JP2002082436A - Photosensitive polyimide precursor composition, method for producing pattern using the same, and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive polyimide precursor resin composition having high sensitivity and high resolution, a method for producing pattern using the composition, and electronic parts. SOLUTION: The photosensitive polyimide precursor composition contains (A) a polyimide precursor having repeating units of formula (I) (where R1 is a tetravalent organic group; R2 is a di-, tri- of tetravalent organic group; each R3 is a monovalent organic group of formula (II-1) or (II-2) (where X is an integer of 3-20; Y and R are each H or CH3; and Z is an integer of 2-10) or H, at least one R3 is such a monovalent organic group; A is a monovalent group exhibiting acidity; and (n) is 0, 1 or 2) and (B) a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide precursor composition 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 a pattern using the same. With regard to manufacturing methods and electronic components,
The present invention relates to a method for producing a negative photosensitive polyimide precursor composition which becomes a polyimide heat-resistant polymer by heat treatment, a method for producing a pattern, and an electronic component.

[0002]

2. Description of the Related Art Photosensitive resin compositions are used in a wide range of industrial fields such as UV inks, printing plates, and holograms using lasers in recent years. In addition, a photosensitive heat-resistant polymer is used as a protective film such as a buffer coat film or a passivation film. As these materials,
For example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene, or the like as a base polymer have been proposed. In particular, photosensitive polyimides have excellent heat resistance and easy removal of impurities. Has received special attention. As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No.
-17374) was first proposed, but this material has advantages such as practical light sensitivity and high film-forming ability, but lacks storage stability, and chromium ions remain in the polyimide. There was a drawback of doing so, and it was not practical.

In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Application Laid-Open No. 54-109828) discloses a method in which a functional group and a photosensitive group in the polyimide precursor are mixed. A method of reacting with a functional group of a compound having a compound to give a photosensitive group (JP-A-56-2
No. 4343, Japanese Unexamined Patent Publication No. 60-100143)
And so on. However, these photosensitive polyimide precursors use a basic skeleton for an aromatic monomer having excellent heat resistance and mechanical properties.Because of the absorption of the polyimide precursor itself, the light transmittance in the ultraviolet region is low and the exposure is low. However, the photochemical reaction in the portion cannot be performed sufficiently effectively, resulting in a problem that the sensitivity is low and the shape of the pattern is deteriorated. In recent years, with the increasing integration of semiconductors, processing rules have become increasingly smaller, and higher resolutions have been required.

In recent years, a reduction projection exposure machine called a stepper used in a semiconductor production line has been used for processing a photosensitive polyimide precursor. Until now, g-line steppers using visible light (monochromatic light with a wavelength of 435 nm) called g-line of an ultra-high pressure mercury lamp have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, It is shifting to an i-line stepper (monochromatic light having a wavelength of 365 nm).

However, since the transmittance of these photosensitive polyimide precursors at the i-line (wavelength: 365 nm) is extremely low, the photochemical reaction in the exposed portion cannot be sufficiently performed, resulting in low sensitivity or low sensitivity. There was a problem that the shape of the pattern deteriorated.

[0006] The photosensitive polyimide precursor generally has a photoreactive site itself. For the photoreaction site, a compound having a group capable of forming a hydrogen bond with a carboxyl group and / or an amide group as a compound containing an ethylenically unsaturated double bond (JP-A-9-115900)
Publication).

[0007] This is usually because the polymer chains approach each other when the film after pre-baking is allowed to stand to lower the developing property. However, the development speed is reduced by forming hydrogen bonds with additives and inserting them between the polymer chains. To reduce delays. However, if the compound to be added does not have an ethylenically unsaturated double bond, the photoreactivity will be reduced due to separation between polymer chains.

[0008] Further, there is also a method in which a group having an ethylenically unsaturated double bond is introduced as a photoreactive site through a covalent bond (JP-A Nos. 11-24257 and 11-38617). In many cases, a compound having an ethylenically unsaturated group is separately added to these photosensitive resin compositions to improve photosensitivity. By adding a compound having an ethylenically unsaturated group, the mobility of a reaction point in a coating film is facilitated, and the bridge density can be increased. However, in the conventional photosensitive resin compositions, these compounds having an ethylenically unsaturated group cannot be added in a large amount in view of compatibility and physical properties of a cured film.

[0009]

SUMMARY OF THE INVENTION The present invention provides a photosensitive polyimide precursor resin composition exhibiting high sensitivity and high resolution. In addition, the present invention has a high sensitivity particularly to i-line, high resolution, and a part of which can realize good development with an alkaline aqueous solution, and is capable of producing a pattern exhibiting excellent heat resistance and chemical resistance. It is intended to provide a manufacturing method. The present invention also provides an electronic component having excellent reliability by having the above-mentioned pattern.

[0010]

(1) The present invention relates to (A)
General formula (I)

Embedded image (Wherein, R ¹ is a tetravalent organic group, R ² is a divalent, trivalent, or
A valent organic group, each R ³ is independently represented by the general formula (II-1) or (II-2)

Embedded image Wherein X is an integer of 3 to 20, Y and R each independently represent H or CH ₃ , and Z represents an integer of 2 to 10. A monovalent organic group or OH represented by at least one R ³ Is a monovalent organic group, A is an acidic monovalent group, n is 0, 1
Or 2), and a photosensitive polyimide precursor composition comprising (B) a photopolymerization initiator.

(2) The present invention also relates to the photosensitive polyimide precursor composition according to (1), which further contains, as a component (C), a compound having at least one ethylenically unsaturated group. (3) In the present invention, the component (A) has a weight average molecular weight of 10,000 to 200,000, and the component (B) has a weight average molecular weight of 100 to 200 parts by weight, and the component (B) has a weight average molecular weight of 1 to 20 parts by weight. The present invention relates to the photosensitive polyimide precursor composition according to the above (2), which contains 5 to 50 parts by weight of the component.

(4) Further, the present invention provides the above (1), (2)
Or a step of forming a film using the photosensitive polyimide precursor composition according to (3), a step of irradiating the film with light through a mask having a predetermined pattern, and a step of applying the light-irradiated film to an organic solvent or The present invention relates to a method for producing a pattern including a step of developing using a basic aqueous solution. (5) The present invention also relates to the method for producing a pattern according to (4), wherein the step of developing is performed using a basic aqueous solution.

(6) The present invention also relates to the method for producing a pattern according to the above (4) or (5), wherein the step of irradiating the light is a step of irradiating i-ray which is monochromatic light having a wavelength of 365 nm as light. . (7) Further, the present invention provides the above (4), (5) or (6)
The present invention relates to an electronic component having a film having a pattern obtained by the manufacturing method described above.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The polyimide precursor (A) used in the present invention is generally a polyamic acid derivative having a repeating unit consisting of a tetracarboxylic acid residue and a diamine residue. It is bound to an acid residue. In the repeating unit represented by the general formula (I), the tetravalent organic group represented by R ¹ is preferably a tetracarboxylic acid residue capable of forming a polyimide resin by reacting with a diamine. From the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film to be obtained, it is preferably a tetravalent organic group having 4 or more carbon atoms. Among the tetravalent organic groups having 4 or more carbon atoms, organic groups having a total carbon number of 6 to 30 including an aromatic ring (benzene ring, naphthalene ring, etc.) are more preferable. Further, it is preferable that the binding sites of the four carboxyl groups of the tetracarboxylic acid are two pairs of two binding sites existing at the ortho position or the peri position of the aromatic ring. In the polyimide precursor molecule, all of the R
¹ may be the same or different.

In the general formula (I), those wherein n is 1 or 2 are preferable in that they have excellent solubility in a basic aqueous solution. Examples of the acidic group represented by A include a sulfonic acid group (—SO ₃ H), a sulfinic acid group (—SO ₂ H),
It is preferable to use any of a carboxyl group (—COOH) and a phenolic hydroxyl group because of good solubility, and the carboxyl group and the phenolic hydroxyl group are more preferable because the synthesis of the polyimide precursor is easy, and a carboxyl group is particularly preferable. In a plurality of the repeating units in one molecule of the polyamic acid ester, all A may be the same or different.

Further, when n is 0, in order to impart solubility to a basic aqueous solution, a hydrogen atom must be contained in the repeating unit of the above general formula (I) or other repeating units ( That is, it is preferably a carboxyl group as a side chain), that is, a partial ester of polyamic acid.

In the general formula (I), the group R ² is usually
It is a diamine residue capable of forming a polyimide precursor by reacting with tetracarboxylic acid or a derivative thereof, and is an organic group containing an aromatic ring from the viewpoint of mechanical properties, heat resistance, and adhesiveness of a polyimide film obtained by curing. From the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by curing, it is more preferable that the polyimide film is an organic group containing an aromatic ring and having 6 to 30 carbon atoms in total. In the polyimide precursor molecule, in the plurality of repeating units, all R ² may be the same or different.

In the general formula (I), the group having an ethylenically unsaturated bond represented by R ³ may be a group represented by the following general formula (II-1) or (II-2)

Embedded image (Wherein X is an integer of 3 to 20, Y and R are each independently H or CH ₃ , and Z is an integer of 2 to 10). it can. Among these, not only high sensitivity is realized but also synthesis is easy. Therefore, in the case of the general formula (II-1), X is preferably 3 to 8, more preferably 3 to 6, Those having X of 4 or 6 are preferred because particularly high sensitivity can be obtained. On the other hand, in the case of the general formula (II-2), R is preferably H, Z is preferably 2 to 8, and 2 is preferred. To 6 are more preferable. The polyamic acid ester may include a repeating unit other than the repeating unit represented by the general formula (I).

In the polyimide precursor of the present invention, when n is 1 or 2, the proportion of the repeating unit represented by the general formula (I) is from 10 to 100 mol% in terms of mol percentage in all the repeating units. It is preferable that the content is excellent because the balance between the developability in a basic aqueous solution and the good pattern shape is excellent, and the content is more preferably 80 to 100 mol%. This adjustment can be made according to the types and amounts of the tetracarboxylic dianhydride, diamine, and ethylenically unsaturated bond-containing compound used as the material. Also,
When n is 0, the ratio of the repeating unit represented by the general formula (I) is preferably from 10 to 100 mol%, since the pattern shape is excellent, and from 30 to 100 mol%.
More preferably, it is 15 mol%, and in order to provide developability in a basic aqueous solution, another unit, for example, the repeating unit of polyamic acid is preferably 15 mol% to 50 mol%.

The polyamic acid ester is reacted with a mixture of a tetracarboxylic dianhydride and a hydroxy group-containing compound having a group represented by the general formula (II) to produce a half ester of tetracarboxylic acid. Synthesis by acid chloride with thionyl, followed by reaction with diamine, acid chloride method of reacting the tetracarboxylic acid half ester with diamine using carbodiimides as condensing agent, method using carbodiimide condensing agent, isoimide method, etc. Can be.

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 represented by the following general formula (III)

Embedded image (Wherein, R ⁸ and R ⁹ each independently represent a monovalent hydrocarbon group (preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group), and s is 1 or more (preferably 1 to 20) Dianhydride of an aromatic tetracarboxylic acid such as a tetracarboxylic acid represented by the following formula:
Used in combination of more than one type.

Further, among the diamine residues in the repeating unit represented by the general formula (I), those in which n is 1 or 2 (R ^1- (A) n) include 3,5
-Diaminobenzoic acid, 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'-diaminodiphenyl ether, 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'-diaminodiphenyl sulfone, 3,3'-dicarboxy-4,4'-diaminodiphenyl sulfone,
1,1,1,3,3,3-hexafluoro-2,2-bis (3-carboxy-4-aminophenyl) propane and the like.

In the repeating unit represented by the general formula (I), the diamine which gives a diamine residue in which n is 0 is 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'-) diaminodiphenyl sulfone, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-)
Diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidinesulfone, 4,4'-methylene-bis- (2,6-
Diethylaniline), 4,4'-methylene-bis-
(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-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} sulfone, 2,2-bis (4-aminophenyl)
And propane. These are used alone or in combination of two or more.

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

Embedded image (Wherein, R ¹¹ and R ¹² each represent a divalent hydrocarbon group, which may be the same or different, and R ¹³ and R ¹⁴ 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. R
^{Examples of 11} and R ¹² include an alkylene group having 1 to 10 carbon atoms 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.
¹³ and R ^{14 each} have 1 carbon atom such as a methyl group or an ethyl group.
And an aryl group such as a phenyl group. t is preferably 1 to 20. When these are used, it is preferably used in an amount of 1 to 30 mol% based on all amine components.

As the diamine, 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.

In the present invention, the polyimide precursor (A)
Has a weight average molecular weight of preferably 10,000 to 200,000, more preferably 20,000 to 80,000. If the molecular weight is less than 10,000, the mechanical strength tends to be poor, and if it exceeds 200,000, the developability tends to be poor. Here, the weight average molecular weight is a molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC).

The components other than the polyimide precursor will be described below. In the present invention, a compound having at least one ethylenically unsaturated group can be used as the component (C). As a specific example, there is a compound obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid. For example, ethylene glycol di (meth)
Acrylate ((meth) acrylate means acrylate or methacrylate, the same applies hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, trimethylolpropane triacrylate ethylene oxide adduct, trimethylolpropane triacrylate propylene oxide adduct, 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, neopentyl glycol di (meth) acrylate, pentaerythritol di Examples thereof include (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tetramethylolpropanetetra (meth) acrylate, and these may be used alone or in combination of two or more.

When the component (C) is used, it is preferably used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the polyimide precursor (A).
It is more preferable to use 〜40 parts by weight. If the amount is less than 5 parts by weight, sensitivity and resolution tend to be poor,
If it exceeds 50 parts by weight, the mechanical properties of the film tend to be inferior.

The present invention further comprises a photopolymerization initiator as the component (B). Examples of the photopolymerization initiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
-T-butylanthraquinone, 2-ethylanthraquinone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2
-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyldisulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6
-Bis (p-diethylaminobenzal) -4-methyl-
4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyimino-
1,3-diphenylpropanedione, 1-phenyl-2
-(O-ethoxycarbonyl) oxyiminopropane-
1-one, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone, 3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6 -Difluoro-3-
(Pyri-1-yl) phenyl] titanium, hexaarylbiimidazole compounds and the like. These are used alone or in combination of two or more.

The content of the photopolymerization initiator (B) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyimide precursor. preferable. If this amount is less than 0.1 parts by weight,
Light sensitivity tends to be inferior, and when it exceeds 15 parts by weight, mechanical properties of the film tend to be inferior.

Further, by adding a hydrogen donor such as an amine together with the photopolymerization initiator, the sensitivity can be further improved. Particularly preferred compounds as the hydrogen donor include arylglycine compounds and mercapto compounds.

As the arylglycine compound, N-
Phenylglycine (NPG), 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. The content of this compound is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the polyimide precursor.

As mercapto compounds, mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzimidazole, 2,5-mercapto-
1,3,4-thiadiazole, 1-phenyl-5-mercapto-1H-tetrazole, 5-methyl-1,3,4
-Thiadiazole-2-thiol, 3-mercapto-4
-Methyl-4H-1,2,4-triazole and the like. The content of this compound is 100%.
The amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 6 parts by weight with respect to parts by weight.

The photosensitive polyimide precursor composition of the present invention may contain a sensitizer if necessary. Examples of the sensitizer include 7-N, N-diethylaminocoumarin and 7-N, N-diethylaminocoumarin.
-Diethylamino-3-thenonylcoumarin, 3,3'-
Carbonyl bis (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, dimethylaminobenzophenone, 4,4'-bis (N, N-diethylamino) benzophenone (EAB or EMK), 4,4'-bis (N-ethyl, N-methyl) benzophenone (MEA
B) and the like. The content of these is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, based on 100 parts by weight of the polyimide precursor. The photosensitive polyimide precursor composition of the present invention may contain other additives, for example, additives such as a plasticizer and an adhesion promoter.

The pattern manufacturing method of the present invention is a method for forming a polyimide film comprising a cured product of the photosensitive polyimide precursor composition of the present invention by photolithography using the composition. 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 a supporting substrate. In the pattern manufacturing method of the present invention, the surface of the support substrate may be previously treated with an adhesion aid in order to improve the adhesion between the film or the polyimide film after heat curing and the support substrate.

The coating 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 method appropriately selected from means such as spin coating using a spinner, dipping, spray printing, and screen printing, depending on the viscosity of the varnish. The thickness of the film can be adjusted by the application conditions, the solid content concentration of the present composition, and the like. In addition, the film formed on the support is peeled off 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 to form the film described above. May be.

Next, after irradiating the film with light through a photomask having a predetermined pattern, an unexposed portion is dissolved and removed with an organic solvent or a basic aqueous solution to obtain a desired relief pattern. In particular, the composition of the present invention can obtain a good pattern even when i-line monochromatic light is used as a light source for exposure.

The developing step is not particularly limited, and may be performed using a normal positive type photoresist developing apparatus. As a solution used for the development, an organic solvent can be used, but a basic aqueous solution is preferable in terms of environmental resistance and the like.

Examples of the organic solvent include γ-butyrolactone, cyclopentanone, N-methylpyrrolidone, dimethylsulfoxide, dimethylacetamide, and a mixed solution thereof. The basic aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is usually 0.1 to 50% by weight, preferably from the influence on the support substrate and the like, and more preferably 0.1 to 30% by weight. In order to improve the solubility of the polyimide precursor, a water-soluble organic solvent such as methanol, ethanol, propanol, isopropyl alcohol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide is used. May be further contained. Examples of the basic compound include hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium ions, and amine compounds.

The resulting relief pattern is subjected to a heat treatment at a temperature selected from the range of 150 ° C. to 450 ° C., whereby the polyimide precursor undergoes a ring-closing reaction, and a polyimide pattern is obtained with high resolution. This pattern has high heat resistance and excellent mechanical properties such as wafer stress.

The photosensitive polyimide precursor composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film, interlayer insulating film, multilayer It can be used for forming an interlayer insulating film or the like of a wiring board. The semiconductor device of the present invention is not particularly limited except that it has a film of a pattern formed using the composition, that is, a surface protective film or an interlayer insulating film, and can have various structures.

An example of the manufacturing process of the semiconductor device of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. A window 6A is provided to perform the process (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, after applying the photosensitive polyimide precursor composition to the surface protective film by spin coating and drying, and irradiating light from a mask on which a pattern for forming the window 6C is drawn in a predetermined portion, Then, the pattern is formed by developing with a developing solution, and heated to form a polyimide film. This polyimide film protects the conductor layer from external stress, α rays, etc.
The obtained semiconductor device has excellent reliability. Note that, in the above example, the interlayer insulating film can be formed using the photosensitive polyimide precursor composition of the present invention, whereby the resist coating and etching steps can be omitted.

[0046]

The present invention will be described below with reference to examples. Synthesis Example 1 Synthesis of Polyimide Precursor 1 (1) Synthesis of Acid Chloride In a 200 ml four-necked flask, 9.31 g of oxydiphthalic tetracarboxylic dianhydride (ODPA) (0.
03 mol), 2-hydroxyethyl methacrylate (H
EMA) 7.809 g (0.06 mol), 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) 0.13
When 7 g, 0.03 g of t-butylcatechol and 40 g of dimethylacetamide (DMAC) were added and stirred at 60 ° C., a clear solution was obtained in 2 hours. After the solution was stirred at room temperature for 7 hours, the flask was cooled with ice, and 7.852 g (0.066 mol) of thionyl chloride 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, 6.36 g (0.02 g) of 2,2'-dimethyl-4,4'-diaminobiphenyl was added.
3 mol), 5.22 g (0.066 mol) of pyridine, t
0.03 g of -butylcatechol and 40 g of dimethylacetamide (DMAC) were added, and the acid chloride solution obtained above was slowly added dropwise over 1 hour while cooling the flask with ice and stirring (maintaining at 10 ° C or lower). Then at room temperature
The mixture was stirred 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 GPC (gel permeation chromatography), it was 28,000 in terms of polystyrene. Synthesis Example 2 Synthesis of polyimide precursor 2 In the synthesis of acid chloride of (1), 7.809 g of 2-hydroxyethyl methacrylate (HEMA) (0.
(0.6 mol) instead of 9.885 g (0.06 mol) of 4-hydroxybutyl methacrylate to obtain a polyamic acid ester in the same manner as in Synthesis Example 1. The weight average molecular weight of this polyamic acid ester measured by GPC (gel permeation chromatography) was 45,000 in terms of polystyrene. Synthesis Example 3 Synthesis of Polyimide Precursor 3 In the synthesis of acid chloride of (1), 7.809 g of 2-hydroxyethyl methacrylate (HEMA) (0.
Polyamide ester was obtained in the same manner as in Synthesis Example 1 except that 11.505 g (0.06 mol) of 6-hydroxyhexyl methacrylate was used instead of (0.6 mol).
The weight average molecular weight of this polyamic acid ester was determined by GPC.
(Gel permeation chromatography), it was 68,000 in terms of polystyrene.

Examples 1 and 2 and Comparative Example 1 (1) Preparation of Polyimide Precursor Composition
After dissolving in 16 g of butyrolactone, and blending the photocrosslinking agent and the photosensitive agent shown in Table 1, the mixture was filtered under pressure using a filter having a pore size of 3 μm to obtain a photosensitive polyimide precursor composition in the form of a solution.

[0049]

[Table 1]

(2) Measurement of Tg The photosensitive polyimide precursor composition prepared in (1) was spin-coated on a silicon wafer and heated on a hot plate at 90 ° C. for 200 seconds to form a 11 μm-thick coating film. Obtained. The Tg of this coating film was used as an apparatus for TMA / SS6000.
(Manufactured by Seiko Instruments Inc.), and measured at a load of 10 g using the penetration method of TMA.
It was shown to.

[0051]

[Table 2]

(2) Pattern formation The photosensitive polyimide precursor composition prepared in the above (1) is spin-coated on a silicon wafer and heated on a hot plate at 90 ° C. for 200 seconds to form a 11 μm thick coating. Obtained. This coating was applied to an i-line stepper at 100 (mJ /
Exposure was performed at 100 to 900 (mJ / cm ² ) in steps of ² cm ² . At that time, the mask pattern was evaluated using two types of patterns, an opening pattern for evaluating the resolution and an island pattern for evaluating the fine line adhesion. Thereafter, paddle development was performed with [γ-butyrolactone / n-butyl acetate = 7/3 (weight ratio)], followed by rinsing with propylene glycol methyl ether acetate. The thickness and shape of the pattern after development were measured and observed. Therefore, the exposure amount (mJ / c) required to adhere a 1 μm line / space pattern closely together
Table 2 shows m ² ) as the sensitivity and the minimum resolution line / space at that time as the resolution.

[0053]

[Table 3]

(3) Formation of polyimide pattern Using the pattern obtained in Example 1, under a nitrogen atmosphere, 100 ° C. for 30 minutes, 200 ° C. for 30 minutes, 350 ° C.
It heated at 60 degreeC for 60 minutes, and obtained the polyimide pattern. The thickness of the obtained polyimide pattern was 7.0 μm, and a good polyimide pattern was obtained.

(4) Measurement of Reaction Rate The photosensitive polyimide precursor compositions of Examples 1 and 2 and Comparative Example 1 were bar-coated on a transparent support film with an applicator to obtain a coating film having a thickness of about 20 μm. . Apply this coating to Photo D
Irradiation was performed for 10 minutes at an irradiation light amount of 1.0 mW / cm ² using SC, the amount of generated heat was measured, and the initial photoreaction rate Rp for 2.5 minutes was calculated. Rp is shown in Table 4.

[0056]

[Table 4]

As is clear from Table 3, the photosensitive polyimide precursor composition using 4-hydroxybutyl methacrylate and 6-hexyl methacrylate of the example is the same as the photosensitive polyimide precursor composition using 2-hydroxyethyl methacrylate of the comparative example. The sensitivity and the resolution are improved as compared with the body composition. As is apparent from Table 4, 4-
Photosensitive polyimide precursor composition using hydroxybutyl methacrylate and 6-hexyl methacrylate,
The photoreaction rate is improved as compared with the photosensitive polyimide precursor composition using 2-hydroxyethyl methacrylate in the comparative example.

Synthesis Example 4 Synthesis of Polyimide Precursor 4 In the synthesis of acid chloride of Synthesis Example 1 (1), instead of oxydiphthalic tetracarboxylic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (s- B
Using 8.82 g (0.03 mol) of PDA), 6.36 g of 2,2'-dimethyl-4,4'-diaminobiphenyl was used in the synthesis of the polyimide precursor (polyamic acid ester) of (2) in Synthesis Example 1. (0.03 mol) 4.104 g of 3,5-diaminobenzoic acid (0.027
Mol) was used to obtain a polyamic acid ester in the same manner as in Synthesis Example 1. The weight average molecular weight of this polyamic acid ester was measured by GPC (gel permeation chromatography).
600.

Synthesis Example 5 Synthesis of polyimide precursor 5 In the synthesis of acid chloride of Synthesis Example 4, 7.809 g of 2-hydroxyethyl methacrylate (HEMA) was used.
A polyamic acid ester was obtained in the same manner as in Synthesis Example 4, except that 9.885 g (0.06 mol) of 4-hydroxybutyl methacrylate was used instead of (0.06 mol). The weight average molecular weight of this polyamic acid ester is determined by GP
When measured by C (gel permeation chromatography), it was 25,800 in terms of polystyrene.

Synthesis Example 6 Synthesis of Polyimide Precursor 6 In the synthesis of acid chloride of Synthesis Example 4, 7.809 g of 2-hydroxyethyl methacrylate (HEMA) was used.
(0.06 mol) instead of Blenmer PE90 (manufactured by NOF Corporation, polyethylene glycol monomethacrylate, Z = 2 in the general formula (II-2)).
A polyamic acid ester was obtained in the same manner as in Synthesis Example 4 except that 440 g (0.06 mol) was used. The weight average molecular weight of this polyamic acid ester measured by GPC (gel permeation chromatography) was 86,400 in terms of polystyrene.

Examples 3 to 4 and Comparative Example 2 (1) Preparation of photosensitive polyimide precursor composition 10 g of the polyimide precursor obtained in the above Synthesis Examples 4 to 6 was dissolved in 16 g of γ-butyrolactone. After blending the indicated photocrosslinking agent and photosensitive agent, the mixture was filtered under pressure using a filter having a pore size of 3 μm to obtain a photosensitive polyimide precursor composition in the form of a solution.

[0062]

[Table 5]

(2) Formation of Pattern The photosensitive polyimide precursor composition prepared in the above (1) is spin-coated on a silicon wafer and heated on a hot plate at 90 ° C. for 200 seconds to form a 11 μm thick coating. Obtained. This coating was applied to an i-line stepper at 100 (mJ /
Exposure was performed at 100 to 900 (mJ / cm ² ) in steps of ² cm ² . At that time, the mask pattern was evaluated using two types of patterns, an opening pattern for evaluating the resolution and an island pattern for evaluating the fine line adhesion. Thereafter, the film was developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) and rinsed with water. The thickness and shape of the pattern after development were measured and observed. Therefore, the exposure amount (mJ / c) required to adhere a 1 μm line / space pattern closely together
Table 6 shows the sensitivity as m ² ) and the minimum resolution line / space at that time as resolution. Further, FIG. 2 shows the relationship between the exposure amount and the minimum island remaining size in Example 3 and Comparative Example 2, and FIG. 3 shows the sensitivity curve showing the relationship between the exposure amount and the remaining film ratio.

[0064]

[Table 6] As is clear from Table 6, FIGS. 2 and 3, Examples 3 and 4
Of the photosensitive polyimide precursor composition of Comparative Example 2
-Sensitivity, resolution, and adhesion are improved as compared with the photosensitive polyimide precursor composition using hydroxyethyl methacrylate.

[0065]

The photosensitive polyimide precursor resin composition of the present invention has a high photoreaction rate and exhibits high sensitivity and high resolution.
Further, according to the method for producing a pattern of the present invention, high resolution can be achieved even in i-line exposure, and a part of the pattern can be developed with an alkaline aqueous solution, and a pattern having excellent heat resistance and chemical resistance can be produced. It is. Further, the electronic component of the present invention has excellent reliability by having the above-mentioned pattern.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

FIG. 2 is a graph showing a relationship between an exposure amount and a minimum island remaining size in Example 3 and Comparative Example 2.

FIG. 3 is a graph showing a relationship between an exposure amount and a residual film ratio in Example 3 and Comparative Example 2.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 3 ... First conductor layer, 4 ... Interlayer insulating film layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window,
7: second conductor layer, 8: surface protective film layer.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/027 502 G03F 7/027 502 7/028 7/028 H01L 21/027 H01L 21/30 502R (72 Inventor Makoto Kaji 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref., Hitachi Chemical Co., Ltd. (72) Inventor Akihiro Kobayashi 14 Goi Minamikaigan, Ichihara, Chiba Pref. Terms (Reference) 2H025 AA01 AA02 AA06 AA07 AA08 AA10 AB15 AB16 AB17 AC01 AD01 BC14 BC32 BC42 BC69 CA01 CA28 CA39 FA03 FA17 FA29 4J011 QA03 QA07 QA08 QA09 QA12 QA13 QA18 QA19 QA22 QA23 QA23 SA18 SAA SA22 SA25 SA26 SA28 SA34 SA38 SA42 SA61 SA62 SA63 SA64 SA74 SA78 SA83 SA86 UA06 WA01 4J027 AD04 BA05 BA07 BA08 BA13 BA14 BA15 B A17 BA18 BA19 BA20 BA21 BA23 BA24 BA26 BA27 BA28 CB10 CC04 CD10 4J043 PA02 PA04 PA19 QB24 QB26 QB31 RA34 RA35 SA06 SA17 SA42 SA43 SA54 SA62 SA63 SA71 SA81 SA82 SB01 SB02 TA01 TA11 TA22 TA35 TA47 TB01 TB02 UA121 UA131 UA132 UA131 UA132 UA362 UB011 UB021 UB022 UB061 UB121 UB122 UB132 UB151 UB152 UB271 UB281 UB301 UB302 UB351 UB352 VA011 VA051 VA091 WA09 ZA23 ZA46 ZB03 ZB50

Claims (7)

[Claims] (A) The general formula (I) (Wherein, R ¹ is a tetravalent organic group, R ² is a divalent, trivalent, or
A valent organic group, each R ³ is independently represented by the general formula (II-1) or (II-2): Wherein X is an integer of 3 to 20, Y and R each independently represent H or CH ₃ , and Z represents an integer of 2 to 10. A monovalent organic group or OH represented by at least one R ³ Is a monovalent organic group, A is an acidic monovalent group, n is 0, 1
Or a photosensitive polyimide precursor composition comprising (B) a photopolymerization initiator. 2. The photosensitive polyimide precursor composition according to claim 1, further comprising, as the component (C), a compound having at least one ethylenically unsaturated group. 3. The component (A) having a weight average molecular weight of 10,000-2.
100,000, and for the amount of 100 parts by weight,
The photosensitive polyimide precursor composition according to claim 2, comprising 1 to 20 parts by weight of the component (B) and 5 to 50 parts by weight of the component (C). 4. A step of forming a film using the photosensitive polyimide precursor composition according to claim 1, 2 or 3, and irradiating the film with light through a mask having a predetermined pattern.
And a step of developing the pattern after the light irradiation using an organic solvent or a basic aqueous solution. 5. The method for producing a pattern according to claim 4, wherein the step of developing comprises developing with a basic aqueous solution. 6. The step of irradiating the light with the light having a wavelength of 365.
5. Irradiation with i-ray which is monochromatic light of nm.
Or the method for producing a pattern according to 5. 7. An electronic component comprising a film having a pattern obtained by the production method according to claim 4, 5 or 6.