JPH11279403A - Photosensitive polyimide precursor composition and production of pattern using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in sensitivity, resolution and cured film characteristics, developable not only with an organic solvent but also with an aqueous solution of an alkali and useful for a protective coat, etc., of semiconductor elements by including a polyimide precursor having photosensitive groups, a specific hexaarylbisimidazole, etc. SOLUTION: This composition is obtained by including (A) a polyimide precursor having photosensitive groups, (B) a hexaarylbisimidazole compound represented by formula I (X<1> to X<5> are each H or the like) [e.g. 2,2'-bis(o- chorophenyl)-4,4',5,5'-tetraphenylbisimidazole] and (C) an arylglycine-based compound represented by formula II (R<4> is H or the like; R<5> is H or the like) (e.g. N-phenylglycine) The amount of the contained components based on 100 pts.wt. of the component A are preferably 0.3-10.0 pts.wt. of the component B and 1-10 pts.wt. of the component C. The component A preferably has 20,000-80,000 weight-average molecular weight expressed in terms of polystyrene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material suitable for a protective film such as a surface coat film of a semiconductor element and an interlayer insulating film of a thin-film multilayer wiring board, and more particularly to a photosensitive material containing a heat-resistant polyimide precursor, In addition, the present invention relates to a negative photosensitive polyimide precursor composition which can be developed even with a basic aqueous solution, and a method for producing a pattern.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive heat-resistant material for obtaining a heat-resistant polymer, an aromatic tetracarboxylic dianhydride described in JP-B-5-67026 is reacted with an olefinically unsaturated alcohol. To synthesize an olefin aromatic tetracarboxylic acid diester, and polymerize the compound and a diamine by a dehydration condensation reaction using carbodiimide to introduce a photosensitive group through a covalent bond, and JP-B-63-31939. It is known that an aromatic tetracarboxylic dianhydride described above is reacted with an aromatic diamine compound to introduce a photosensitive group by ionic bonding.

In each of these prior arts, a varnish dissolved in an appropriate organic solvent is applied to a substrate, dried to form a film, and then irradiated with ultraviolet rays through an appropriate photomask to expose the exposed portion to light. By curing, developing and rinsing with an organic solvent, a negative relief pattern is obtained.

In addition to these materials, as a material that can be developed with an aqueous liquid, for example, a positive polymer in which a naphthoquinonediazidosulfonylamide group is introduced into a carboxyl group of a polyamic acid has been proposed (Japanese Patent Laid-Open No. 6-1994). 2
No. 58835). This polymer has a feature that the naphthoquinonediazidosulfonylamide group is changed to a carboxyl group by light irradiation, so that the exposed portion is solubilized in a basic aqueous solution, and is used as a positive photosensitive material. However, at present, such a positive photosensitive polyimide precursor composition has not been obtained which has high sensitivity, excellent pattern shape, and performance for practical use.

However, these photosensitive polyimide precursors use an aromatic monomer having excellent heat resistance and mechanical properties as a basic skeleton, and have low light transmittance in the ultraviolet region due to absorption of the polyimide precursor itself. In addition, the photochemical reaction in the exposed portion cannot be performed sufficiently effectively, resulting in a problem that the sensitivity is low or the pattern shape is deteriorated. In recent years, with the increasing integration of semiconductors, processing rules have become increasingly smaller, and higher resolutions have been required.

[0006] For this reason, a conventional contact / proximity exposure apparatus using parallel light beams has been replaced by a 1: 1 projection exposure apparatus called mirror projection and a reduced projection exposure apparatus called a stepper. The stepper uses a monochromatic light such as an excimer laser and a high-power oscillation line of an ultra-high pressure mercury lamp. Until now, g-line steppers using visible light (wavelength: 435 nm) called g-line of ultra-high pressure mercury lamps have been the mainstream stepper, but the stepper used to respond to the demand for further refinement of processing rules Needs to be shortened. Therefore, the exposure apparatus used is shifting from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 365 nm).

However, the base polymer of photosensitive polyimide generally has low transparency as described above, and has almost no transmittance particularly at the i-line (wavelength: 365 nm). It is very difficult to get. In addition, a polyimide film for surface protection is required to be a thicker film corresponding to LOC (lead-on-chip), which is a high-density mounting method of a semiconductor element. The problem gets worse.
For this reason, there is a strong demand for a photosensitive polyimide which has sufficient sensitivity even at the bottom where the illuminance by the i-line stepper is extremely low and which can obtain a good pattern shape. This is the same for the negative photosensitive polyimide precursor composition.

[0008]

The invention according to claims 1 to 4 has excellent photosensitive characteristics, provides a good pattern having a good shape even at a low exposure dose, and further provides not only an organic solvent but also an alkaline aqueous solution. The present invention provides a photosensitive polyimide precursor resin composition which can be developed by the following method. The invention according to claim 5 provides a method for producing a polyimide pattern exhibiting excellent heat resistance and chemical resistance.

[0009]

According to the present invention, there are provided (A) a polyimide precursor having a photosensitive group, (B) (b1) a general formula (I)

Embedded image (Wherein X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom, an alkyl group, a halogen atom, a trihalomethyl group, a nitro group, an alkoxy group, COR ′ or COOR ″).
(Wherein R ′ and R ″ represent an alkyl group) and a hexaarylbisimidazole compound represented by the general formula (II):

Embedded image (Wherein, R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom, a cyano group, an alkyl group, a halogen atom or an alkoxy group). Composition.

The present invention also provides (b1) a hexaarylbisimidazole compound represented by the general formula (I):
General formula (III)

Embedded image (Wherein X is each independently an alkyl group, a halogen atom,
Trihalomethyl group, nitro group, alkoxy group, COR '
Or a hexaarylbisimidazole compound represented by COOR "(wherein R 'and R" represent a substituent represented by an alkyl group).

Further, according to the present invention, the polyimide precursor (A) having a photosensitive group is represented by the general formula (IV):

Embedded image (Wherein, R ¹ represents a tetravalent organic group, R ² represents a trivalent or tetravalent organic group containing an aromatic ring, and two R ³ each independently represent a monovalent group having a photosensitive group. And A represents an acidic monovalent group, and n is 1 or 2.) The photosensitive polyimide precursor composition has a repeating unit represented by the following formula:

The present invention also relates to the photosensitive polyimide precursor composition, which further comprises (C) an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure in addition to the components (A) and (B). About things.

Further, the present invention provides a step of forming a film using the photosensitive polyimide precursor composition, a step of irradiating the film with light through a mask having a predetermined pattern, and a step of irradiating the film after light irradiation with an organic compound. The present invention relates to a method for producing a pattern, comprising a step of developing using a solvent or a basic aqueous solution.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the photosensitive polyimide precursor composition of the present invention, (A) the polyimide precursor having a photosensitive group generally has a structural unit formed from a tetracarboxylic acid residue and a diamine residue. Polyamic acid or a derivative thereof. The photosensitive group is a group that is desorbed by light irradiation, a group that can be dimerized or copolymerized by light irradiation,
This photosensitive group may be bonded to a tetracarboxylic acid residue or a diamine residue. Further, the photosensitive group may be introduced via a covalent bond such as an ester bond or an amide bond, or may be introduced via an ionic bond. As the photosensitive group, for example, a group having a carbon-carbon unsaturated double bond is preferable because good photosensitivity can be imparted, and a group having an acryloyl group or a methacryloyl group is more preferable. (A) It is preferable that the polyimide precursor having a photosensitive group has a photosensitive group and an acidic group, since it can be easily developed with a basic aqueous solution.

Among these, the photosensitive polyimide precursor used in the present invention exhibits good photosensitive characteristics and developability in a basic aqueous solution. A polyimide precursor in which an acidic group is covalently bonded to the residue is preferable, and specifically,
Those having the structural unit represented by the general formula (IV) are more preferable because they are easy to produce and have particularly excellent photosensitive characteristics when used in combination with the component (B).

In the structural unit represented by the general formula (IV), the tetravalent organic group represented by R ¹ may be a tetracarboxylic acid or a derivative thereof capable of reacting with a diamine to form a polyimide precursor. It is preferably a residue, and is preferably a tetravalent organic group having 4 or more carbon atoms from the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by curing. Preferred examples thereof are shown in the following structural formula group. In addition, among the tetravalent organic groups having 4 or more carbon atoms, organic groups having 6 to 30 carbon atoms in total including an aromatic ring (benzene ring, naphthalene ring, etc.) are more preferable. It is preferable that the binding sites of the four carboxyl groups consist of two sets of two binding sites at the ortho or peri position of the aromatic ring. In the plurality of repeating units in the polyimide precursor molecule, all R ^{1 s} may be the same or different.

[0017]

Embedded image

[0018]

Embedded image

In the general formula (IV), the acidic group, that is, the group represented by A includes a sulfonic acid group (—SO ₃ H), a sulfinic acid group (—SO ₂ H), and a carboxyl group. It is preferable to use either (—COOH) or a phenolic hydroxyl group because of good solubility, and a carboxyl group or a phenolic hydroxyl group is more preferable because the synthesis of the polyimide precursor is easy. In addition,
In the plurality of repeating units in the polyimide precursor molecule, all A may be the same or different.

In the general formula (IV), the group R ² to which the acidic group A is bonded is preferably a diamine residue capable of forming a polyimide precursor by reacting with a tetracarboxylic acid or a derivative thereof. In view of the mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by curing, it is preferably an organic group containing an aromatic ring, and the mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by curing In view of the above, an organic group having a total carbon number of 6 to 30 including an aromatic ring is more preferable. Specific preferred examples are shown in the following structural formula groups. In the polyimide precursor molecule, in the plurality of repeating units, all R ² are
They may be the same or different.

[0021]

Embedded image (However, Z is

Embedded image Indicates)

In the formula (IV), the monovalent organic group having a photosensitive group represented by R ³ is preferably a group having a polymerizable carbon-carbon unsaturated double bond. For example, the following general formula (V)

Embedded image (Wherein R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group, a phenyl group, a vinyl group or a propenyl group, and R ⁷ represents a divalent organic group) The group is preferable because it can impart high sensitivity photosensitivity.

The alkyl group has 1 to 1 carbon atoms.
Four are preferred. The divalent organic group represented by R ⁷ is preferably an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group. In particular, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (having an alkyl group having 1 to 20 carbon atoms) are suitable for the present invention because they not only realize high sensitivity but also are easy to synthesize.

The polyimide precursor used in the present invention may contain a repeating unit other than the repeating unit represented by the general formula (IV). A unit without a group corresponding to
A unit in which R ^{3 of the} repeating unit represented by the general formula (IV) is a hydrogen atom or an organic group containing no photosensitive group. Examples of the repeating unit having no group corresponding to A in the repeating unit represented by the general formula (IV) include the following repeating units in which the group corresponding to R ² in the general formula (IV) is shown below.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

In the polyimide precursor of the present invention, the proportion of the repeating unit represented by the general formula (IV) is preferably from 10 to 100 mol% in terms of mol percentage of all the repeating units in a basic aqueous solution. Is preferable because of excellent balance between developability and good pattern shape.
More preferably, it is 100 mol%. The molecular weight of the polyimide precursor in the present invention is, in terms of the properties of a cured film after imidization, a weight average molecular weight of 10,000 to
200,000 is preferred, and 20,000 to 80,00
0 is more preferred. The weight average molecular weight is measured by GPC (gel
Permeation chromatography) and can be calculated in terms of polystyrene.

The polyimide precursor used in the present invention is prepared by mixing and reacting a tetracarboxylic dianhydride and a hydroxy group-containing compound to produce a half ester of tetracarboxylic acid, followed by acid chloride with thionyl chloride. It can be synthesized by a method of reacting with a diamine, a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent, or the like.

The tetracarboxylic dianhydride includes:
For example, oxydiphthalic acid, pyromellitic acid, 3,
3 ', 4,4'-benzophenonetetracarboxylic acid,
3,3 ', 4,4'-biphenyltetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid, 2,
3,6,7-naphthalenetetracarboxylic acid, 1,4
5,8-naphthalenetetracarboxylic acid, 2,3,5,6
-Pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ', 4,4'-tetracarboxylic acid,
p-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,
2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis {4'-
(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, 1,1,1,3,3,3-hexafluoro-2,2-bis {4 ′-(2,3- or 3, 4-dicarboxyphenoxy) phenyl} propane having the following general formula (VI)

Embedded image (Wherein, R ¹¹ and R ¹² each represent a monovalent hydrocarbon group, and may be the same or different, and s is an integer of 1 or more). Examples include tetracarboxylic dianhydrides such as acids, which are used alone or in combination of two or more.

Examples of the diamine providing the diamine residue R ² in the structural unit represented by the general formula (IV) include 3,5-diaminobenzoic acid and 4,4'-dihydroxy-3,3'-diaminobiphenyl , 3,4-diaminobenzoic acid, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,3-diamino-4-hydroxypyridine, 2,2-bis (4-hydroxy-3-aminophenyl) Hexafluoropropane, 2,4-diaminophenol, 2,4-diaminobenzoic acid, 3-carboxy-4,4'-diaminodiphenyl ether, 3,3'-
Dicarboxy-4,4'-diaminodiphenylether, 3-carboxy-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4 '-
Diaminobiphenyl, 3,3 ', 5,5'-tetracarboxy-4,4'-diaminobiphenyl, 3-carboxy-4,4'-diaminodiphenylsulfone, 3,3'
-Dicarboxy-4,4'-diaminodiphenylsulfone, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (3-carboxy-4-aminophenyl) propane and the like.

Examples of the diamine providing a diamine residue other than the structural unit represented by the general formula (IV) include, for example, 4,
4'- (or 3,4'-, 3,3'-, 2,4'-,
2,2 '-) diaminodiphenyl ether, 4,4'-
(Or 3,4'-, 3,3'-, 2,4'-, 2,2 '
-) Diaminodiphenylmethane, 4,4'- (or 3,
4 '-, 3,3'-, 2,4 '-, 2,2'-) diaminodiphenylsulfone, 4,4'- (or 3,4'-,
3,3 '-, 2,4'-, 2,2 '-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone ,
4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene,
5-diaminonaphthalene, 4,4'-benzophenonediamine, bis- {4- (4'-aminophenoxy) phenyl} sulfone, 1,1,1,3,3,3-hexafluoro-2,2-bis ( 4-aminophenyl) propane,
2,2-bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4 '-Diaminodiphenylmethane, bis @ 4-
(3'-aminophenoxy) phenyl disulfone, 2,
2-bis (4-aminophenyl) propane and the like are used, and these are used alone or in combination of two or more.

In addition, as a diamine residue, the following general formula (VII) is used in order to improve adhesiveness.

Embedded image (Wherein, R ¹³ and R ¹⁴ each represent a divalent hydrocarbon group, which may be the same or different, and R ¹⁵ and R ¹⁶ each represent a monovalent hydrocarbon group, each of which may be the same or different. Often, t is an integer of 1 or more.) It is also possible to use a diamine such as diaminopolysiloxane.

Examples of R ¹³ and R ¹⁴ include an alkylene group such as a methylene group, an ethylene group and a propylene group, an arylene group such as a phenylene group, and a bonding group thereof.
^{Examples of 15} and R ¹⁶ include an alkyl group such as a methyl group and an ethyl group, and an aryl group such as a phenyl group. When these are used, it is preferable to use 1 to 30 mol% based on all amine components.

As diamines, 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-
4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,
Use of a diamine compound having a sulfonamide group or a carboxamide group such as 4'-diaminodiphenyl ether-4-carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide, and 3,3'-diaminodiphenyl ether-4-carboxamide. Can also. When these are used, 1 to all amine components
Preferably, it is used in an amount of up to 30 mol%. These diamines are used alone or in combination of two or more.

The above-mentioned polyimide precursor of the present invention comprises:
It is used as a raw material of a negative photosensitive material in which an exposed part is cured. The components other than the polyimide precursor of the photosensitive polyimide precursor composition containing the polyimide precursor of the present invention will be described below.

The photosensitive polyimide precursor composition of the present invention comprises (B) (b1) a compound of the general formula (I)

Embedded image (Wherein X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom, an alkyl group, a halogen atom, a trihalomethyl group, a nitro group, an alkoxy group, COR ′ or COOR ″).
(Wherein R ′ and R ″ represent an alkyl group) and a hexaarylbisimidazole compound represented by the general formula (II):

Embedded image (Wherein, R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom, a cyano group, an alkyl group, a halogen atom or an alkoxy group).

The alkyl group in the general formulas (I) and (II) includes, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples include a t-butyl group, an isobutyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decanyl group. Formula (I) and Formula (II)
Examples of the halogen atom include fluorine, chlorine, iodine and the like. Examples of the alkoxy group in the general formulas (I) and (II) include, for example,
Methoxy, ethoxy, propoxy, butoxy,
Examples include a pentyloxy group and a hexyloxy group.

In the present invention, (b1) the general formula (I)
As an example of a hexaarylbisimidazole compound represented by the following general formula (III):

Embedded image (Wherein X is each independently an alkyl group, a halogen atom,
Trihalomethyl group, nitro group, alkoxy group, COR '
And a hexaarylbisimidazole compound represented by COOR "(wherein, R 'and R" represent a substituent represented by an alkyl group).

Examples of the (b1) hexaarylbisimidazole compound represented by the general formula (I) include, for example, 2,2'-bis (o-fluorophenyl)
-4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (o-trifluoromethylphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2 ' -Bis (o-chlorophenyl) -4,
4 ', 5,5'-tetraphenylbisimidazole,
2,2'-bis (o-bromophenyl) -4,4 ',
5,5'-tetraphenylbisimidazole, 2,2 '
-Bis (o-iodophenyl) -4,4 ', 5,5'-
Tetraphenylbisimidazole, 2,2'-bis (o
-Nitrophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (o-methoxyphenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2, 2'-bis (o- (carboxymethyl) phenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (o- (methoxycarbonyl) phenyl) -4,4', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,6-
(Difluorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2,4-
Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole and the like. These are used alone or in combination of two or more.

The content of the (b1) hexaarylbisimidazole compound represented by the general formula (I) in the photosensitive polyimide precursor composition of the present invention is 0.1 to 100 parts by weight based on 100 parts by weight of the polyimide precursor. The amount is preferably 15.0 parts by weight, more preferably 0.3 to 10.0 parts by weight.

The (b2) arylglycine compounds represented by the general formula (II) in the present invention include, for example, N-phenylglycine, N- (p-chlorophenyl) glycine, N- (p-bromophenyl) ) Glycine, N- (p-cyanophenyl) glycine, N- (p
-Methylphenyl) glycine, N-methyl-N-phenylglycine, N- (p-bromophenyl) -N-methylglycine, N- (p-chlorophenyl) -N-ethylglycine and the like. These are used alone or in combination of two or more.

In the photosensitive polyimide precursor composition of the present invention, (b2) the content of the arylglycine-based compound represented by the above general formula (II) is 100%.
It is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on parts by weight. In addition, (b2) the arylglycine-based compound represented by the general formula (II) acts as a hydrogen donor.

The photosensitive polyimide precursor composition of the present invention further comprises (C) an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure, in addition to the components (A) and (B). Use is preferred because good photosensitive characteristics can be obtained. When the boiling point is lower than 100 ° C. at normal pressure, when the solvent contained in the system is removed by drying or the like or when irradiating with an actinic ray, the addition polymerizable compound also volatilizes, and tends to have an adverse effect on characteristics. There is.

(C) Examples of the addition-polymerizable compound having a boiling point of 100 ° C. or more at normal pressure include compounds obtained by condensing a polyhydric alcohol with an α, β-unsaturated carboxylic acid; Glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropanetri (Meth) acrylate, 1,2-propylene glycol di (meth) acrylate, di (1,2-propylene glycol) di (meth)
Acrylate, tri (1,2-propylene glycol)
Di (meth) acrylate, tetra (1,2-propylene glycol) di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.], styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-
Hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, neopentylglycol di (meth) acrylate, pentaerythritol di Preferred examples include (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tetramethylolpropanetetra (meth) acrylate, and these are used alone or in combination of two or more.

(C) When an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure is used, the amount of the compound is 1 to 100 parts by weight of the polyimide precursor.
The amount is preferably from 100 to 100 parts by weight, more preferably from 5 to 50 parts by weight, even more preferably from 10 to 30 parts by weight.

The (C) addition-polymerizable compound having a boiling point of 100 ° C. or more at normal pressure is preferably soluble in the organic solvent contained in the photosensitive polyimide precursor composition of the present invention.

Examples of the organic solvent include acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-butanol,
t-butanol, ethylene glycol monomethyl ether, xylene, tetrahydrofuran, dioxane, cyclopentanone, N, N-dimethylacetamide, N, N
-Dimethylformamide, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2
-Pyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethylene carbonate, propylene carbonate, sulfolane, hexamethylenephosphortriamide,
Preferred examples include N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. These may be used alone or as a mixed system. The amount of the organic solvent used is not particularly limited, but is preferably 100 to 300 parts by weight based on 100 parts by weight of the polyimide precursor.

The photosensitive polyimide precursor composition of the present invention may contain another sensitizer, if necessary. Examples of the sensitizer include 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin,
3,3'-carbonylbis (7-N, N-diethylamino) coumarin, 3,3'-carbonylbis (7-N, N
-Dimethoxy) coumarin, 3-thienylcarbonyl-7
-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N, N-methoxycoumarin, 3- (4'-methoxybenzoyl) coumarin, 3,
3'-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenzal-4-methoxyacetophenone and the like.
When these are used, it is preferable to mix 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyimide precursor,
It is more preferable to add 0.3 to 20 parts by weight.

The photosensitive polyimide precursor composition of the present invention may contain other additives, for example, additives such as a plasticizer and an adhesion promoter.

In the method for producing a pattern of the present invention, a polyimide film comprising a cured product of the photosensitive polyimide precursor composition of the present invention is obtained by photolithography using the above-described photosensitive polyimide precursor composition of the present invention. Is formed.

In the pattern manufacturing method of the present invention, first,
A film made of the photosensitive polyimide precursor composition of the present invention is formed on the surface of the supporting substrate. In the pattern manufacturing method of the present invention, the surface of the support substrate may be previously subjected to a surface treatment with an adhesion aid or the like in order to improve the adhesion between the film or the polyimide film after heat curing and the support substrate. .

The film made of the photosensitive polyimide precursor composition is formed, for example, by forming a varnish film of the photosensitive polyimide precursor composition and then drying it. The varnish film is formed by a means appropriately selected from means such as spin coating using a spinner, dipping, spray printing, screen printing, etc., according to the viscosity of the varnish and the like. The thickness of the film can be adjusted by the application conditions, the solid content concentration of the photosensitive polyimide precursor composition, and the like. In addition, the coating formed on the support in advance is peeled from the support to form a sheet made of the polyimide precursor composition, and the sheet is attached to the surface of the support substrate, whereby the coating is formed. It may be formed.

Next, after irradiating the film with light (such as ultraviolet rays) through a photomask having a predetermined pattern, the unexposed portion is dissolved and removed with an organic solvent or a basic aqueous solution.
Obtain a desired relief pattern. The photosensitive polyimide precursor composition of the present invention is particularly suitable for i-line exposure. The developing step may be performed using a normal photoresist developing device. When the component (A) in the present invention has a repeating unit of the general formula (IV),
It is preferred to use a basic aqueous solution.

The obtained relief pattern is a polyimide precursor of the present invention which is usually partially imidized. This relief pattern is changed from 150 ° C. to 450
By performing heat treatment at a temperature selected from the range up to ° C., a pattern made of polyimide can be obtained with high resolution. This pattern has high heat resistance and excellent mechanical properties. Therefore, it is used as a surface protective film of a semiconductor element and an interlayer insulating film of a thin multilayer wiring board.

[0056]

The present invention will be described below with reference to examples. Synthesis Example 1 Synthesis of polyimide precursor (1) Synthesis of acid chloride In a 200 ml four-necked flask, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) 9.4 was added.
2 g (0.032 mol), 8.32 g (0.064 mol) of 2-hydroxyethyl methacrylate (HEMA),
5.06 g (0.064 mol) of pyridine, 0.03 g of t-butylcatechol, N-methyl-2-pyrrolidone (N
MP) and stirred at 60 ° C for 2 hours to obtain a clear solution. The solution was then stirred at room temperature for 7 hours,
The flask was cooled with ice and 9.88 g of thionyl chloride (0.
083 mol) was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

(2) Synthesis of Polyimide Precursor (Polyamic Acid Ester) In another 200 ml four-necked flask, 4.72 g (0.031 mol) of 3,5-diaminobenzoic acid and 5.0 parts of pyridine were added.
6 g (0.064 mol), t-butylcatechol 0.0
3 g and 50 ml of N-methyl-2-pyrrolidone (NMP) were added, and the flask was stirred while cooling with ice (keeping the temperature at 10 ° C. or lower), and the acid chloride solution obtained in the above (1) was slowly added over 1 hour. Was dropped. Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice with water, and dried under vacuum to obtain 22 g of a polyamic acid ester. When the weight average molecular weight of this polyamic acid ester was measured by gel permeation chromatography (GPC), it was 44,000 in terms of polystyrene.

Examples 1 to 9 and Comparative Examples 1 to 5 (i) Preparation of polyimide precursor composition 10 g of the polymer obtained in the above (2) was dissolved in 16 g of γ-butyrolactone and 2 g of cyclopentanone, and 2.5 g of glycol diacrylate and Tables 1 and 2
After mixing the photosensitive agents shown in Table 3 and Table 3, the mixture was filtered under pressure using a filter having a pore size of 3 μm to obtain a photosensitive polyimide precursor composition in a solution state.

(Ii) Preparation of hexaarylbisimidazole compound 2,2'-bis (o-chlorophenyl) -4,4 ',
5,5'-tetraphenylbisimidazole (Cl-H
ABI) is commercially available, and 2,2'-bis (o
-Methylphenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (Me-HABI), 2,2'-
Bis (o-methoxyphenyl) -4,4 ', 5,5'-
Tetraphenylbisimidazole (OMe-HAB
I), 2- (2-fluorophenyl) -4,5-diphenylbiimidazole (F-HABI), 2,2'-bis (2,6- (difluorophenyl) -4,4 ', 5,
5'-tetraphenylbisimidazole (2,6F-H
ABI) and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (2,4Cl-HABI)
The compound was synthesized according to the method described in J. Org. Chem., 36, 2262-2267 (1971) by Scon et al.

Hereinafter, a method for synthesizing F-HABI will be described. 2-
(2-fluorophenyl) -4,5-diphenylimidazole (3.14 g) and N-methylpyrrolidone 20 g
Was added and dissolved at room temperature with stirring. To this, 6.0 g of potassium ferricyanide and 3.6 g of sodium hydroxide were added.
Was dissolved in 100 ml of water, and the reaction temperature was adjusted to 10 to 20.
The solution was slowly added dropwise while maintaining the temperature. After the dropwise addition, stirring was continued for another 10 hours at room temperature to terminate the reaction, and then the reaction product was filtered, washed with water, and dried. Next, the product is recrystallized from acetone to give the desired 2- (2-fluorophenyl) -4,5-diphenylbiimidazole (FH).
ABI) was obtained (purity: 98% (HPLC)).

F-HABI; melting point: 219 ° C. (DS
C), maximum absorption wavelength λmax: 268 (in acetonitrile) Me-HABI; melting point: 116 ° C. (DSC), maximum absorption wavelength λmax: 268 (in acetonitrile) OMe-HABI; melting point: 215 ° C. (DSC), maximum absorption wavelength λmax: 269 (in acetonitrile) 2,6F-HABI; melting point: 154 ° C (DSC), maximum absorption wavelength λmax: 264 (in acetonitrile) 2,4Cl-HABI; melting point: ° C (DSC), maximum absorption wavelength λmax: ( In acetonitrile)

(Iii) Pattern formation The photosensitive polyimide precursor composition prepared in the above (i) is spin-coated on a silicon wafer and heated on a hot plate at 80 ° C. for 200 seconds to form a 10 μm thick coating film. I got This coating film was subjected to 40 (mJ / cm ² ) using an i-line stepper.
40-360 in step ^{(mJ / cm 2), 100} (mJ / cm 2)
Exposure was performed at 100 to 900 (mJ / cm ² ) in steps. Thereafter, immersion development was performed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, followed by rinsing with water. The pattern shape after development was measured and observed for each exposure dose, and the obtained sensitivities and resolutions are shown in Tables 1, 2 and 3. The sensitivity is such that the film thickness after development is the film thickness before development (10
μm), the exposure (mJ) exceeding 50% (5 μm)
/ cm ² ). The film thickness is a stylus type (device name: Dektak)
Was measured. In addition, the resolution was determined by observing a pattern with an exposure amount of 300 mJ / cm ² using an optical microscope, and expressed by a minimum line width (μm) at which a fine line and space pattern was obtained.

The compounds used in Examples 1 to 9 and Comparative Examples 1 to 5 are shown below. The hexaarylbisimidazole compounds (HABIs) are as follows.

[0064]

Embedded image

[0065]

Embedded image

The aryl glycine compounds are as follows.

Embedded image

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

Example 10 Using the patterns obtained in Examples 1 to 9, under a nitrogen atmosphere at 100 ° C. for 30 minutes, at 200 ° C. for 30 minutes,
Heating was performed at 0 ° C. for 60 minutes to obtain a polyimide pattern. A good polyimide pattern was obtained.

[0071]

The photosensitive polyimide precursor resin compositions according to claims 1 to 4 are excellent in sensitivity, resolution and cured film properties. The method for producing a polyimide pattern according to claim 5 exhibits excellent heat resistance and chemical resistance, and a good polyimide pattern can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 514 514 7/028 7/028 H01L 21/027 H01L 21/312 B 21/312 D C07D 233/58 // C07D 233/58 233/64 101 233/64 101 H01L 21/30 502R

Claims (5)

[Claims] (A) a polyimide precursor having a photosensitive group, (B) (b1) a general formula (I) (Wherein X ¹ , X ² , X ³ , X ⁴ and X ⁵ are each independently a hydrogen atom, an alkyl group, a halogen atom, a trihalomethyl group, a nitro group, an alkoxy group, COR ′ or COOR ″).
(Wherein R ′ and R ″ represent an alkyl group) and a hexaarylbisimidazole compound represented by the general formula (II): (Wherein, R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom, a cyano group, an alkyl group, a halogen atom or an alkoxy group). Composition. (B1) A hexaarylbisimidazole compound represented by the general formula (I) is a compound represented by the general formula (III): (Wherein X is each independently an alkyl group, a halogen atom,
Trihalomethyl group, nitro group, alkoxy group, COR '
Or a hexaarylbisimidazole compound represented by COOR "(wherein R 'and R" represent a substituent represented by an alkyl group). 3. The polyimide precursor (A) having a photosensitive group is represented by the general formula (IV): (Wherein, R ¹ represents a tetravalent organic group, R ² represents a trivalent or tetravalent organic group containing an aromatic ring, and two R ³ each independently represent a monovalent group having a photosensitive group. The photosensitive polyimide precursor composition according to claim 1 or 2, wherein A is a monovalent group exhibiting acidity, and n is 1 or 2. . 4. The photosensitive composition according to claim 1, further comprising (C) an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure, in addition to the components (A) and (B). Polyimide precursor composition. 5. A step of forming a film using the photosensitive polyimide precursor composition according to claim 1, 2, 3, 4 or 5, and a step of irradiating the film with light through a mask having a predetermined pattern. A method for producing a pattern, comprising a step of developing a film after irradiation using an organic solvent or a basic aqueous solution.