JP2001272777A - 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 a pattern in which part of the composition can be subjected to good development with an aqueous alkali solution and a pattern having superior heat and chemical resistances is produced and electronic parts excellent in reliability. SOLUTION: The photosensitive polyimide precursor composition contains (A) a polyimide precursor, (B) a compound having 0.001-0.1 Pa.s viscosity at 25 deg.C and having at least one ethylenically unsaturated group and (C) a photoinitiator. The composition is prepared in such a way that the glass transition temperature (Tg) of a prebaked film having 10-12 μm thickness ranges from 0 to 60 deg.C when the prebaked film is obtained by applying the composition on a silicon wafer and drying it at a temperature in the range of 70-120 deg.C for 150-300 sec and the temperature Tg of the film is measured by a penetration method as a thermomechanical analysis(TMA) under 10 g load.

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.

Among the constituents of the photosensitive resin composition, a photoinitiator is one having the greatest influence on the sensitivity. A compound having an ethylenically unsaturated group may be added to improve the photosensitivity. Photosensitive polyimide precursors generally have photoreactive sites themselves, but by adding compounds with ethylenically unsaturated groups, aid in the mobility of reaction points in the coating, Density can be increased. As the photosensitive polyimide precursor to which the compound having an ethylenically unsaturated group is added, a compound using a compound having a group capable of forming an ethylenically unsaturated double bond and a hydrogen bond with a carboxyl group and / or an amide group (particularly, No. Hei 9-115900).

[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. In addition, those in which an ethylenically unsaturated compound is simply added (Japanese Unexamined Patent Publication No.
121435, JP-A-61-249046, JP-A-2-14643, etc.). Here, unsaturated carboxylic acid esters, such as acrylic acid and methacrylic acid, having no group capable of hydrogen bonding are used.

[0008] These compounds having an ethylenically unsaturated group can increase the bridging density and can also assist the mobility of reaction points in a coating film. The viscosity of the photosensitive layer greatly affects photoreactivity, that is, sensitivity. It has also been reported that the sensitivity is related to the glass transition temperature of the photosensitive layer (MF Moire; J. Polym. Sc).
i. , Polym. Chem. Ed. , 20,847
(1982)). However, at present, a photosensitive polyimide precursor composition having a sufficiently high sensitivity and high resolution corresponding to the recent development of semiconductor devices has not been obtained.

[0009]

SUMMARY OF THE INVENTION The present invention provides a photosensitive polyimide precursor resin composition exhibiting high sensitivity and high resolution. Further, the present invention provides a method for producing a pattern which has high sensitivity to i-rays, high resolution, and a part of which can realize good development with an aqueous alkali solution and can produce a pattern exhibiting excellent heat resistance and chemical resistance. It provides a method. The present invention also provides an electronic component having excellent reliability by having the above-mentioned pattern.

[0010]

The present invention relates to (A) a polyimide precursor, and (B) a polyimide having a viscosity at 25 ° C. of 0.001 to 0.001.
A photosensitive polyimide precursor composition containing a compound having at least one ethylenically unsaturated group, which is 0.1 Pa · s, and (C) a photoinitiator, and the photosensitive polyimide precursor composition Thing is applied on a silicon wafer,
The glass transition temperature (Tg) of the prebaked film having a thickness of 10 to 12 μm obtained by drying at a temperature in the range of 70 to 120 ° C. for 150 to 300 seconds is measured by a penetration method of thermomechanical analysis (TMA) under a load of 10 g. The present invention relates to a photosensitive polyimide precursor composition which is adjusted so that the measured value is 0 to 60 ° C.

In the present invention, the component (A) preferably 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. (C) A photosensitive polyimide precursor composition containing 1 to 20 parts by weight of a component. In the present invention, the component (A) is preferably
The present invention relates to a photosensitive polyimide precursor composition which is a polyimide precursor having an ethylenically unsaturated group and an acidic group.

The present invention also 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 the light irradiation. The present invention relates to a method for producing a pattern including a step of developing using an organic solvent or a basic aqueous solution. Further, the present invention relates to a method for producing a pattern, wherein the temperature when irradiating light through the mask having the predetermined pattern is 18 to 28 ° C.

The present invention also relates to a method for producing a pattern, wherein the step of developing is a step of developing using a basic aqueous solution. Further, the present invention relates to a method for producing a pattern, wherein the step of irradiating the light includes irradiating i-line which is monochromatic light having a wavelength of 365 nm as light. Furthermore, the present invention
The present invention relates to an electronic component having a film having a pattern obtained by each of the above-described manufacturing methods.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) polyimide precursor used in the present invention refers to a polyimide precursor having a structure capable of forming a polyimide structure by ring closure, and includes polyamic acid, polyamic acid ester, polyamic acid amide and one of them. Although there is no particular limitation, there is an ethylenically unsaturated bond group (photopolymerizable carbon-carbon double bond group) in the molecular chain.
Is preferable. As a polyimide precursor having an ethylenically unsaturated bond,
By mixing a polyamic acid unsaturated ester having a structure in which a compound having an ethylenically unsaturated bond is covalently bonded to a polyamic acid as a side chain, a polyamic acid unsaturated amide, and a polyamic acid mixed with an amine compound having a carbon-carbon double bond. And those having a carbon-carbon double bond introduced by an ionic bond between a carboxyl group and an amino group. The carbon-carbon unsaturated double bond is preferably contained in the form of an acryloyl group or a methacryloyl group.

Among these, a polyamic acid having a repeating unit represented by the following general formula (I), because excellent sensitivity and shortening of the development time can be achieved by using in combination with the component (B) used in the present invention. Unsaturated esters are preferred.

Embedded image (Wherein, R ¹ is a tetravalent organic group, R ² is a divalent, trivalent or tetravalent organic group, and R ³ is a group having an ethylenically unsaturated bond.
A is a monovalent organic group, A is an acidic monovalent group, and n is 0, 1 or 2.)

In the repeating unit represented by the general formula (I), the tetravalent organic group represented by R ¹ is usually a tetracarboxylic acid or a derivative thereof which can react with a diamine to form a polyimide precursor. It is 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. Among tetravalent organic groups having 4 or more carbon atoms, the total number of carbon atoms including aromatic rings (benzene ring, naphthalene ring, etc.) is 6 to 3;
More preferably, it is 0. 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 a plurality of the repeating units in one molecule of the polyamic acid ester, all R ^{1 s} may be the same or different.

In the general formula (I), those wherein n is 1 or 2 are preferred 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) and a sulfinic acid group (—SO ₃ H).
_{2 H),} preferably exhibits good solubility be either a carboxyl group (-COOH) and a phenolic hydroxyl group, a carboxyl group and a phenolic hydroxyl group, more preferably their ease of synthesis of the polyimide precursor, in particular carboxyl groups Is preferred. 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, in addition to the repeating unit of the general formula (I), R ³ of the repeating unit represented by the general formula (I) It is preferable to have a unit of a hydrogen atom (being a carboxyl group), that is, a partial ester of polyamic acid.

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

In the general formula (I), the group having an ethylenically unsaturated bond represented by R ³ is represented by the following general formula:

Embedded image (However, R ⁴ , R ⁵ and R ⁶ are each independently a group selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ⁷ represents a divalent organic group) The organic group represented is preferable because it can impart high sensitivity photosensitivity. Examples of the alkyl group include those having 1 to 4 carbon atoms. Examples of the divalent organic group represented by R ⁷ include an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group. Among them, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (having 1 to 20 carbon atoms in alkyl) not only realize high sensitivity but also are easy to synthesize, and thus are suitable for the present invention. 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 mole percentage of 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 mixed with a tetracarboxylic dianhydride and a hydroxy group-containing compound having an unsaturated group and reacted to produce a half ester of tetracarboxylic acid, which is then acid chlorided with thionyl chloride. Then, it can be synthesized by a method of reacting with a diamine, an acid chloride method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent, a method using a carbodiimide condensing agent, an isoimide method, 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 represented by the following general formula (II)

Embedded image (Wherein, R ⁸ and R ⁹ each independently represent a monovalent hydrocarbon group, and s is an integer of 1 or more). A dianhydride of an aromatic tetracarboxylic acid such as a tetracarboxylic acid represented by And these may be used alone or in combination of two or more.

Further, among the diamine residues in the repeating unit represented by the general formula (I), those having n of 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 giving a diamine residue in which n is 0 includes 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 (III) is used in order to improve adhesion.

Embedded image (Wherein, R ¹¹ and R ^{12 each} represent a divalent hydrocarbon group;
R ¹³ and R may be the same or different.
¹⁴ represents a monovalent hydrocarbon group, which may be the same or different, and t is an integer of 1 or more.) It is also possible to use a diamine such as diaminopolysiloxane. Examples of R ¹¹ and R ¹² 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 13} and R ¹⁴ 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, 1 to 30 with respect to all amine components
It is preferable to use mol%.

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.

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 inferior, and if it exceeds 100,000, the developability tends to be inferior. Here, the weight average molecular weight is a molecular weight in terms of polystyrene by a GPC method.

Next, components other than the polyimide precursor will be described. The compound (B) having at least one ethylenically unsaturated group in the present invention has a viscosity of 0.001 to 0.1 Pa · s (1 to 10) at 25 ° C.
0 cps). Here, the viscosity of the component (B) is more preferably 0.001 to 0.05 Pa · s.
When the viscosity is larger than 0.1 Pa · s, the sensitivity and the resolution are reduced. In addition, good characteristics cannot be obtained even if it is smaller than 0.001 Pa · s.

When the viscosity at 25 ° C. is 0.0
Examples of the component (B) of 01 to 0.1 Pa · s include, for example,
Allyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, 2 (2-ethoxyethoxy) ethyl acrylate, tetrahydrofurfuryl acrylate, lauryl methacrylate, stearyl methacrylate, lauryl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isodecyl Acrylate, isobornyl methacrylate, isooctyl acrylate, tridecyl acrylate, tridecyl methacrylate, caprolactone acrylate, isobornyl acrylate, allyl methacrylate PO (propylene oxide) adduct, methoxypolyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, nonylphenol methacrylate EO (ethylene oxide) adduct, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butane Diol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate,
Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, tripropylene glycol diacrylate, neo Pentyl glycol diacrylate PO adduct, alkoxylated aliatic diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate,
Trimethylolpropane triacrylate EO adduct,
Trimethylolpropane triacrylate PO adduct,
Glyceryl triacrylate PO adduct, cyclohexyl methacrylate, n-hexyl methacrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-methoxyethyl acrylate, t-butyl acrylate, benzyl acrylate, hexyl acrylate, diethylaminoethyl acrylate , Dimethylaminoethyl acrylate, polypropylene glycol monoacrylate,
Butanediol monoacrylate, neopentyl glycol diacrylate PO adduct, isoamyl acrylate, stearyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate , 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, perfluorooctylethyl acrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, phenoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, 2-hydroxy , 3-dimethacryloxypropane propane, polypropylene glycol diacrylate, 2-hydroxy, 1- acryloxy, 3- methacryloxy propane.

Among them, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate EO adduct and the like are particularly sensitive,
It is preferable because of excellent resolution.

The amount of the component (B) is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polyimide precursor (A). . If this amount is less than 5 parts by weight,
When the amount exceeds 50 parts by weight, the mechanical properties of the film tend to be inferior.

In the present invention, two or more of the above-mentioned component (B) may be used in combination, or another compound having at least one ethylenically unsaturated group may be used in combination.
Specific examples thereof include EO and PO adducts of bisphenol A diacrylate or methacrylate, and these are used alone or in combination of two or more.

When these other compounds having at least one ethylenically unsaturated group are used, (A)
It is preferably at most 50 parts by weight, more preferably at most 40 parts by weight, based on 100 parts by weight of the polyimide precursor. If this amount exceeds 50 parts by weight,
The mechanical properties of the film tend to be poor.

The present invention further comprises (C) a photoinitiator. Examples of the photoinitiator include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4, -bis (diethylamino) benzophenone, acetophenone,
Benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyldisulfide, phenanth Lenquinone, 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) oxyiminopropan-1-one, 3,3
4,4, -tetra (t-butylperoxycarbonyl)
Benzophenone, 3,3, -carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl)
-Bis- [2,6-difluoro-3- (pyr-1-yl) phenyl] titanium, hexaarylbiimidazole compound and the like. These are used alone or in combination of two or more.

(C) The content of the photoinitiator 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. . If the amount is less than 0.1 part by weight, the light sensitivity tends to be poor, and if it exceeds 15 parts by weight, the mechanical properties of the film tend to be inferior.

Further, by adding a hydrogen donor such as an amine together with the photoinitiator, 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.

The mercapto compounds include mercaptobenzoxazole, mercaptobenzothiazole, mercaptobenzimidazole, and 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,
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, dimethylaminobenzophenone, diethylaminobenzophenone (EAB), 4,
4'-bis (N-ethyl, N-methyl) benzophenone (MEAB) 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.

Further, the photosensitive polyimide precursor composition of the present invention is coated and dried on a silicon wafer, and the glass transition temperature (Tg) of the prebaked film is measured by the penetration method of thermomechanical analysis (TMA).
It is necessary to adjust so as to be 0 to 60 ° C. when measured under a load of 10 g. Tg of prebaked film is 0-4
The temperature is preferably set to 0 ° C, more preferably 0 to 35 ° C. If it is higher than 60 ° C., the sensitivity tends to decrease, and if it is lower than 0 ° C., tack tends to occur. In the present invention, the pre-baked film adjusted for the measurement of the glass transition temperature is formed by applying a photosensitive polyimide precursor composition on a silicon wafer, and applying a temperature between 70 to 120 ° C.
Preferably at a temperature between 75-115 ° C, more preferably at a temperature between 85-105 ° C, for 150-300 seconds, preferably 180-220 seconds, more preferably 190-21.
A film having a thickness of 10 to 12 μm obtained by drying for 0 seconds.

The influence on the Tg of the prebaked film is as follows.
Mainly (A) polyimide precursor, (B) at least 1
It is a compound having two ethylenically unsaturated groups. That is,
The Tg of the component (A), the viscosity and the mixing ratio of the component (B)
It is a main factor in determining the Tg of the composition, and can be adjusted by appropriately selecting these. Tg of pre-baked film
The lower the Tg of the polyimide precursor as the component (A), the lower the Tg of the prebaked film. Also, the lower the viscosity of the component (B), the lower the Tg of the prebaked film, and the higher the blending ratio of the component (B), the lower the Tg of the prebaked film.

Since the thickness of the film to be formed and the drying process such as prebaking also influence the value of Tg, the above-mentioned conditions are employed for measuring the Tg of the prebaked film in the present invention. This is mainly because the amount of the residual solvent in the film changes. It is preferable that the actual pattern forming conditions are such that the pattern is manufactured by setting the film thickness and the drying conditions to be the Tg.

The pattern production 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 is used as a light source for exposure.

The environment for exposure is usually a clean room maintained at an environment of 18 to 28 ° C., generally around 23 ° C. Therefore, in the present invention, the photosensitive polyimide precursor composition having a Tg of the prebaked film of 0 to 60 ° C., preferably 0 to 40 ° C. so that the photoreaction proceeds sufficiently to obtain a good pattern under the above conditions. It is important to use

The developing step may be performed using a usual positive type photoresist developing device. 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 generally 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, methanol, ethanol, propanol, isopropyl alcohol, N-methyl-2-pyrrolidone, N,
A water-soluble organic solvent such as N-dimethylformamide and N, N-dimethylacetamide 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 pattern was heated from 150 ° C. to 450
By performing the heat treatment at a temperature selected from the range up to ° C., the pattern made of the polyimide of the present invention can be 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 parts such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film, interlayer insulating film, and multilayer wiring of semiconductor devices It can be used for forming an interlayer insulating film or the like of a plate. The electronic component of the present invention is not particularly limited except that it has a pattern film formed using the composition as a surface protective film, an interlayer insulating film, and the like, 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, by using a well-known photographic etching 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 polymer composition to the surface protective film by spin coating and drying, and irradiating a predetermined portion with a mask on which a pattern for forming the window 6C is drawn,
A pattern is formed by developing with a developer and heated to form a polyimide film. This polyimide film protects the conductor layer from external stress, α-rays and the like, and the resulting 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.

[0055]

The present invention will be described below with reference to examples. Synthesis Example 1 Synthesis of polyimide precursor (1) Synthesis of acid chloride 3,3 ′, 4,4′- was placed in a 200 ml four-necked flask.
Biphenyltetracarboxylic dianhydride (BPDA) 9.
42 g (0.032 mol), 2-hydroxyethyl methacrylate (HEMA) 8.32 g (0.064 mol), pyridine 5.06 g (0.064 mol), t-butylcatechol 0.03 g, N-methyl-2 When 70 ml of pyrrolidone (NMP) was added and stirred at 60 ° C., a clear solution was obtained in 2 hours. After stirring the solution at room temperature for 7 hours, the flask was cooled with ice and 9.88 g (0.083 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, 4.72 g (0.031 mol) of 3,5-diaminobenzoic acid and 5.35 g of pyridine were added.
06 g (0.064 mol), t-butyl catechol 0.
03 g, N-methyl-2-pyrrolidone (NMP) 50 m
The acid chloride solution obtained above was slowly added dropwise over 1 hour while cooling the 1-liter flask with ice and stirring (keeping the temperature at 10 ° C. or lower). 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.
After repeated washing and vacuum drying, 22 g of a polyamic acid ester was obtained. When the weight average molecular weight of this polyamic acid ester was measured by GPC (gel permeation chromatography), it was 44,0 in terms of polystyrene.
00.

Examples 1 and 2 and Comparative Examples 1 and 2 (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.

[0058]

[Table 1] NPG: N-phenylglycine, EMK: 4,4'-bis (N-ethyl, N-methyl) benzophenone, PDO: 1-phenyl-1,2-propanedione-2-
(O-ethoxycarbonyl) oxime The viscosity was measured using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

THE330:

Embedded image

(2) Measurement of Tg The photosensitive polyimide precursor composition prepared in the above (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. Obtained. The Tg of this coating film was used as an apparatus for TMA / SS6000.
(Seiko Instruments Co., Ltd.)
Measured at a load of 10 g using the penetration method of A,
The results are shown in Table 2.

[0061]

[Table 2]

(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 /
cm ²⁾ was exposed at 100 to 900 (mJ / cm ²⁾ in step (23 ° C.). 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.
Then, [γ-butyrolactone / n-butyl acetate = 7/3
(Weight ratio)], and rinsed with propylene glycol methyl ether acetate. The thickness and shape of the pattern after development were measured and observed. Therefore, the sensitivity (mJ / cm ² ) required to make a 1 μm line / space pattern adhere to the sensitivity, the minimum resolution line /
Table 3 shows the space as a resolution.

[0063]

[Table 3]

Example 3 Using the pattern obtained in Example 2, 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.

Examples 4 to 7, Comparative Example 3 (1) Preparation of Polyimide Precursor Composition 10 g of the polyamic acid ester prepared in Synthesis Example 1 was dissolved in 16 g of γ-butyrolactone. And a photosensitive agent, and 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.

[0066]

[Table 4]

(2) Measurement of Tg The photosensitive polyimide precursor composition prepared in the above (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. Obtained. The Tg of this coating film was measured at a load of 10 g using the penetration method of TMA, and is shown in Table 4.

[0068]

[Table 5]

(3) Measurement of Reaction Rate The photosensitive polyimide precursor composition prepared in the above (1) was bar-coated on a transparent support film with an applicator to obtain a coating film having a thickness of 20 μm. This coating film was irradiated using a photo DSC at an irradiation light amount of 1.0 mW / cm ^{2 for} 10 minutes.
The amount of generated heat was measured, and the light reaction rate Rp was calculated from the reaction rate in the initial 2.5 minutes. FIG. 2 shows the relationship between the Tg of the prebaked film and the photoreaction rate.

From Table 3, it can be seen that the viscosity is 0.1 Pa · s (25
C) The composition using a compound having an ethylenically unsaturated group of not more than the composition using a compound having an ethylenically unsaturated group exceeding 0.1 Pa · s (25 ° C) in Comparative Example Sensitivity and resolution are improved. From FIG. 2, the reaction rate increases when the Tg of the prebaked film is 40 ° C. or less.

[0072]

The photosensitive polyimide precursor resin composition of the present invention exhibits high sensitivity and high resolution. Further, according to the pattern manufacturing method of the present invention, high resolution can be obtained even in i-line exposure,
In addition, a part thereof can be favorably developed with an alkaline aqueous solution, and a pattern having excellent heat resistance and chemical resistance can be produced. 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 Tg of a prebaked film and a reaction rate in Examples and Comparative Examples of the present invention.

[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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 73/10 C08G 73/10 5F046 G03F 7/028 G03F 7/028 7/38 501 7/38 501 H01L 21 / 027 H01L 21/30 502R 565 F term (reference) 2H025 AA01 AA02 AA06 AA07 AA08 AA10 AB16 AB17 AC01 AD01 BC31 BC32 BC42 BC69 BC84 BC92 CA01 CA20 CA27 CA28 FA03 FA15 FA17 2H096 AA25 AA27 BA05 BA06 GA20 AEA EA02 AC05 PA97 PB38 PC02 QA03 QA07 QA12 QA13 QA17 QA18 QA22 QA24 QB16 SA04 SA05 SA22 SA32 SA34 SA63 SA64 SA78 SA82 SA86 UA01 VA01 WA01 4J026 AB35 BA27 BA28 BA29 BA30 GA06 GA07 4J043 QB31 RA34 SA54 SA62 SA71 UA UA UA 121 UA UA UA UA UA UA UB121 UB292 UB301 UB351 UB352 VA011 VA051 VA092 VA102 ZA46 ZB03 ZB11 ZB22 5F046 CA02 JA 14 JA22 JA24 LA12 LA14

Claims (8)

[Claims] 1. A (A) polyimide precursor, (B) a compound having a viscosity at 25 ° C. of 0.001 to 0.1 Pa · s and having at least one ethylenically unsaturated group, and (C) photoinitiation A photosensitive polyimide precursor composition containing an agent, and the photosensitive polyimide precursor composition is applied on a silicon wafer, and dried at a temperature in the range of 70 to 120 ° C. for 150 to 300 seconds. Obtained thickness 10
When the glass transition temperature (Tg) of the 12 μm prebaked film was measured by a penetration method of thermomechanical analysis (TMA) under a load of 10 g, the value was 0 to 60 ° C.
A photosensitive polyimide precursor composition adjusted to be: 2. The component (A) having a weight average molecular weight of 10,000 to 2
100,000, and for the amount of 100 parts by weight,
The photosensitive polyimide precursor composition according to claim 1, comprising 5 to 50 parts by weight of the component (B) and 1 to 20 parts by weight of the component (C). 3. The photosensitive polyimide precursor composition according to claim 1, wherein the component (A) is a polyimide precursor having an ethylenically unsaturated group and an acidic group. 4. A step of forming a film using the photosensitive polyimide precursor composition according to claim 1, 2 or 3, irradiating the film with light through a mask having a predetermined pattern, and A method for producing a pattern, comprising a step of developing a film after light irradiation using an organic solvent or a basic aqueous solution. 5. The method for producing a pattern according to claim 4, wherein the temperature when irradiating light through a mask having a predetermined pattern is 18 to 28 ° C. 6. The method according to claim 4, wherein the step of developing comprises developing with a basic aqueous solution. 7. The step of irradiating light includes the step of using light having a wavelength of 365.
7. The method for producing a pattern according to claim 4, wherein the i-ray is monochromatic light having a wavelength of nm. 8. An electronic component comprising a film having a pattern obtained by the production method according to claim 4, 5, 6, or 7.