.)

(In General Formula (3), R ³ to R ¹⁰ are each independently hydrogen or a monovalent organic group, except for the case of a halogen atom and a monovalent organic group having a halogen atom.)

Hereinafter, each component is demonstrated.

1. (a) component: polyimide precursor

The polyimide precursor used in the present invention has a structural unit represented by the general formula (1). A in General Formula (1) is a structure derived from a tetracarboxylic dianhydride used as a raw material for a polyimide precursor.

In order to reduce the stress of the cured film obtained from the composition, A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d).

(In general formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which each is bonded.)

As the tetracarboxylic dianhydride imparting a tetravalent organic group represented by formulas (2a) to (2d), pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4 '-Biphenyltetracarboxylic dianhydride and tetracarboxylic dianhydride represented by the following formulas (9) to (15) are mentioned.

In the polymerization of the polyimide precursor, these may be used alone, or two or more tetracarboxylic dianhydrides may be used in combination. Among these, from the viewpoint of low thermal expansion of the cured film, pyromellitic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, and tetracarboxylic dianhydride represented by formulas (9) and (11) are used. It is preferable to use pyromellitic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, and more preferably using tetracarboxylic dianhydride represented by formula (9), and pyromellitic acid It is more preferable to use a dianhydride or 4,4'-biphenyltetracarboxylic dianhydride.

B in General Formula (1) is a structure derived from diamine used as a raw material for a polyimide precursor. From the viewpoint of low stress and i-ray transmittance, it is preferable that B is a divalent organic group represented by the following general formula (3).

R ³ to R ¹⁰ each independently represent hydrogen or a monovalent group. However, the case of a halogen atom and a monovalent organic group having 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, there is a fear that the bond between carbon-halogen atoms is deheated and the cured film is deteriorated.

Examples of the monovalent group represented by R ³ to R ¹⁰ include an alkyl group having 1 to 20 carbon atoms (such as a methyl group) and an alkoxy group (such as a methoxy group) having an alkyl group having 1 to 20 carbon atoms.

As a raw material diamine, 2,2'-dimethylbenzidine, 2,2'-diaminobenzidine, 3,3'-dimethylbenzidine, 3,3'-diaminobenzidine, 2,2',3,3'-tetra Methylbenzidine, 2,2'-dimethoxybenzidine, 3,3'-dimethoxybenzidine, and the like can be used.

In the polymerization of the polyimide precursor, these may be used alone or in combination of two or more diamines. Among these, it is preferable to use 2,2'-dimethylbenzidine, 2,2'-diaminobenzidine, 3,3'-dimethylbenzidine, and 3,3'-diaminobenzidine from the viewpoint of low stress, and 2 It is more preferable to use ,2'-dimethylbenzidine.

R ¹ and R ² in the polyimide precursor represented by the general formula (1) 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 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 include an acryloxyalkyl group and a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group.

The polyimide precursor has a monovalent organic group having a carbon-carbon unsaturated double bond at least in part, and is combined with a compound that generates a radical by irradiation with active light (e.g., i-line exposure), and a molecular chain by radical polymerization Crosslinking of the liver becomes possible, and it becomes easy to obtain a negative resin composition.

Specific 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, n-dodecyl group, etc. Can be mentioned.

Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like.

Examples of the acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include an acryloxyethyl group, an acryloxypropyl group, and an acryloxybutyl group.

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.

By the way, as a method of imparting photosensitivity to a polyimide precursor, a method of adding a tertiary amine compound having a carbon-carbon unsaturated double bond to a corresponding polyamic acid is known. However, the carboxyl group in the polyamic acid and the tertiary amine form an ionic bond, and the ionic bond state changes under the influence of the pH or moisture of the varnish, and storage stability may decrease. Therefore, it is preferable that R ¹ and R ² are not hydrogen but a group introduced by an ester bond. Among them, it is preferable that R ¹ and R ² are an acryloxyethyl group, an acryloxybutyl group, a methacryloxyethyl group, and a methacryloxybutyl group introduced by an ester bond from the viewpoint of good photosensitive properties.

From the viewpoint of lowering the stress of the resulting cured film, it is preferable that the polyimide precursor has a structure represented by the general formula (1) at least 10 mol%, more preferably at least 20 mol% based on all structural units. .

The polyimide precursor used in the resin composition of the present invention may have a structure represented by the following general formula (7) from the viewpoint of improving i-line transmittance, improving adhesion after curing, and improving mechanical properties.

(In general formula (7), D is a tetravalent organic group represented by general formula (8), and B, R ¹ and R ² are the same as in general formula (1).)

(In general formula (8), Z is an ether bond (-O-) or a sulfide bond (-S-).)

Examples of the tetracarboxylic dianhydride giving the structure of the general formula (8) include 4,4'-oxydiphthalic anhydride and thioetherdiphthalic anhydride. When synthesizing the polyimide precursor, these may be used alone, or two may be used in combination. From the viewpoint of adhesion after curing, it is preferable to use 4,4'-oxydiphthalic dianhydride.

In a polyimide precursor, when it has a structural unit represented by general formula (1) and a structural unit represented by general formula (7) at the same time, the polyimide precursor is copolymerized. As a copolymer, a block copolymer and a random copolymer are mentioned, for example, but there is no restriction|limiting in particular.

In the polyimide precursor having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (7), from the viewpoint of both low stress and good adhesion, the general formula (1) and the general formula The molar ratio [Formula (1)/Formula (7)] of (7) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and 2/8 to 7/3 It is more preferable to be.

The polyimide precursor of the present invention may have structural units other than the structural units represented by the general formula (1) and the structural units represented by the general formula (7). Specifically, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-[isopropylidenebis Structural units derived from tetracarboxylic dianhydrides, such as [(p-phenylene)oxy]]diphthalic acid 1,2:1',2'-dianhydride, are mentioned.

In addition, structures derived from diamines such as 4,4'-oxydianiline, 4,4'-diaminodiphenylmethane, 1,4-cyclohexanediamine, and 1,3'-bis(3-aminophenoxy)benzene Unit.

From the viewpoint of reducing stress, these tetracarboxylic dianhydrides and diamines are preferably 20 mol% or less, more preferably 10 mol% or less, based on the total amount of tetracarboxylic dianhydride and diamine used as raw materials, It is more preferable to use only the tetracarboxylic dianhydride and diamine giving the structures of the general formulas (1) and (7).

As for the molecular weight of the polyimide precursor of the present invention, the weight average molecular weight in terms of polystyrene is preferably 10000 to 100000, more preferably 15000 to 100000, and still more preferably 20000 to 850,000. From the viewpoint of sufficiently reducing the stress after curing, the weight average molecular weight is preferably 10000 or more. Moreover, it is preferable that it is 100000 or less from a viewpoint of the solubility in a solvent and the handleability of a solution. In addition, the weight average molecular weight can be measured by a gel permeation chromatography method, and can be calculated|required by conversion using a standard polystyrene calibration curve.

When using the polyimide precursor of the present invention as a resin composition, the polyimide precursor is preferably contained in a resin composition in an amount of 20 to 60 mass%, more preferably 25 to 55 mass%, and a 30 to 55 mass% It is more preferable to contain %.

The molar ratio of tetracarboxylic dianhydride and diamine used when synthesizing the polyimide precursor of the present invention is usually preferably 1.0, but for the purpose of controlling molecular weight or terminal residue, the molar ratio in the range of 0.7 to 1.3 Also works. 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 lowered.

In the polyimide precursor of the present invention, after inducing tetracarboxylic dianhydride as a raw material into a diester derivative represented by the following general formula (16), it is converted into an acid chloride represented by the following general formula (17), and diamine and It can be synthesized by an acid chloride method condensed in the presence of a basic compound.

(In formula (16), E is a tetravalent organic group, and represents the structure of a tetravalent group including A in formula (1) and D in formula (7), and R ¹ and R ² are in formula (1) Same as R ¹ and R ² .)

(In formula (17), E is a tetravalent organic group and represents the structure of a tetravalent group including A in formula (1) and D in formula (7), and R ¹ and R ² are R ¹ in formula (1) And R2.)

The diester derivative represented by formula (16) can be synthesized by reacting at least 2 mol equivalents or more of alcohols in the presence of a basic catalyst with respect to 1 mol of tetracarboxylic dianhydride as a raw material. However, in the case of converting the diester derivative represented by formula (16) to the acid chloride represented by formula (17), if unreacted alcohols remain, the chlorinating agent reacts with the unreacted alcohols and discards them as acid chlorides. I am concerned that the conversion of is not proceeding sufficiently. Therefore, the equivalent of alcohols is preferably 2.0 to 2.5 molar equivalents, more preferably 2.0 to 2.3 molar equivalents, and still more preferably 2.0 to 2.2 molar equivalents per 1 mole of tetracarboxylic dianhydride.

As alcohols, alcohols having 1 to 20 carbon atoms or cycloalkyl groups of 3 to 20 carbon atoms, and alcohols having 1 to 10 carbon atoms acryloxyalkyl groups or 1 to 10 carbon atoms methacryloxyalkyl groups as the alkyl group can be used. .

Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, n-hexanol, cyclohexanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacryl Rate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate And acrylate. These may be used individually, or two or more types may be mixed and used for them.

As the basic catalyst, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, or the like can be used.

When two or more types of tetracarboxylic dianhydrides are used as raw materials, one derived from each tetracarboxylic dianhydride separately as an ester derivative may be mixed and used. Moreover, after mixing two or more types of tetracarboxylic dianhydrides in advance, you may induce to an ester derivative at the same time.

In order to convert the diester derivative represented by formula (16) into the acid chloride represented by formula (17), it is carried out by reacting usually 2 molar equivalents of a chlorinating agent with respect to 1 mole of the diester derivative. In order to control the molecular weight of the polyimide precursor, the equivalent may be appropriately adjusted.

As the chlorinating agent, thionyl chloride or dichlorooxalic acid can be used, and the equivalent is preferably 1.5 to 2.5 molar equivalents, from the viewpoint of increasing the molecular weight of the polyimide precursor to be formed to sufficiently lower the stress after curing, and 1.6 to 2.4 molar equivalents are more preferred, and 1.7 to 2.3 molar equivalents are still more preferred.

The polyimide precursor used in the present invention can be obtained by adding diamine as a raw material to the acid chloride represented by formula (17) in the presence of a basic compound. The basic compound is used for the purpose of capturing hydrogen chloride generated when an acid chloride and diamine react.

As the basic compound, pyridine, 4-dimethylaminopyridine, triethylamine, or the like can be used. The amount used is preferably 1.5 to 2.5 molar equivalents, more preferably 1.7 to 2.4 molar equivalents, and even more preferably 1.8 to 2.3 molar equivalents based on the amount of the chlorinating agent. If it is less than 1.5 molar equivalents, the molecular weight of the polyimide precursor is lowered, there is a fear that the stress after curing may not be sufficiently reduced, and if it is more than 2.5 molar equivalents, the polyimide precursor may be colored.

In addition, the above-described polyimide precursor can also be synthesized by an isoimide method or a DCC method in addition to the above-described acid chloride method. In the isoimide method, a raw material tetracarboxylic dianhydride and diamine are polycondensed to synthesize a polyamic acid, trifluoromethyl acetic anhydride is added to convert to isoimide, and an alcohol compound is added to form an ester bond. Eggplants synthesize polyimide precursors. In the DCC method, a polyimide precursor can be obtained by reacting a diester derivative represented by formula (16) with 2 molar equivalents of DCC (dicyclohexylcarbodiimide) and then adding diamine.

The alcohol compound to be used is preferably an alcohol having an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group or a methacryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group. Specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Butyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc. are mentioned. These may be used individually, or two or more types may be mixed and used for them.

Further, for the purpose of controlling the molecular weight, a part of the starting material tetracarboxylic dianhydride may be reacted with the alcohol compound in advance to convert to an ester compound represented by formula (18), and then polycondensation with diamine may be performed.

(In formula (18), G is a tetravalent organic group and represents a tetravalent structure including A in formula (1) and D in formula (7), and R ²² is R ¹ or R ² in formula (1) Is the same as)

The addition polymerization and condensation reaction and synthesis of the diester derivative or acid chloride are preferably carried out in an organic solvent. As the organic solvent to be used, a polar solvent that completely dissolves the synthesized polyimide precursor is preferable, and N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide Seeds, tetramethylurea, hexamethylphosphate triamide, γ-butyrolactone, and the like.

2.(b) component: oxime ester compound

Component (b) is used as a photoinitiator. Although there is no restriction|limiting in particular as a component (b), From the viewpoint of obtaining favorable sensitivity and film residual film rate, the compound represented by the following formula (4), the compound represented by the following formula (5), and the following formula ( It is preferable that it is any one of the compounds represented by 6).

In formula (4), 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, and an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, or a phenyl group It is preferable that it is a C1-C4 alkyl group, a C4-C6 cycloalkyl group, or a phenyl group is more preferable, and it is still more preferable that it is a methyl group, a cyclopentyl group, or 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, and H, O(CH ₂ )OH , O(CH ₂ ) ₂ OH, COO(CH ₂ ) OH or COO(CH ₂ ) ₂ OH is preferable, and H, O(CH ₂ ) ₂ OH or COO(CH ₂ ) ₂ OH is more preferable .

In formula (5), R ₁₄ each represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group.

R ₁₅ represents NO ₂ or ArCO (here, Ar represents an aryl group), and Ar is preferably a tolyl group.

Each of R ₁₆ and R ₁₇ 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.

(In formula (6), 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 of the compound represented by Formula (6-1) described below.

R ₂₀ and R ₂₁ each represent a C 1 to C 12 alkyl group, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group, and more preferably a methyl group.

As the compound represented by the above formula (4), a compound represented by the following formula (4-1) and a compound represented by the following formula (4-2) are exemplified. The compound represented by the following formula (4-1) can be obtained as IRGACURE OOXE-01 (manufactured by BASF Corporation, brand name).

As a compound represented by the said formula (5), the compound represented by following formula (5-1) is mentioned, for example. This compound can be obtained as DFI-091 (manufactured by Daito Chemicals Co., Ltd., a brand name).

As a compound represented by the said formula (6), the compound represented by the following formula (6-1) is mentioned, for example. It can be obtained as Adeka Optomer N-1919 (manufactured by ADEKA, a brand name).

As other oxime ester compounds, it is preferable to use the following compounds.

These oxime ester compounds may be used alone or in combination of two or more.

Further, in addition to the oxime ester compound as the component (b), a conventionally known one may be added as a photoinitiator.

As the content of the component (b), it is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polyimide precursor as the component (a). , It is particularly preferably 0.5 to 5 parts by mass, and very preferably 1 to 5 parts by mass. When the blending amount is 0.1 parts by mass or more, the crosslinking of the exposed portion tends to proceed more sufficiently, and the photosensitive properties (sensitivity, resolution) tend to be better, and when it is 20 parts by mass or less, the heat resistance of the cured film can be improved.

The resin composition of the present invention has excellent photosensitivity and lowers the stress of the formed cured film by combining the component (a) and the component (b). In particular, when a polyimide precursor having a structural unit represented by formula (1) as a component (a) and an oxime ester compound represented by formulas (4) to (6) as component (b) are used in combination, the general formula Since the oxime ester compounds represented by (4) to (6) exhibit high activity particularly when irradiated with electron beams such as i-rays, favorable photosensitive properties can be realized. In addition, it has a characteristic of showing low stress due to its rigid skeleton when it becomes polyimide by heat treatment.

3. (c) ingredient: solvent

As the component (c), a polar solvent that completely dissolves the polyimide precursor as the component (a) is preferable. Specifically, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphate triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, N,N' -Dimethyl propylene urea, etc. are mentioned. These may be used alone, or two or more may be used in combination.

It is preferable to contain a solvent in a resin composition from 40 to 80 mass %, it is more preferable to contain 45 to 75 mass %, It is still more preferable to contain 45 to 70 mass %.

4. Other ingredients

When the photosensitive resin composition of the present invention is used on a copper substrate, it is preferable to contain a tetrazole derivative or a benzotriazole derivative from the viewpoint of preventing the occurrence of a developing residue in an unexposed portion.

As a tetrazole derivative, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5' -Bis-1H-tetrazole, 1-methyl-5-ethyltetrazole, 1-methyl-5-mercaptotetrazole, 1-carboxymethyl-5-mercaptotetrazole, etc. are mentioned. Among these, 1H-tetrazole or 5-amino-1H-tetrazole is preferable.

Examples of benzotriazole derivatives include benzotriazole, 1H-benzotriazole 1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, mercaptobenzoxazole Can be mentioned. Among these, benzotriazole is preferable.

The tetrazole derivative or the benzotriazole derivative is used alone or in combination of two or more. These are usually 0.1 to 10 parts by weight per 100 parts by weight of the component (A), or 0.1 to 10 parts by weight in total when two or more types are combined. It is more preferably in the range of 0.2 to 5 parts by weight.

The resin composition of the present invention may contain an organosilane compound in order to improve adhesion to a silicone substrate or the like after curing. As an organosilane compound, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycy Doxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanate propyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltri Ethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane, etc. are mentioned.

The content in the case of containing an organosilane compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the polyimide precursor, from the viewpoint of adhesion after curing. It is more preferable to set it as 10 mass parts.

In the resin composition of the present invention, if necessary, an addition polymerizable compound may be blended. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. , Trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanedioldimethacrylate, 1,6-hexanedioldimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol 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, methylenebisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, and the like. These may be used alone or in combination of two or more.

The content in the case of containing the addition polymerizable compound is preferably 1 to 100 parts by mass, and 1 to 75 parts by mass, based on 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 more preferable, and it is still more preferable to set it as 1-50 mass parts.

Further, in the resin composition of the present invention, in order to ensure good storage stability, a radical polymerization inhibitor or a radical polymerization inhibitor may be blended. Examples of the radical polymerization inhibitor or inhibitor of radical polymerization include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, Metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosoamine, and the like. These may be used alone or in combination of two or more.

The content in the case of containing a radical polymerization inhibitor or a radical polymerization inhibitor is preferably 0.01 to 30 parts by mass, based on 100 parts by mass of the polyimide precursor, from the viewpoint of storage stability of the resin composition and heat resistance of the resulting cured film. It is more preferable that it is 10 mass parts, and it is still more preferable that it is 0.05-5 mass parts.

In addition, the resin composition of the present invention may substantially consist of at least one of the components (a) to (c) and the other components described above, or may consist only of these components. "Consisting substantially" means that the composition is mainly composed of the components (a) to (c), and optionally at least one of the other components described above, for example, 95 It means mass% or more, or 98 mass% or more.

(Pattern cured film, pattern cured film manufacturing method, semiconductor device)

The patterned cured film of the present invention can be obtained by heating the resin composition of the present invention described above. The patterned cured film of the present invention is preferably used as a protective layer of a Low-k material which is an interlayer insulating film. Examples of the low-k material include porous silica, benzocyclobutene, hydrogen silsesquioxane, and polyallyl ether.

The method for producing a patterned cured film of the present invention includes a step of applying and drying the resin composition of the present invention on a substrate to form a coating film, a step of irradiating the coating film formed in the above step with active light to expose it in a pattern, and the There is a step of removing an unexposed portion other than the exposed portion by development, and a step of heat treating the pattern obtained in the above step to form a polyimide pattern.

Examples of a method of applying the resin composition of the present invention onto a substrate include an immersion method, a spray method, a screen printing method, and a spin coating method. As a substrate, a silicon wafer, a metal substrate, a ceramic substrate, etc. are mentioned. Since the resin composition of the present invention can form a cured film of low stress, it is particularly suitable for application to a silicone wafer having a large diameter of 12 inches or more.

After applying the resin composition on the substrate, the solvent is removed (dried) by heating, whereby a coating film (resin film) with little adhesiveness can be formed. Further, the heating temperature during drying is preferably 80 to 130°C, and the drying time is preferably 30 to 300 seconds. Drying is preferably carried out using a device such as a hot plate.

Next, the coating film obtained by the above method is irradiated with actinic light through a mask on which a desired pattern is drawn, and is exposed in a pattern. The resin composition of the present invention is suitable for i-ray exposure, but ultraviolet rays, far ultraviolet rays, visible rays, electron rays, X-rays, and the like can be used as active light to be irradiated.

Next, by dissolving and removing the unexposed part with an appropriate developer, a desired patterned resin film can be obtained. 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, N, Good solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, and acetic acid esters, and these good solvents and lower alcohols, water, aromatic hydrocarbons, etc. A mixed solvent with a poor solvent, etc. are used. After development, rinse and wash with a poor solvent (e.g., water, ethanol, 2-propanol) or the like as necessary.

By heating the pattern obtained as described above at, for example, at 80 to 400°C for 5 to 300 minutes, the polyimide precursor contained in the resin composition can be imidized to obtain a pattern cured film. In this heat treatment step, in order to suppress oxidation deterioration of the polyimide during heating, it is preferable to use a curing furnace capable of curing at a low oxygen concentration of 100 ppm or less. For example, an inert gas oven or vertical type (縱型) It can be carried out using a diffusion furnace (擴散爐).

[Example of use of cured film or patterned cured film]

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 redistribution layer, or the like of a semiconductor device.

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 interlayer insulating layer (interlayer insulating film) (1), and also protects the surface of the device. A layer (surface protective film) 4 is formed. In the put portion 5 of the wiring layer 2, a redistribution layer 6 is formed and extends to the upper part of the core 8, which is a connection portion with a conductive ball 7 formed of solder, gold, etc., which are external connection terminals. . On the surface protective layer 4, a cover coat layer 9 is further formed. The rewiring layer 6 is connected to the conductive balls 7 through the barrier metal 10, but a collar 11 is provided to hold the conductive balls 7. When mounting a package having such a structure, in order to further relieve stress, an underfill 12 is also interposed.

In the case of manufacturing a semiconductor device using copper for the redistribution layer 6, in the photosensitive composition using IRGACURE OOXE-01 (manufactured by BASF Corporation, brand name), a polyimide residue is formed in the opening when forming the patterned cured film. It may occur. It is estimated that this may occur on copper because a specific oxime ester compound generates a radical during prebaking and hardens the unexposed part. This can be suppressed by including a tetrazole derivative or a benzotriazole derivative in the photosensitive resin composition.

Since the photosensitive resin composition contains a tetrazole derivative or a benzotriazole derivative, the tetrazole derivative or the benzotriazole derivative forms a thin film on copper to prevent direct contact between the active metal surface and the resin composition, thereby preventing unexposed areas. It is presumed that it becomes possible to suppress the decomposition of unnecessary photoinitiators and radical polymerization reactions, thereby ensuring the photosensitive properties on the copper substrate.

The cured film or pattern cured film of the present invention can be used for a so-called package application such as a cover coat material, a core material for rewiring, a color material for balls such as solder, an underfill material, and the like of the above embodiment.

The cured film or pattern cured film of the present invention is excellent in adhesion to a metal layer or a sealing agent, as well as excellent copper migration resistance and a high stress relaxation effect. A semiconductor device having a cured film is extremely reliable.

The semiconductor device of the present invention has a patterned cured film obtained by the manufacturing method of the present invention. Examples of the semiconductor device include logic-based semiconductor devices such as MPU, memory-based semiconductor devices such as DRAM and NAND flash, and the like.

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1-12, Comparative Example 1-6

(1) Synthesis of polyamic acid ester (polyimide precursor)

2 equivalents of 2-hydroxyethyl methacrylate based on tetracarboxylic dianhydride 1 and tetracarboxylic dianhydride 1 shown in Table 1 or 2, and a catalytic amount of 1,8-diazabicyclo[5.4.0] Undeca-7-ene (DBU) was dissolved in 4 times the amount of N-methyl-2-pyrrolidone of tetracarboxylic dianhydride 1 in a mass ratio, and stirred at room temperature for 48 hours to obtain ester solution 1.

In addition, if necessary, 2 equivalents of 2-hydroxyethyl methacrylate, and a catalytic amount of DBU with respect to the tetracarboxylic dianhydride component 2 and tetracarboxylic dianhydride 2 shown in Table 1 were used as a mass ratio of tetracarboxylate. It dissolved in N-methyl-2-pyrrolidone in the amount of 4 times the amount of acid dianhydride 2, and stirred at room temperature for 48 hours to obtain ester solution 2.

After mixing the ester solution 1 and the ester solution 2, while cooling in an ice bath, 2.2 equivalents of thionyl chloride was added dropwise with respect to the total amount of tetracarboxylic dianhydrides 1 and 2, and then 1 The mixture was stirred for an hour to prepare an acid chloride solution.

Separately, a solution obtained by dissolving diamine 1 shown in Table 1 and, if necessary, pyridine in the amount of 2 times the equivalent of diamine 2 and thionyl chloride in N-methyl-2-pyrrolidone 4 times the amount of diamine 1 and 2 by mass ratio It was added dropwise while cooling in an ice bath to the prepared and first prepared acid chloride solution. After completion of the dropwise addition, the reaction solution was added dropwise to distilled water, and the resulting precipitate was collected by filtration, washed a plurality of times with distilled water, and dried under vacuum to obtain a polyamic acid ester.

(2) Preparation of photosensitive resin composition

100 parts by mass of polyamic acid ester [component (a)], 20 parts by mass of tetraethylene glycol dimethacrylate, and a predetermined amount of a photoinitiator [component (b)] that generates radicals by irradiation with active light shown in Table 1 or 2 After stirring until it dissolves uniformly in 150 parts by mass of N-methyl-2-pyrrolidone [component (c)], a resin composition was obtained by pressure filtration using a 1 µm filter.

(Measurement of weight average molecular weight)

The weight average molecular weight of the obtained polyamic acid ester was determined in terms of standard polystyrene by gel permeation chromatography (GPC). In addition, the measurement conditions of the weight average molecular weight by the GPC method are as follows.

It measured using a solution of 1 ml of a solvent [THF/DMF=1/1 (volume ratio)] with respect to 0.5 mg of a polymer.

Measuring device: Detector L4000UV manufactured by Hitachi Seisakusho Co., Ltd.

Pump: L6000 manufactured by Hitachi Seisakusho Co., Ltd.

C-R4A 　Chromatopac manufactured by Shimadzu Seisakusho Co., Ltd.

Measurement conditions: Column 　Gelpack 　GL-S300MDT-5×2

Eluent: THF/DMF=1/1 (volume ratio)

LiBr (0.03 mol/l), H ₃ PO ₄ (0.06 mol/l)

Flow rate: 1.0ml/min, detector: UV270nm

(Measurement of i-line transmittance)

100 parts by mass of the obtained polyamic acid ester was dissolved in 150 parts by mass of N-methyl-2-pyrrolidone, and the polyamic acid ester solution was spin-coated on a glass plate, heated on a hot plate at 100° C. for 3 minutes, A coating film having a thickness of 20 µm was prepared, and the transmittance of 365 nm was measured. The measurement of the i-ray transmittance was measured by the cast film method using a visible infrared spectrophotometer U-3310 manufactured by Hitachi High Technologies. The transmittance of 20% or more was H, 10% or more and less than 20% was M, and L was less than 10%.

(Evaluation of photosensitive properties)

The obtained photosensitive resin composition was applied onto a 6-inch silicon wafer by spin coating and dried on a hot plate at 100° C. for 3 minutes to form a coating film having a thickness of 10 μm. Through a photomask to the coating film, and the i line manufactured by Canon whether or using the i-line stepper FPA-3000iW and 50~500mJ / cm ² irradiated to 50mJ / cm ² ml each of a predetermined pattern, and subjected to exposure . In addition, twice the time until completely dissolved by immersing an unexposed coating film of the same thickness in cyclopentanone is set as the development time, and the exposed wafer is immersed in cyclopentanone to develop a puddle, Rinse washing was performed with isopropanol. At this time, the minimum exposure amount at which the dissolution amount of the coating film of the exposed portion was less than 10% of the initial film thickness was used as the sensitivity, and the minimum value of the mask dimension of the square hole opening was evaluated as the resolution.

Sensitivity is that of 300mJ / cm ² ○ below, greater than 300mJ / cm ² △ that of 500mJ / cm ² or less, and is larger than 500mJ / cm ² as ×. The ones having a resolution of 10 µm or less were set as ?, the ones having a resolution greater than 10 µm and less than 30 µm were set to?

(Measurement of residual stress)

The obtained photosensitive resin composition was applied to a 6-inch silicon wafer having a thickness of 625 µm, and spin-coated to a film thickness of 10 µm after curing. This was heat-cured at 375°C for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace made by Koyolindberg, to obtain a polyimide film (cured film). The residual stress of the polyimide film after curing was measured at room temperature using a thin film stress measuring device FLX-2320 manufactured by KLATencor. The stress of 30 MPa or less was set as ○, the one having a stress greater than 30 MPa and less than 35 MPa was △, and the one having a stress greater than 35 MPa was set as x.

(Evaluation of drug resistance)

The cured silicon wafer prepared for measuring the residual stress was immersed in NMP at 70°C for 20 minutes, washed with pure water, and the moisture adhering to the surface of the cured film was wiped off, followed by air drying. )did. The rate of change of the film thickness of the cured film after air-drying with respect to the initial film thickness was set to ○, greater than ±10%, Δ for less than ±20%, and × for greater than ±20%.

The measurement results are shown in Table 1 or 2.

In Tables 1 and 2, the numerical values in parentheses of the photoinitiator represent parts by mass of the photoinitiator relative to 100 parts by mass of the polyamic acid ester.

In addition, the abbreviation in the table represents the following compounds, and the substance amount in parentheses is the charged amount of the raw material.

· Polyimide precursor raw material

PMDA: Pyromellitic dianhydride

s-BPDA: 4,4'-biphenyltetracarboxylic 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

· Photoinitiator

Compound 1: BASF Corporation 　IRGACURE 　OXE-01, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime)

Compound 2: BASF Corporation 　IRGACURE 　OXE-02, 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyloxime

Compound 3: 4,4'-bis(diethylamino)benzophenone

Compound 4: Bis[4-(2-hydroxy-2-methylpropionyl)phenyl]methane

Compound 5: bis(η ⁵ -cyclopentadienyl)bis[2,6-difluoro-3-(1H-pil-1-yl)]phenyltitanium

In Examples 1 to 12 using photoinitiators having an oxime ester structure, in contrast to exhibiting excellent photosensitivity properties, Comparative Example 1 using a benzophenone fluorescent initiator, Comparative Example 2 using an acetphenone type photo initiator, and using a titanocene photoinitiator. In Comparative Example 3, the photosensitive properties were deteriorated. In addition, in Examples 1 to 12 in which PMDA, s-BPDA, and MMXDA were used as tetracarboxylic dianhydrides, low stress was exhibited, whereas in Comparative Example 6 in which only ODPA was used, high stress was exhibited. In addition, in Examples 1 to 12 using DMAP not having a fluorine atom and a monovalent organic group having a fluorine atom as the diamine, comparative example 4 using a diamine TFDB having a trifluoromethyl group while exhibiting good chemical resistance. In and 5, it was found that the chemical solution resistance was lowered.

Example 13

[Preparation and evaluation of photosensitive resin composition]

100 parts by mass of the same polyamic acid ester [(a) component] as in Examples 5 to 9, 20 parts by mass of tetraethylene glycol dimethacrylate, 1-[4-(phenylthio)phenyl]-1,2-octanedione After stirring until uniformly dissolved in 150 parts by weight of N-methyl-2-pyrrolidone [component (c)] 3 parts by weight of 2-(O-benzoyloxime) and 3 parts by weight of benzotriazole, 1 μm filter A resin composition was obtained by pressure-filtering using. About the obtained resin composition, in addition to the evaluation similar to Examples 1-12, evaluation of the residue on a copper substrate was evaluated by the following method. The results are shown in Table 3.

Example 14

[Preparation and evaluation of photosensitive resin composition]

100 parts by mass of the same polyamic acid ester [(a) component] as in Examples 5 to 9, 20 parts by mass of tetraethylene glycol dimethacrylate, 1-[4-(phenylthio)phenyl]-1,2-octanedione After stirring until uniformly dissolved 3 parts by weight of 2-(O-benzoyloxime) and 3 parts by weight of tetrazole 150 parts by weight of N-methyl-2-pyrrolidone [(c) component], a 1 μm filter The resin composition was obtained by pressure filtration using. About the obtained resin composition, in addition to the evaluation similar to Examples 1-12, evaluation of the residue on a copper substrate was evaluated by the following method. The results are shown in Table 3.

[0094]

Example 15

[Preparation and evaluation of photosensitive resin composition]

100 parts by weight of the same polyamic acid ester as in Examples 5 to 9, 20 parts by weight of tetraethylene glycol dimethacrylate, 2 parts by weight of the compound represented by the above formula (4-2), and 3 parts by weight of benzotriazole N-methyl After stirring until uniformly dissolved in 150 parts by weight of -2-pyrrolidone, the photosensitive resin composition was obtained by pressure filtration using a 1 μm filter. About the obtained resin composition, in addition to the evaluation similar to Examples 1-12, evaluation of the residue on a copper substrate was evaluated by the following method. Table 3 shows the results.

Example 16

[Preparation and evaluation of photosensitive resin composition]

100 parts by weight of the same polyamic acid ester as in Examples 5 to 9, 20 parts by weight of tetraethylene glycol dimethacrylate, 2 parts by weight of the compound represented by the formula (4-2) and 3 parts by weight of tetrazole N-methyl- After stirring until uniformly dissolved in 150 parts by weight of 2-pyrrolidone, the photosensitive resin composition was obtained by pressure filtration using a 1 μm filter. About the obtained resin composition, in addition to the evaluation similar to Examples 1-12, evaluation of the residue on a copper substrate was evaluated by the following method. Table 3 shows the results.

(Evaluation of residue on copper substrate)

A copper substrate prepared to measure the residue on the copper substrate (a patterned cured film was formed on the copper substrate by the same method as in the evaluation of the photosensitive properties (a) above) using a vertical diffusion furnace made by Koyolindberg, under a nitrogen atmosphere at 375°C. And it heat-cured at 300 degreeC for 1 hour, and obtained the polyimide film (cured film) with a pattern. Ashing for 2 minutes with an O2 ashing device (manufactured by Yamaha Chemical Co., Ltd.), immersed in Cu oxide film removal solution Z-200 (manufactured by World Metal Co., Ltd.) for 5 minutes, washed with pure water, and adhered to the surface of the cured film. After wiping off the moisture, it was air-dried. The residue at the opening of the pattern was observed using an SEM manufactured by Hitachi High-Technology, and the absence of a polyimide residue in the opening was set to ○. The case where the residue could be confirmed was set to x.

Regarding the compositions prepared in Examples 1 to 12, residue evaluation on the copper substrate was also performed. The results are shown in Table 4.

From Table 4, it can be seen that when benzotriazole or tetrazole is added to the resin composition of the present invention, no developing residue is generated on the copper substrate.

Industrial availability

The resin composition of the present invention can be used as a material for forming a protective film or a pattern film for electronic components such as semiconductor devices.

Although the embodiments and/or examples of the present invention have been described in some detail above, those skilled in the art make many changes to these exemplary embodiments and/or examples without substantially departing from the novel teachings and effects of the present invention. It is easy to apply. Accordingly, many of these modifications are included within the scope of the present invention.

All the contents of the document described in this specification and the Japanese application specification which becomes the basis for Paris priority of this application are used here.

Claims (9)

A resin composition containing the following components (a) to (c).
(a) a polyimide precursor having a structural unit represented by the following general formula (1)
(b) a compound represented by the following general formula (4), a compound represented by the general formula (5), or a compound represented by the general formula (6)
(c) solvent

(In general formula (1), A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following general 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 group having a carbon-carbon unsaturated double bond.)

(In general formula (2d), X and Y each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which each is bonded.)

(In General Formula (3), R ³ to R ¹⁰ are each independently hydrogen or a monovalent organic group. However, R ³ to R ¹⁰ are not monovalent organic groups having a halogen atom and a halogen atom.)

(In formula (4), 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.
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.)

(In formula (5), R ₁₄ represents an alkyl group having 1 to 6 carbon atoms, respectively, R ₁₅ represents NO ₂ or ArCO (here, Ar represents an aryl group), and R ₁₆ and R ₁₇ each represent It represents a C1-C12 alkyl group, a phenyl group, or a tolyl group.)

(In formula (6), R ₁₈ represents an alkyl group having 1 to 6 carbon atoms, R ₁₉ represents an organic group having an acetal bond, and R ₂₀ and R ₂₁ each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or Show.) The method of claim 1,
The resin composition, wherein the polyimide precursor of the component (a) further has a structural unit represented by the following general formula (7).

(In general formula (7), D is a tetravalent organic group represented by the following general formula (8), and B, R ¹ and R ² are the same as in general formula (1).)

(In general formula (8), Z is an ether bond (-O-) or a sulfide bond (-S-).) The method according to claim 1 or 2,
A resin composition further containing a tetrazole derivative or a benzotriazole derivative. Applying the resin composition according to claim 1 or 2 on a substrate and drying to form a coating film,
A step of exposing the coating film formed in the above step to light in a pattern by irradiating actinic light,
A step of removing unexposed portions other than the exposed portions by developing;
A method for producing a patterned cured film comprising a step of heat treating the pattern obtained in the above step to form a polyimide pattern. A semiconductor device having a patterned cured film obtained by the method for producing a patterned cured film according to claim 4. The method according to claim 1 or 2,
The resin composition, wherein the polyimide precursor of the component (a) has 10 mol% or more of the structural unit represented by the general formula (1) with respect to all structural units. The method according to claim 1 or 2,
The polyimide precursor of the component (a) is represented by the structural unit represented by the general formula (1) and the following general formula (7) with respect to the total number of moles of tetracarboxylic dianhydride and diamine used as raw materials. A resin composition, wherein the total number of moles of tetracarboxylic dianhydride and diamine that imparts structural units other than the structural unit to be formed is 20 mol% or less.

(In general formula (7), D is a tetravalent organic group represented by the following general formula (8), and B, R ¹ and R ² are the same as in general formula (1).)

(In general formula (8), Z is an ether bond (-O-) or a sulfide bond (-S-).) The method of claim 7,
The polyimide precursor of the component (a) uses only tetracarboxylic dianhydride and diamine that give the structural unit represented by the general formula (1) and the structural unit represented by the general formula (7) as raw materials. Consisting of a resin composition. delete

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